BASIC

DENTAL
MATERIALS
 BASIC
DENTAL
MATERIALS
Fourth Edition

JOHN J MANAPPALLIL  MDS

The Health Sciences Publisher

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Basic Dental Materials
First Edition: 1998
Second Edition: 2003
Reprint: 2004, 2007, 2008
Third Edition: 2010
Fourth Edition: 2016
ISBN: 978-93-5250-048-2
Printed at
 Dedicated to
The teachers
who have inspired us
 Contributors

Akshay Bhargava Jacob Kurien

Dean Professor and Head
Faculty of Dental Sciences Department of Conservative
Shree Guru Gobind Singh Tricentenary (SGT) Dentistry and Endodontics
University, Gurgaon Kannur Dental College
Haryana, India Kannur, Kerala, India

G Vinaya Kumar Rajashekar Sangur

Professor and Head Professor and Head
Department of Prosthodontics Department of Prosthodontics
College of Dental Sciences Rama Dental College
Davangere, Karnataka, India Hospital and Research Centre
Kanpur, Uttar Pradesh, India
 Preface

A successful dentist has to combine technical skills along with sound clinical knowledge.
Knowledge of dental materials is one of the keys to a successful dental practice. To the beginner,
the task may appear formidable because of the wide array of materials available. This is quite
normal and fortunately disappears with use and familiarity. Intimate knowledge of dental materials
is required throughout one’s career for a successful practice. As with dentistry in general, the
science of dental materials combines a wide array of disciplines, including chemistry, physics,
mechanics, and biology with clinical sciences.

Format
Basic Dental Materials, first published in 1998, is now in its 18th year. Its publication was inspired
by the desire to help students navigate the complex field of dental materials from the very first
year of the course. Being the first published book on dental materials from India, it had set new
standards, including moving away from traditional formats. Its unique student friendly format
has contributed much to its popularity particularly among dental students from India and around
the world, and has made the understanding of this subject within the grasp of the novice. Over
the years, readers have contributed valuable information as well as suggestions, many of which
have been incorporated in the current edition. Comments and suggestions are welcome and
readers are encouraged to send in their feedback via e-mail ([email protected]).

Challenges
With each new edition, the challenges continue to grow, and revising the previous edition was
certainly no exception. Dental material is a vibrant subject as new products and technology are
constantly appearing in the market. A few of the materials have been eliminated from the book
or have just briefly been mentioned as they are no longer marketed. Knowledge of the history
of dental materials is useful to understand the evolution of materials and why newer materials
were developed. Over the past decade, the field of ceramics has seen vast improvements. Current
developments in CAD/CAM and 3D printing are opening new frontiers. Knowledge of values
helps improve depth of understanding and is useful for making comparisons. Actual values of
the various materials have been presented wherever possible. However, one must remember that
values are not necessarily absolute, variations can occur over time, between brands and methods
of testing. Climatic differences affect properties like working and setting times.

New chapters
Another challenge is defining dental materials. Traditionally, the subject of dental materials
primarily included materials used in restorative dentistry and related auxiliary materials. Currently,
the trend is to be more inclusive of materials from other specialties, which have traditionally been
excluded. This has been partly addressed in this edition with the inclusion of two new chapters on
endodontic materials. With succeeding editions, it is hoped to be even more inclusive and cover
the entire spectrum of materials used in dentistry, including surgical and orthodontic materials.
Materials such as anesthetics and drugs are not within the scope of this book. Metallurgy which
was not included earlier, has been included in the current edition (Structure and properties of
x  BASIC DENTAL MATERIALS

metals and alloys). Another new chapter is in the field of ‘additive manufacturing’, popularly
known as 3D printing. Biomaterials is another exciting area of development with an explosion
of new materials and technology.

Differences in information
One of the challenges faced by the readers is the wide variation in information between different
books. Differences do exist between various books and the reader is often in a dilemma as to
which information to follow. The best source is the original source, which includes original
studies, information from the manufacturers and publications of the International Standards
Organization (ISO). The ‘International Standards Organization’ is a significant reference source
for manufacturers as well as authors and researchers. The technical committees in-charge of the
specification constantly strive to keep pace with changes in knowledge and technology, through
publication of new editions of the specifications periodically. The edition is indicated by the
year attached to the specification. Most dental product manufacturers strive to keep pace with
changes in standards. Significant changes have taken place in the specifications and classifications
of many products. The fourth edition of Basic Dental Materials too has reflected these changes
and therefore, differences will exist between the current edition and previous editions as well as
other textbooks on the subjects, particularly in the area of classifications and technical details.
Readers and teaching staff in particular are requested to look out for these changes and refer to
the source when available. Explanatory footnotes have been provided wherever needed.

International Standards Organization (ISO)

Many nations, including India and the US are members of the ISO. Founded in 1947 with just
26 members, its membership has grown to 162, including 119 full members, 38 correspondent
members and 5 subscriber members. India has not only been a full member since its inception,
but has also assumed council positions and has been a part of technical committees at various
times. Current ADA specifications have been adopted from the ISO. In its website, the ADA has
stated that their specifications are identical to the relevant ISO standards. Therefore, use of both
specifications for the same product is repetitive. The fourth and subsequent editions of the book
will therefore gradually phase out the ADA specifications and replace them with those of the
ISO. Other specifications, including the ADA will be used only if ISO standards are not available
for the particular product.

Organization of the book

Other changes include the reorganization of the book into segments. The 30 chapters in the
book have been organized into 7 parts for ease of reference. Another new feature is the chapter
outline at the beginning of each chapter as requested by some readers. Many materials adversely
affect the other’s property, and therefore, material interactions have been introduced where
information is available. A familiar one to most readers is the effect of eugenol from ZOE-based
products on resin-based composites. A relatively less familiar one is that occurring between
provisional composites and elastomeric impression materials, which if not managed well, can
introduce significant errors in the impression.

Critical assessment of new products

Today’s dentists in India are fortunate to have a wide choice of materials. The economic liberalization
of the late 1980s saw the opening of the market to a range of high quality international products.
Dental practitioners should have a good understanding of basic dental materials science to
 Preface  xi

enable them to select and critically assess the plethora of new materials that are constantly being
introduced and aggressively marketed. It is also advisable to request long-term in vitro and in
vivo independently acquired evidence of the performance of a material before deciding to use it.
It is not possible to cover all aspects of the material in the book; therefore, the operator should
read the information which comes with a particular product whenever available.

Information exchange and update

Students are encouraged to read from a wide source of materials for greater understanding
and depth of knowledge. Thanks to journals, scientific conferences and the internet, there is
exchange of information between individuals, transcending geographical barriers. Concepts
are constantly changing with improved understanding and new research. It is encouraging to
see a lot of new publications within the country and abroad. Encouragement from professional
publishing houses and new regulations by the DCI have in no small measure, contributed to
this increase. Indian professionals are now contributing significantly to international research,
literature and education world over.

Educational challenges
Dental institutions today are facing innumerable challenges, and constant adaptation is required
to reflect changing curricula around the world and higher expectations among the student
community. The challenge now is in reorganizing and streamlining the courses to changing
times. It is encouraging to see some leading institutions take bold new initiatives in instituting
improved learning techniques and investing in infrastructure to raise standards of education. In
this regard, the roles of regulatory bodies, including the Dental Council of India and various Dental
Associations are critical to ensure that the profession continues to develop. It is my fervent hope
that a new generation of young, highly trained and motivated dentists will emerge, providing
improved patient care and upholding the dignity of the profession.
 Acknowledgments

Every book has its share of contributors and influences, and this book is certainly no exception.
I am deeply indebted to professors Akshay Bhargava, Jacob Kurien, G Vinaya Kumar and Rajashekar
Sangur who over the years have contributed their knowledge and experience to the various
chapters in the book. It is my honor and privilege to have you all associated with this book.
My deepest gratitude goes to all those who helped with the proofreading and corrections of the
manuscripts. In this regard, I thank Rajanikant AV and Preeti Pachauri from Rama Dental College,
Hospital and Research Centre, Kanpur, Uttar Pradesh, India; Ginu Philip, Vijayasree Sreekumar and
Jojen Thomas from Bneid Al Gar Dental Center, Kuwait; and my wife Dr Divya Susan.
The countless hours spent on the project meant hours away from my family. My deep appreciation
goes to my family especially my wife Divya and kids Reuben and Jordan and my parents. Without
their encouragement, support and tolerance, this project would not have been possible.
This edition is dedicated to our respected teachers who have influenced all of us. This includes
not only the professors and clinicians who taught us at dental school, but also those who shared
their information at the continuing education programs and conferences. I wish to acknowledge
the significant influence of the brilliant authors from around the world whose books have been a
source of so much knowledge and inspiration. I pay tribute to these great individuals who have
inspired us all.
I wish to express my appreciation to those who contributed to the previous editions, in particular
my former colleagues, Shubha Rao and Atley George from BDCH, Davangere. In spite of the
significant modifications many of the chapters contain portions created by them.
I also take this occasion to once again renew bonds of friendship and affection with all my students
and readers. I thank all the readers who have given their feedback and suggestions. Your support
is what gives me the inspiration to continue this book. It is a privilege to have you all on board.
Last but not least, a special thanks to Shri Jitendar P Vij (Group Chairman), Mr Ankit Vij (Group
President), Mr Tarun Duneja (Director-Publishing) and staff of M/s Jaypee Brothers Medical
Publishers (P) Ltd, New Delhi, India, for their great expertise in creating a truly remarkable book.

John J Manappallil MDS

 Undetailed Contents

Section 1: Structure and 15. Elastic Impression Materials—

Agar and Alginate 258
Properties of Dental Materials 16. Elastomeric Impression Materials 277

1. Overview of Dentistry and

Dental Materials 3 Section 5: Dental Laboratory—
2. Structure and Properties of Materials and Processes
Dental Materials 9
3. Structure and Properties of 17. Model, Cast and Die Materials 301
Metals and Alloys 39 18. Gypsum Products 310
4. Electrochemical Properties of 19. Waxes in Dentistry 327
Materials 56
20. Dental Investments and Refractory
5. Biological Properties of Dental Materials 345
Materials 61
21. Dental Casting and Metal Fabrication
Procedures 358
Section 2: Direct Restorative 22. Abrasion and Polishing 378
Materials 23. Metal Joining and Dental Lasers 392
24. Additive Manufacturing in Dentistry 407
6. Introduction to Restorations,
Luting and Pulp Therapy 73
7. Cavity Liners and Varnish 80
Section 6: Alloys in Dentistry
8. Dental Cements 84 25. Dental Casting Alloys 421
9. Dental Amalgam 128 26. Dental Implant Materials 452
10. Direct Filling Gold 156 27. Wrought Metals and Alloys 466
11. Resin-based Composites and
Bonding Agents 167
Section 7: Indirect Restorative
Section 3: Endodontic Materials and Prosthetic Materials
12. Endodontic Medicaments 28. Dental Ceramics 479
and Irrigants 207 29. Denture Resins and Polymers 529
13. Endodontic Sealers and 30. Maxillofacial Prosthetic Materials 572
Obturating Materials 216
Appendices 579
Section 4: Impression Materials Further Reading 589
Index 595
14. Rigid Impression Materials—
Impression Compound and
ZOE Paste 243
 Contents in Detail

Section 1: Structure and Rheology 25

Terms and Properties in Rheology  26
Properties of Dental Materials Physical Properties  27
Forms of Matter  27
Melting Point  28
1. Overview of Dentistry and Boiling Point  28
Dental Materials 3 Density 28
Dental Treatment  3 Glass Transition Temperature (TG) 28
Maintenance Phase  5 Solubility 29
The Dental Specialties  5 Thermal Properties  29
The Dental Laboratory  6 Thermal Conductivity  29
Classification of Dental Materials  6 Thermal Diffusivity  30
International Standards Organization (ISO) 7 Thermal Expansion  30
US Standards for Dental Materials  8 Coefficient of Thermal Expansion (CTE) 30
Optical Properties and Color  31
2. Structure and Properties of Dimensions of Color  31
Dental Materials 9 Measurement of Color  32
Structure of Matter  9 Metamerism 32
Interatomic Bonds  10 Tooth Esthetics  32
Crystal Structure  11 Transparence, Translucence, and Opacity  32
Noncrystalline Structure  12 Fluorescence 33
Stress and Strain  12 Clinical Considerations  34
Diffusion 12 Radiological Properties  34
Surface Tension  12 Magnetic Properties of Matter  36
Wetting 13 Classification 36
Properties of Dental Materials  14 Terms 36
Mechanical Properties  14 Types 37
Stress 14 Uses 37
Strain 15
Complex Stresses  15 3. Structure and Properties of
Poisson’s Ratio  16 Metals and Alloys 39
Proportional Limit  16 Uses in Dentistry  39
Elastic Limit  16 Metallurgy 42
Yield Strength  16 Periodic Table  42
Modulus of Elasticity  17 General Properties of Metals  42
Flexibility 17 Valence Electron  42
Resilience 17 Metallic Bonding  43
Impact 18 Alloys 43
Impact Strength  18 Phase 44
Permanent Deformation  19 Solid Solutions  44
Strength 19 Dental Applications  46
Weibull Statistics  21 Solidification and Microstructure of Metals and
Stress Concentration  22 Alloys 46
Fatigue 22 Time-temperature Graph  48
Toughness 23 Equilibrium Phase Diagrams  49
Brittleness 23 Eutectic Alloys  50
Ductility 23 Peritectic Alloys  51
Malleability 23 Solid State Reactions  52
Hardness 24 Classification of Alloys  54
Abrasion Resistance  25 Functions of Alloying Elements  54
xvi  BASIC DENTAL MATERIALS

4. Electrochemical Properties of 7. Cavity Liners and Varnish 80

Materials 56 Cavity Liners  80
Definitions 56 Supplied as  80
Electromotive Force Series (EMF) 57 Composition 80
Classification of Corrosion  58 Properties 80
Types of Electrolytic Corrosion  58 Manipulation 81
Factors Affecting Corrosion of Restorations in the Other Liners  81
Mouth   60 Cavity Varnish  81
Protection against Corrosion   60 Application 81
Supplied as  81
5. Biological Properties of Dental Composition 81
Materials 61 Properties 81
Biomaterials 61 Manipulation 82
Biological Requirements of Dental Materials  61 Precautions 82
Classification of Materials from a Biological Clinical Considerations  82
Perspective 62 Contraindications 82
Biohazards Related to the Dental Materials  62 Fluoride Varnishes  82
Biological Considerations of Restoration Design  63 Composition 83
Physical Factors Affecting Pulp Health   64 Manipulation 83
Classification of Adverse Reactions from Dental Contraindications 83
Materials 65
Toxicity Evaluation  66 8. Dental Cements 84
Therapeutic Effects of Dental Materials  67 Classification   84
Osseointegration 67 General Structure  85
Effect of Pressure on Tissues  67 Uses of Cements  85
Effect of Pontic Design  68 General Properties of Cements  86
Effect of Material – Porcelain versus Resin  68 Silicate Cements  88
Infection Control  69
Zinc Phosphate Cement  88
Applications 89
Section 2: Direct Restorative Classification 89
Available as  89
Materials Composition   89
Manufacture 90
Setting Reaction  90
6. Introduction to Restorations, Properties   91
Luting and Pulp Therapy 73 Manipulation 92
Advantages and Disadvantages of Zinc
Restorations 73 Phosphate 93
Temporary Restorations   73
Copper Cements  93
Intermediate Restorations   74
Applications 94
Requirements of a Temporary Filling Material  74
Classification 94
Permanent 74
Composition 94
Direct and Indirect Restorations  75
Properties 94
Esthetic and Nonesthetic  75
Manipulation 94
Luting 75
Zinc Polycarboxylate Cement  94
Types 75
Applications 95
General Requirements of Luting Materials  76
Available as  95
Pulp Capping  76 Composition   95
Criteria for Pulp Capping  76 Manufacture 96
Types of Pulp Capping  77 Setting Reaction  96
Bases 77 Properties   96
Types 78 Manipulation 97
Properties   78 Advantages and Disadvantages  98
Clinical Considerations  79 Zinc Oxide Eugenol Cement  98
Liners and Varnish  79 Classification (ISO 3107:2011)  99
 Contents  xvii

Available as  99 Supplied as  125

Composition 100 Composition   125
Setting Reaction  100 Setting Reaction  125
General Properties of Zinc Oxide Eugenol Bonding and Curing  126
Cements 101 Manipulation 126
Manipulation   102 Properties 126
Modified Zinc Oxide Eugenol Cements  102 Advantages and Disadvantages  127
Eba-alumina Modified Cements  102
Polymer Reinforced Zinc Oxide Eugenol
9. Dental Amalgam 128
Cement 104 Indications 129
Other Zinc Oxide Eugenol Products  105 Contraindications 129
Zinc Oxide/Zinc Sulphate Cements  105 Classification of Amalgam Alloys  130
Manufacture of Alloy Powder   130
Glass Ionomer Cements  106
Supplied as  131
Application 107
Composition 132
Classification 107
Comparison of Lathe Cut and Spherical Alloys  133
Available as  107
Composition   108 Low Copper Alloys  133
Manufacture 109 Composition 133
Setting Reaction  109 Available as  134
Properties   110 Setting Reaction  134
Manipulation 111 High Copper Alloys  135
Packable Glass Ionomer for Posterior Admixed Alloy Powder  135
Restorations 114 Types 135
Fissure Sealing (Special Applications)  115 Composition 135
Modified Glass Ionomers  115 Setting Reaction  136
Metal Modified Glass Ionomer Cement  115 Single Composition Alloys  137
Types 115 Composition 137
Uses 115 Setting Reaction  137
Properties   116 Advantages/Disadvantages of Spherical High-
Resin-modified Glass Ionomer  116 copper Amalgam  137
Classification 116 Properties of Set Amalgam  138
Supplied as  117 Technical Considerations   143
Composition 117 Mulling 148
Setting Reaction  118 Condensation 148
Manipulation 118 Shaping and Finishing   150
Properties 118 Amalgam Bonding  151
Calcium Hydroxide Cement  118 Mercury Toxicity  152
Applications 119 Amalgam Disposal  153
Available as  119 Advantages and Disadvantages of Amalgam
Composition   119 Restorations 154
Setting Reaction  120
10. Direct Filling Gold 156
Properties 120
Manipulation 120 Applications 157
Setting Time  120 Contraindications 157
Light Activated Calcium Hydroxide Cement  121 Types 157
Calcium Hydroxide Root Canal Sealing Pastes  121 Composition and Purity  158
Resin Cements  121 Gold Foil  158
Applications 122 Manufacture 158
Classification 122 Supplied as  158
Supplied as  122 Electrolytic Precipitate  159
Composition 123 Available as  160
Polymerization 123 Mat Gold  160
Properties 123 Mat Foil  160
Manipulation and Technical Considerations  123 Alloyed Electrolytic Precipitates  160
Compomer (Polyacid-modified Composite Powdered Gold  160
Resins) 124 Manufacture 160
Applications 124 Available as  160
xviii  BASIC DENTAL MATERIALS

Manipulation of Direct Filling Gold  161 Paste-type Obturating Materials   224

Properties of Compacted Gold   164 Root Canal Sealers  225
Advantages and Disadvantages  165 Zinc Oxide-eugenol-based Sealers   226
Epoxy Resin-based Sealers  228
11. Resin-based Composites and
Calcium Hydroxide based Sealers  229
Bonding Agents 167 Glass Ionomer-based Sealers  231
Composite Resins  168 Silicon-based Sealers  231
Uses 168 Mineral Trioxide Aggregate (MTA) 232
Types 169 Endodontic Solvents  237
Restorative Composite Resins  171
Supplied as  171
Indications for Various Composite Resins  172 Section 4: Impression Materials
Composition and Structure  172
Polymerization (Setting) Mechanisms  177
Microfilled Composite  181
14. Rigid Impression Materials—
Composition 181 Impression Compound and
Clinical Considerations  181 ZOE Paste 243
Hybrid Composite Resins  182 Advantages of Using a Cast or Model  243
Nano and Nanohybrid Composite Resins  182 Desirable Properties of an Impression Material  244
Properties of Composite Resins  182 Classification of Impression Materials  244
Problems in the Use of Composites for Posterior Rigid Impression Materials  245
Restorations 186 Impression Compound  245
Manipulation and Placement of Composite Classification 245
Resins 187 Supplied as  245
Techniques of Insertion  188 Applications 246
Finishing and Polishing  189 Requirements of Impression Compound  246
Bonding 189 Composition 247
Acid Etch Technique  190 Properties of Impression Compound  247
Enamel Bond Agents  192 Manipulation   248
Enamel/Dentin Bond Systems  192 Removal of Impression from the Mouth  249
Repair of Composites  196 Disinfection 250
Sandwich Technique  197 Pouring the Cast and Cast Separation  250
Specialized Composite Resins  197 Advantages and Disadvantages  250
Advantages and Disadvantages of Restorative Zinc Oxide Eugenol Impression Paste  250
Composite Resins  203 Classification 251
Available as  251
Section 3: Endodontic Materials Composition 252
Setting Reaction  252
Microstructure 252
12. Endodontic Medicaments Setting Time  252
Properties   253
and Irrigants 207
Manipulation 254
Root Canal Irrigants  208 Impression Tray  254
Chemically Active Irrigants  209 Disinfection 255
Intracanal Medicaments  211 Pouring the Impression  255
Phenol and Related Compounds  212 Advantages and Disadvantages  255
Antibiotics 213 Other Zinc Oxide Pastes  255
Halogens 214
Quaternary Ammonium Compounds  215 15. Elastic Impression Materials—
Calcium Hydroxide  215 Agar and Alginate 258
Chlorhexidine (CHX) Gluconate  215 Hydrocolloids   259
Reversible Hydrocolloids—Agar  260
13. Endodontic Sealers and
Classification Based on Viscosity
Obturating Materials 216 (ISO 21563:2013)  260
Root Canal Obturating Materials  217 Uses 260
Silver Points   217 Supplied as  261
Gutta-percha 218 Composition 261
 Contents  xix

Gelation or Setting of Agar  262 Addition Silicones (Polyvinyl Siloxane)  286

Manipulation 262 Supplied as  286
Impression Trays  263 Composition 286
Making the Impression  263 Chemistry and Setting Reaction  286
Working and Setting Time  263 Properties 287
Removal of Impression  263 Polyether Rubber Impression Material  287
Storage of Agar Impression  263 Available as  287
Separation from Cast  264 Composition 288
Properties of Agar Hydrocolloids  264 Chemistry and Setting Reaction  288
Laminate Technique (Agar–Alginate Combination Properties 289
Technique) 265 Manipulation of Elastomeric Impression
Wet Field Technique  265 Materials 289
Cast Duplication  265 Impression Techniques  291
Impression Disinfection  266 Removal of the Impression  294
Advantages and Disadvantages of Agar Infection Control  294
Hydrocolloid 266 Impression Errors  294
Irreversible Hydrocolloid—Alginate  267 Specialized Materials  297
Types 267
Supplied as  267
Applications 268 Section 5: Dental Laboratory—
Composition 268
Setting Reaction  269
Materials and Processes
Properties of Alginate Hydrocolloid   269
Shelf Life and Storage  271 17. Model, Cast and Die Materials 301
Manipulation 271
Types of Die Materials  302
Mixing Time  272
Ideal Requirements of Die Materials  302
Working Time  272
Alternate Die Materials  303
Gelation Time (Setting Time)  272
Tray Selection  272 Improved Dental Stone or Die Stone  303
Loading the Tray  273 Advantages 303
Seating the Tray  273 Disadvantages 303
Time of Removal and Test for Set  273 Electroformed/Electroplated Casts and
Removal of the Impression  274 Dies 303
Impression Disinfection  274 Advantages 304
Storage of Alginate Impression  275 Disadvantages 304
Construction of Cast  275 Electroforming 304
Advantages and Disadvantages of Alginate  276 Components of an Electroplating Apparatus  304
Composition of the Electroplating Bath  305
16. Elastomeric Impression Materials 277 Procedure 305
Chemistry and Structure of Elastomeric Polyurethane 306
Polymers 278 Mode of Supply  306
Types 279 Indications 306
Uses of Elastomeric Impression Materials  280 Properties 306
Supplied as  280 Manipulation 306
General Properties of Elastomeric Materials  280 Epoxy Resin Die Materials  307
Polysulfides 282 Advantages 307
Supplied as  282 Disadvantages 307
Composition 282 Available as  307
Chemistry and Setting Reactions  282 Refractory Cast for Wax Patterns  307
Properties 283 Refractory Cast for Ceramics  308
Silicone Rubber Impression Materials  283 Die Stone-investment Combination
Types 284 (Divestment) 308
Condensation Silicone  284 Divestment Phosphate or DVP 308
Supplied as  284
Composition   285 18. Gypsum Products 310
Chemistry and Setting Reaction  285 Applications   310
Properties 285 Classification 311
xx  BASIC DENTAL MATERIALS

Type 1 or Dental Plaster, Impression  311 Setting Reaction  348

Type 2 or Dental Plaster, Model, Mounting   312 Setting Time  348
Type 3 or Dental Stone, Model  312 Properties of Gypsum Investments   348
Type 4 or Dental Stone, Die, High Strength, Low Hygroscopic Thermal Inlay Casting Investment  351
Expansion 313 Investments for Casting High Melting Alloys  351
Type 5 or Dental Stone, Die, High Strength, High Phosphate Bonded Investment  351
Expansion 313 Uses 351
Manufacture of Gypsum Products  314 Classification 351
Setting Reaction  315 Supplied as  352
Theories of Setting  315 Composition 352
The Microstructure of Set Gypsum  316 Setting Reaction  352
Manipulation   317 Manipulation 352
Setting Time  318 Properties 353
Properties 321 Specialized Refractory Materials  354
Setting Expansion  321 Silica Bonded Investments  356
Strength 322 Types 356
Hardness and Abrasion Resistance  323 Manipulation 356
Flow 323
Brazing (Soldering) Investment  356
Reproduction of Detail  323
Uses 357
Specialized Gypsum Products  324
Types 357
Care of Gypsum  325
Composition 357
Infection Control  326
Properties 357
Differences between Dental Plaster and Dental
Procedure 357
Stone 326
21. Dental Casting and Metal Fabrication
19. Waxes in Dentistry 327
Procedures 358
Components of Dental Waxes  327
Metal Restorations in Dentistry  358
Chemical Nature of Waxes  327
Classification of Dental Waxes  330 Casting 360
General Properties  330 Steps in Making a Small Cast Restoration  360
Tooth/Teeth Preparation  360
Pattern Waxes  331
Die Preparation  360
Inlay Casting Wax   332
Die Spacer  360
RPD Casting Wax  336
Wax Pattern  360
Milling Wax  337
Sprue Former  361
Baseplate Wax  337
Casting Ring Lining  361
Processing Waxes  339 Investing 362
Boxing Wax and Beading Wax  339 Wax Elimination (Burnout) and Thermal
Utility Wax   340 Expansion 362
Sticky Wax  340 Casting-process and Equipment  363
Carding Wax  340
Casting Defects  366
Shellac 341
Types of Casting Defects  366
Impression Waxes  342 Other Methods of Fabricating Restorations and
Corrective Impression Wax  342 Prostheses 371
Bite Registration Wax   343
Capillary Casting Technique (Captek)  371
20. Dental Investments and Refractory Mode of Supply  372
Materials 345 Capillary Casting  372
Overall Composition after Capillary Casting  373
Requirements of an Investment Material  345
Coping Thickness  373
Classification of Refractory Materials in Dentistry
Coping Microstructure  373
(ISO 15912:2006)  346
Technique 373
General Composition of Investments  346
CAD/CAM Milling  373
Gypsum Bonded Investments   347
Advantages of CAD/CAM  374
Classification 347
Uses 347 Copy Milling  374
Supplied as  347 Electroforming 374
Composition 347 Electrical Discharge Machining  375
Manipulation 348 Applications 375
 Contents  xxi

Technique 375 Resistance Spot Welding  400

Advantages 376 Tungsten Inert Gas (TIG) Welding and Plasma
Disadvantages 376 Arc Welding (PAW)   401
Additive Manufacturing  376 Procedure 401
Types of Metal in Additive Manufacturing Advantages and Disadvantages  401
Technologies 377 Laser Welding  402
Applications 377 Commercial Names  404
Metals Available for 3D Printing  377 Indications 404
Mechanism 405
22. Abrasion and Polishing 378
Advantages of Laser Welding  405
Abrasion 378 Cast-joining 406
Defined as  378 Radiographic Assessment of Joints  406
Types of Abrasion  379
Supplied as  379 24. Additive Manufacturing in Dentistry 407
Mechanism of Abrasive Action  380 Applications 407
Stress, Strain and Heat Production during Fundamentals of 3D Printing  408
Abrasion 380 Classification of Additive Manufacturing (AM)
Rate of Abrasion  380 Technologies 409
Classification 381 Description of Some Additive Manufacturing (AM)
Types of Abrasives  381 Technologies 410
Desirable Characteristics of an Abrasive  383 3D Dental Printers  412
Grading of Abrasive and Polishing Agents  383 Support Structures for 3D Printed Objects  412
Binder 383 Raw Materials for 3D Printing  414
Diamond Burs  383 Post-manufacturing Processing  414
Polishing 384 3D Printed Maxillofacial Prostheses  414
Difference between Abrasion and Polishing  384 3D Printing Technology in Surgical Planning  415
Nonabrasive Polishing  385 Tissue Engineering  415
Technical Considerations (Procedure)  385 Bioink 416
Dentifrices 387 Osteoink 417
Function 387 Comparison of Additive and Subtractive
Available as  387 Manufacturing 418
Classification of Dentifrices  387 Advantages of 3D Printing  418
Composition 388
Prophylactic Abrasives  390
Function 390
Section 6: Alloys in Dentistry
Prophyjet 390
Denture Cleansers  391 25. Dental Casting Alloys 421
Brushing 391 Terminology 421
Soaking 391 History and Classification of Dental Casting
23. Metal Joining and Dental Lasers 392 Alloys 422
Classification According to Use of Dental Casting
Terms and Definitions  392
Alloys 425
Ideal Requirements of a Brazing Material (Dental
General Requirements of Casting Alloys  425
Solder) 393
Types of Solders or Brazing Materials  393 Alloys for All Metal Restorations  426
Applications of Soldering  394 Classification (ANSI/ADA Sp. No. 5)  426
Composition   394 Uses 426
Properties of Dental Brazing Materials   395 Types 427
Fluxes 396 Gold Alloys (for All-metal Restorations)  427
Antiflux 397 Gold Content  427
Technical Considerations  397 Composition of Gold Alloys  428
Technique of Soldering  398 Properties of Gold Alloys  429
Pitted Solder Joints  399 Heat Treatment of Gold Alloys  431
Advantages and Disadvantages  399 Low Gold Alloys  431
Welding 400 Silver-palladium Alloys  432
Indications 400 Nickel-chrome and Cobalt-chromium
Types 400 Alloys 433
xxii  BASIC DENTAL MATERIALS

Titanium and Titanium Alloys  433 Composition 470

Aluminum-bronze Alloy  433 Properties 470
Metal-ceramic Alloys  433 Wrought Base-metal Alloys  470
Evolution of Metal-ceramic Alloys  434 Stainless Steel  470
Requirements of Alloys for Porcelain Bonding  434 Ferritic Stainless Steels  471
Uses of Metal-ceramic Alloys  434 Martensitic Stainless Steels  471
Types (Classification) of Metal-ceramic Alloys  434 Austenitic Stainless Steels  471
The High Noble (Gold-based) Metal-ceramic Braided and Twisted Wires  473
Alloys 435 Solders for Stainless Steel  473
Gold-palladium-platinum Alloys  436 Fluxes 473
Gold-palladium-silver Alloys  437 Wrought Cobalt-chromium-nickel Alloys  473
Gold-palladium Alloys  438 Composition 473
Noble (Palladium-based) Metal-ceramic Heat Treatment  473
Alloys 438 Physical Properties  474
Common Features of Palladium-based (Noble) Nickel-titanium Alloys  474
Alloys 438 Properties of Nitinol Alloys  474
Palladium-silver Alloys  439 Titanium Alloys  475
Palladium-copper Alloys  439 Composition 476
Palladium-cobalt Alloys  440 Mechanical Properties  476
Palladium-gallium Alloys  440
Base Metal Alloys for Metal-ceramic
Restorations 440 Section 7: Indirect Restorative
Nickel-chromium Alloys  441
Titanium and Its Alloys for Metal-ceramic and Prosthetic Materials
Applications 443
Removable Denture Alloys  446 28. Dental Ceramics 479
Cobalt-chromium Alloys  447
Technical Considerations for Casting Alloys  449 Uses and Applications  479
Advantages and Disadvantages of Base Metal Evolution of Dental Ceramics  480
Alloys 451 Classification of Dental Porcelains  481
Comparison of a Gold Alloy and a Base Metal Basic Constituents and Manufacture of Feldspathic
Alloy 451 Porcelain 482
Manufacture 485
26. Dental Implant Materials 452 Porcelain/Ceramic Systems  485
Definition 452 Metal-ceramic Restorations  486
Types of Implants  453 Types of Metal-ceramic Systems  487
Materials Used  454 Cast Metal-ceramic Restorations  487
Implant Parts  455 Uses 487
Implant Abutment Connection  458 Composition of Ceramic for Metal Bonding  487
Platform Switching  459 Supplied as  488
Biointegration and Osseointegration  459 Manipulation and Technical Considerations  488
Titanium Allergy  461 Porcelain-metal Bond  492
Zirconia Implants  461 Advantages and Disadvantages of Metal-ceramic
Zirconia Anatomic Root-form Implants  461 Restorations 492
Implant Surfaces and Coatings  462 Other Metal-ceramic Systems  493
All-ceramic Restorations  494
27. Wrought Metals and Alloys 466
Porcelain Jacket Crown  494
Manufacture of Wrought Alloys  466 Castable Glass Ceramic  496
Structure of Wrought Alloys  467 Heat Pressed (Hot-isostatically Pressed)
Annealing 467 Ceramics 498
Uses of Wrought Alloys  468 Glass Infiltrated Ceramics  500
Orthodontic Wires  468 CAD/CAM Ceramics  503
General Properties of Orthodontic Wires  469 Advantages and Disadvantages of CAD/CAM
Types 469 Ceramic Restorations  514
Wrought Gold Alloys   469 General Properties of Fused Ceramics  515
Uses 469 Cementing of Ceramic Restorations  520
Classification 470 Repair of Ceramic Restorations  522
 Contents  xxiii

Porcelain Denture Teeth  523 Processing Errors   559

Monolithic Restorations  524 Repair of Acrylic Resin Dentures  561
Ceramic Posts  526 Infection Control for Dentures  561
Pediatric Zirconia Crowns  526 Care of Acrylic Dentures  561
Zirconia Implants and Abutments  526 Denture Cleansers  562
Zirconia Anatomic Root-form Implants  527 CAD/CAM Dentures  562
29. Denture Resins and Polymers 529 Denture Reliners  564
Heat Cured Acrylic Resin (Hard Liner)  564
Polymers 531 Chairside Reliners (Hard Short-term Liner)  564
Nature of Polymers  531 Soft or Resilient Denture Liners  564
Structure of Polymers (Spatial Structure)  532 Long-term Soft Liners  564
Polymerization—Chemistry 533 Tissue Conditioners (Short-term Soft Liner)  566
Copolymerization 535
Denture Adhesives  567
Cross-linking 536
Supplied as  567
Plasticizers 537
Composition 567
Classification of Denture Base Materials  537
Properties 567
Synthetic Resins  538
Rebasing of Dentures  568
Classification of Resins  538
Provisional Crown and FDP Materials  568
Ideal Requirements of Dental Resins  538
Uses of Resins in Dentistry  539 30. Maxillofacial Prosthetic Materials 572
Acrylic Resins  540 Evolution of Maxillofacial Materials  573
Poly (Methyl Methacrylate) Resins  540 3D Printed Maxillofacial Prostheses  577
Heat Activated Denture Base Acrylic Resins  540 3D Bioprinting  577
Chemically Activated Denture Base Acrylic
Resins 548
Light Activated Denture Base Resins  552 Appendices 579
Microwave Cured Denture Resins  553
Specialized Poly (Methyl Methacrylate) Further Reading 589
Materials 553
Properties of Methylmethacrylate Denture
Index 595
Resins 555
Section-1
Structure and Properties
of Dental Materials
Chapter 1 Overview of Dentistry and Dental Materials,  3
Chapter 2 Structure and Properties of Dental Materials,  9
Chapter 3 Structure and Properties of Metals and Alloys,  39
Chapter 4 Electrochemical Properties of Materials,  56
Chapter 5 Biological Properties of Dental Materials,  61
 1
Chapter

Overview of Dentistry
and Dental Materials
Chapter Outline
• Prevention • Classification of Dental Materials • Ada Certification
• Rehabilitation • International Standards • Summary
• The Dental Laboratory • US Standards for Dental Materials

Dentistry over the years has evolved into a highly complex field and materials play a crucial
role in every aspect of treatment. Dental treatment not only includes the practice of medicine
and surgery but also restoration of missing or lost structures. Besides restorations, appliances
for various functions are also constructed for use in the mouth. The oral cavity is a challenging
environment and materials placed in the mouth have to withstand high masticatory forces
as well as corrosion. Besides direct use in the oral cavity, many materials are also used in the
laboratory to aid in the fabrication of appliances or prostheses. Thus dentistry incorporates
the knowledge of various materials as well as principles of engineering.

Dental treatment
For convenience of description, dental care may be divided into various phases. These include
preventive, disease control and elimination, restorative, rehabilitative and maintenance phases.

Preventive
The preventive phase is very important. It includes educating the patient on how to maintain his
oral hygiene through regular brushing, flossing and periodic checkup at the dental office. Regular
brushing with a suitable brush and paste has been shown to be very effective at controlling
caries as well as gum (periodontal) problems. The role of fluorides and fluoride therapy in the
control of dental caries has been known to us for a long time. Fluoridation of drinking water
and fluoride therapy at the dental office has played a significant role in reducing dental caries
especially in children. Caries often begins in deep fissures in teeth. Fissure sealants is another
preventive measure especially in children to prevent caries.

Disease control and elimination

The next stage in the progress of dental disease is the actual development of dental caries and
periodontal disease. This phase of treatment focuses on eliminating or controlling diseases of
the mouth to halt their destruction. Commonly, patients will come to a dental office because
4  Part 1  Structure and Properties of Dental Materials
of pain caused by cavities or infection. This phase focuses on treating cavities (by placing
fillings), eliminating infection (by root canal or tooth removal), and managing gum health
(oral prophylaxis and other periodontal procedures).
Caries involves the demineralization and destruction of tooth structure. The focus is to arrest
the caries process. This involves removing the carious tooth structure and restoring the cavity
with a suitable temporary or permanent filling material. The famous silver filling has been in
use for more than a century and is currently the most widely used filling material. The silver
amalgam restoration would certainly look unpleasant if used for the front (anterior) teeth.
Therefore anterior teeth are restored with an esthetic (tooth colored) material. Other ways to
restore teeth involve the use of gold inlays and ceramic inlays.
As caries progresses, it gets closer to the pulp, which can lead to pain (pulpitis) and infection
of the pulp. If the pulp is only mildly affected, pulp therapy is started using materials which
have a therapeutic effect on the pulp. These materials can be soothing and promote healing
by forming a new layer of dentin (secondary dentin).
If the pulp is infected, it is removed (pulpectomy) and root canal treatment popularly known
as RCT is initiated. After removing the pulp, the canal is made sterile and sealed using root
canal filling materials. The root canal treated tooth is weak and is prone to fracture if not
protected with a crown or onlay.

Restorative
This phase of treatment focuses on restoring the function and/or form of the teeth and mouth
following the destruction caused by the original disease process. Common treatments during
this phase include prosthesis (implants, bridges, partials, and dentures) to replace missing
teeth and crowns to protect teeth.
Before the discovery of tooth colored crown materials, metallic crowns were given (the
famous gold tooth). Modern dentists are able to provide crowns that are natural looking
and pleasing. Many of these structures are processed outside the mouth, in the laboratory.
The dental technician uses an accurate model of the teeth to fabricate these restorations.
Models are made from a negative record of the mouth called an impression. This is sent to the
laboratory where the technician pours a mix of plaster or stone into the impression. When
the mix hardens, we obtain a model.
If the coronal tooth structure is entirely gone or destructed, even a crown would not stay. In
this case, the dentist has to place a post and core. The part placed into the root canal is known
as post and the rest of it is known as the core. The crown is then constructed and cemented
onto the core.
Following extraction of teeth, the patient often desires that it be replaced with an artificial
tooth. There are many ways of replacing the tooth. Today implants have become very popular.
A titanium screw can be implanted into the jaw surgically followed by an artificial crown.
Another next choice is the fixed partial denture (bridge). Usually the teeth by the side of the
missing tooth is reduced in size (prepared) in order to receive the bridge. The bridge is then
cemented onto these teeth.
If too many teeth are missing, we might have to consider the removable partial denture which
replaces the missing teeth but is not fixed in the mouth. It can be removed by the patient for
cleaning and hygiene. The ideal removable partial denture is usually made of a combination
of metal and plastic (cast partial denture). Interim or temporary partial dentures are made
entirely of plastic also and are often referred to as treatment partial dentures.
The final stage is when all the teeth have to be replaced. One is, of course, familiar with the
complete denture which is often seen in elderly individuals. These artificial teeth replace the
 Overview of Dentistry and Dental Materials  Chapter 1  5
entire dentition and are usually of the removable type (fixed complete dentures are also available
which are supported and retained by implants). The complete denture is usually made of a
type of plastic called acrylic. The teeth used in the denture can be made of acrylic or porcelain.
Besides all the materials mentioned above, different specialties in dentistry have their special
materials. Some of these are not covered in this book. For example, endodontists use root
canal files along with various irrigants to clean and debride the root canal. A variety of root
canal sealing pastes and medicaments are also available. The periodontists use different
types of graft material to restore lost periodontal bone and tissue. Unfortunately, not all the
materials used in dentistry are within the scope of this book.

Maintenance Phase
Once the treatment is completed, a maintenance phase focuses on keeping the dental work
in functioning order through periodic recalls, maintaining health (oral prophylaxis), and
screening for oral cancer at each six-month exam.

The DENTAL SPECIALTIES

Currently nine specialties are recognized by the Dental Council of India.
1. Conservative Dentistry and Endodontics
2. Periodontics
3. Prosthodontics
4. Public Health Dentistry
5. Oral Medicine and Radiology
6. Oral and Maxillofacial Surgery
7. Orthodontics and Dentofacial Orthopedics
8. Oral and Maxillofacial Pathology
9. Pedodontics and Preventive Dentistry

Conservative dentistry  That phase of dentistry concerned with restoration of parts of the
teeth that are defective through disease, trauma, or abnormal development to a state of
normal function, health, and esthetics, including preventive, diagnostic, biologic, mechanical,
and therapeutic techniques, as well as material and instrument science and application.*1
Endodontics  Endodontics is the branch of dentistry which is concerned with the morphology,
physiology and pathology of the human dental pulp and periradicular tissues. Its study and
practice encompass the basic and clinical sciences including biology of the normal pulp,
the etiology, diagnosis, prevention and treatment of diseases and injuries of the pulp and
associated periradicular conditions.*1
Periodontics  Periodontics is that specialty of dentistry which encompasses the prevention,
diagnosis and treatment of diseases of the supporting and surrounding tissues of the teeth or
their substitutes and the maintenance of the health, function and esthetics of these structures
and tissues.
Prosthodontics  Prosthodontics is the dental specialty pertaining to the diagnosis, treatment
planning, rehabilitation and maintenance of the oral function, comfort, appearance and health
of patients with clinical conditions associated with missing or deficient teeth and/or oral and
maxillofacial tissues using biocompatible substitutes.*2

*1 Free Dictionary
*2 Adapted from the Council on Dental Education and Licensure, American Dental Association
6  Part 1  Structure and Properties of Dental Materials
Public health dentistry  Dental Public Health is the science and art of preventing and
controlling dental diseases and promoting dental health through organized community
efforts. It is that form of dental practice which serves the community as a patient rather than
the individual. It is concerned with the dental health education of the public, with applied
dental research, and with the administration of group dental care programs as well as the
prevention and control of dental diseases on a community basis.*2
Oral medicine and radiology
 Oral medicine is concerned with clinical diagnosis and nonsurgical management of
nondental pathologies affecting the orofacial region (the mouth and the lower face).
 Oral and maxillofacial radiology is the specialty of dentistry and discipline of radiology
concerned with the production and interpretation of images and data produced by all
modalities of radiant energy that are used for the diagnosis and management of diseases,
disorders and conditions of the oral and maxillofacial region.*2

Oral and maxillofacial surgery  Oral and Maxillofacial Surgery is the specialty of dentistry
which includes the diagnosis, surgical and adjunctive treatment of diseases, injuries and
defects involving both the functional and esthetic aspects of the hard and soft tissues of the
oral and maxillofacial region.*2
Orthodontics and dentofacial orthopedics  Orthodontics and dentofacial orthopedics
is the dental specialty that includes the diagnosis, prevention, interception, and correction
of malocclusion, as well as neuromuscular and skeletal abnormalities of the developing or
mature orofacial structures.*2
Oral and maxillofacial pathology  Oral Pathology is the specialty of dentistry and discipline
of pathology that deals with the nature, identification, and management of diseases affecting
the oral and maxillofacial regions. It is a science that investigates the causes, processes, and
effects of these diseases. The practice of oral pathology includes research and diagnosis of
diseases using clinical, radiographic, microscopic, biochemical, or other examinations.*2
Pedodontics and preventive dentistry  Pediatric Dentistry is an age-defined specialty that
provides both primary and comprehensive preventive and therapeutic oral health care for
infants and children through adolescence, including those with special health care needs.*2

The dental laboratory

Many materials are used in the dental laboratory to aid in the fabrication of stents, prostheses,
appliances and other structures used in and around the mouth. These include cutting, abrading
and polishing materials. Investment materials are used in the creation of moulds in the casting
of metal structures. Waxes are used in various stages of construction of different structures.
Gypsum products are used to make casts, models, molds and to secure articulators.

Classification of Dental Materials

Traditionally the subject of dental materials primarily included materials used in Restorative
Dentistry including related auxiliary material. Currently, there is a trend to be more inclusive
and include materials from specialties, which have traditionally been excluded like the
Endodontic and Surgical specialties.
There is no classification that satisfactorily categorizes all materials used in dentistry. This is
because many of the materials have multiple utilities and overlapping functions.

*1 Free Dictionary
*2 Adapted from the Council on Dental Education and Licensure, American Dental Association
 Overview of Dentistry and Dental Materials  Chapter 1  7
General classification of all materials
All materials can be classified into four classes
1. Metals
2. Ceramics
3. Polymers
4. Composites
Classification of dental materials
1. Preventive materials 5. Appliance materials
2. Restorative materials 6. Biomaterials
3. Auxiliary materials 7. Therapeutic agents
4. Prosthetic materials
Preventive materials include pit and fissure sealants and other materials used to prevent the
onset of dental diseases.
Restorative materials include materials used to repair or replace tooth structure. This includes
materials like amalgam, composites, ceramics, cast metal structures and denture materials.
Auxiliary materials are substances that aid in the fabrication process but do not actually become
part of the restoration, appliance or prosthesis. This includes materials like gypsum products,
impression materials, casting investments, waxes, etching gels, custom tray materials, etc.
Prosthetic materials are materials used to replace missing teeth and oral and maxillofacial
structures. These include the alloys, ceramics and polymers used in fixed and removable
partial denture construction and maxillofacial prostheses.
A biomaterial is a biological or synthetic substance which can be introduced into body tissue
as part of an implanted medical device or used to replace an organ, bodily function. Although
many traditional materials qualify as biomaterials, this term has been introduced to include
bone and tissue grafts.
Therapeutic agents include various chemicals, medicaments, antimicrobials and other locally
applied agents that are capable of producing a specific effect in the area to which it is applied.
In reality, many materials have dual or multiple uses and so the above categorization is difficult
to strictly apply.

International standards ORGANIZATION (ISO)

The Federation Dentaire Internationale (FDI) and the International Organizations for
Standardization (ISO) are two organizations working for the development of specifications
and terminology on an international level. The FDI is restricted to dental products whereas
the ISO covers all products. The ISO is a nongovernmental body composed of the national
organizations of more than 80 countries including India (Bureau of Indian Standards). The
ISO standards (Fig. 1.1A) (see also appendix) are formulated by a ‘technical committee’ (TC).
Dental products are covered by TC 106. Various subgroups known as ‘subcommittees’ (SC)
cater to specific areas. The subcommittees are further divided into ‘working groups’ (WG) to
cover individual products or items. For example, TC 106/SC 1: WG 7 covers dental amalgam
and mercury.
Considering the worldwide supply and demand for dental products the benefits from the ISO
are invaluable. Suppliers and consumers can be assured of impartial reliable data to assess
the quality of products and equipment regardless of its country of origin and use. Standards
are constantly revised; therefore, it is imperative for manufacturers and researchers alike to
refer to the latest edition of the ISO specifications to stay abreast of changes in requirements
and classifications.
8  Part 1  Structure and Properties of Dental Materials

A B
Figures 1.1A and B  Examples of standards: (A) International Standards Organization’s specification
for zinc oxide eugenol cement (ISO). (B) ANSI/ ADA specification No. 122 for dental waxes.

US Standards for Dental Materials

Standards are specifications by which the quality of a product can be gauged. Standards
identify the requirements of physical and chemical properties of a material which ensures
satisfactory performance for the function for which it is intended.
The earliest standards in the US were developed by the National Bureau of Standards in 1919
on the request of the US Army for the purchase and use of dental amalgam. The task was
assigned to a team led by Wilmer Souder. Souder’s report and testing methods were well
received by the dental profession and test data were requested for other dental materials.
By 1928, the responsibility for continued research into standards was assumed by the ADA.

ADA certification
Currently the ADA under direction of the ANSI (American National Standards Institute)
sponsors two committees. The ADA Standards Committee for Dental Products develops
specifications for all dental products, instruments and equipment (excluding drugs and X-ray
films). The ADA’s Council on Scientific Affairs is responsible for the evaluation of drugs, teeth
cleaning agents, teeth whitening agents, therapeutic agents used in dentistry and dental
X-ray films. After formulation of the specifications by the ADA, it is submitted to the ANSI. On
approval, it becomes a national standard (Fig. 1.1B).
Manufacturers can submit their product for the ADA seal of approval. This falls into three
categories – Accepted, Provisionally Accepted, and Unaccepted. ADA certification is an
important symbol of a dental product safety and effectiveness. ADA acceptance is effective
for a period of 5 years.
Currently, the ADA have adopted the ISO specifications. The ADA specification for a particular
product is identical to its ISO counterpart.

Summary
Materials used for dentistry are highly specialized. Each one is designed with a specific set
of properties depending on what it is intended for. For example, materials used as tooth
restorations should be able to withstand occlusal forces as well as bond to tooth structure.
Impression materials should be highly accurate and stable in order to duplicate the original
structure. Modern science, research and technology has provided dentistry with an ever-
expanding selection of unique combinations of materials and techniques to serve dental
treatment needs.
 2
Chapter

Structure and Properties

of Dental Materials
Chapter Outline
• Structure of Matter • Strength –– Newtonian
• Forms of Matter –– Tensile Strength –– Pseudoplastic
• Change of State –– Compressive Strength –– Dilatant
• Interatomic Bonds –– Shear Strength • Physical Properties
–– Primary Bonds –– Transverse or Flexural • Forms of Matter
–– Secondary Bonds Strength • Melting Point
• Thermal Expansion • Fatigue • Boiling Point
• Crystal Structure –– Static Fatigue • Density
• Noncrystalline Structure • Toughness • Glass Transition Temperature
• Stress and Strain • Brittleness (Tg)
• Diffusion • Ductility • Solubility
• Surface Tension • Malleability • Thermal Properties
• Wetting • Hardness –– Thermal Conductivity
• Contact Angle –– Brinell –– Thermal Diffusivity
• Physical Properties of Dental –– Rockwell Hardness Number –– Thermal Expansion
Materials (RHN) –– Coefficient of Thermal
• Stress –– Vickers Hardness Test Expansion (CTE)
• Complex Stresses (VHN) • Optical Properties and Color
• Poisson’s Ratio –– Knoop Hardness Test (KHN) • Dimensions of Color
• Proportional Limit –– The Shore and the Barcol • Measurement of Color
• Elastic Limit • Rheology • Metamerism
• Yield Strength –– Viscosity • Translucence, Transparence and
• Modulus of Elasticity –– Creep Opacity
• Flexibility –– Flow • Fluorescence
• Resilience –– Thixotropic • Radiopacity and Radiolucency
• Impact –– Relaxation –– Measurement of Radiopacity
• Impact Strength –– Shear Stress and Shear • Magnetic Properties
• Permanent Deformation Strain Rate

All materials are made up of atoms. If the reaction of a material and its properties are to be
predicted, a basic knowledge of matter is essential. All dental restorations, whether they be
ceramic, plastic or metal, are built from atoms.

Structure of Matter
Atom  An atom is the smallest unit of matter that defines the chemical elements. Atoms are
very small. The size of atoms is measured in picometers, which is trillionths (10–12) of a meter.
Every atom is composed of a nucleus and one or more electrons that orbit the nucleus (Fig. 2.1).
10  Part 1  Structure and Properties of Dental Materials

Figure 2.1  Building blocks of matter.

Protons, neutrons and electrons  The nucleus is made of one or more protons and neutrons.
Over 99.94% of the atom’s mass is in the nucleus. The protons have a positive electric charge,
the electrons have a negative electric charge, and the neutrons have no electric charge. If the
number of protons and electrons are equal, that atom is electrically neutral. If an atom has
in excess or lesser number of electrons relative to protons, then it has an overall positive or
negative charge, and is called an ion.
Electrons of an atom are attracted to the protons in an atomic nucleus by the electromagnetic
force. The protons and neutrons in the nucleus are attracted to each other by a different force,
the nuclear force, which is usually stronger than the electromagnetic force repelling the
positively-charged protons from one another. The number of protons in the nucleus defines to
what chemical element the atom belongs, for example, all copper atoms contain 29 protons.
Quarks  Protons and neutrons are made up of subatomic particles called quarks. Quarks are
believed to be the basic building blocks of matter.

INTERATOMIC BONDS
Atoms are held together by some force. These interatomic bond­ing forces that hold atoms
together are cohesive forces.
Interatomic bonds may be classified as
1. Primary bonds, or
2. Secondary bonds

Primary Bonds
These are chemical in nature.
1. Ionic 2. Covalent 3. Metallic

Ionic Bonds  These are simple chemical bonds, resulting from mutual attraction of positive
and negative charges. The classic example is sodium chloride Na+ Cl¯.
Covalent Bonds  In many chemical compounds, two valence electrons are shared. The
hydrogen molecule (H2) is an example of covalent bonding. Another example is methane.
The carbon atom has 4 valence electrons that can be stabilized by joining with hydro­gen.
H
.
:

4H + C H:C:H
:

H
 Structure and Properties of Dental Materials  Chapter 2  11
Metallic Bonds  One of the chief characteristics of a metal is its ability to conduct heat and
electricity. Such conduction is due to the mobility of the so-called free electrons present in
the metals. The outer shield valence electrons can be removed easily from the metallic atom
leaving the balance of the electrons tied to the nucleus, thus forming a positive ion.
The free valence electrons are able to move about in the metal space lattice to form what is,
sometimes, described as an electron ‘cloud’ or ‘gas’. The electrostatic attraction between this
electron ‘cloud’ and the positive ions in the lattice bonds the metal atoms together as a solid.

Secondary Bonds (Van der waals forces)

A second type of bond between molecules may be seen. They are also known as van der Waals
forces (named after Dutch scientist Johannes Diderik van der Waals. They differ from covalent
and ionic bonding in that they are caused by correlations in the fluctuating polarizations
(dipole) of nearby particles. They are defined as weak, short-range electrostatic attractive
forces between uncharged molecules, arising from the interaction of permanent or transient
electric dipole moments.
Dipole van der Waals Forces are due to the formation of dipole. A dipole is formed when
electrons shift to one side of the atoms or molecules resulting in the formation of a negative
polarity on the side and on the other half a positive polarity. This attracts other similar dipoles.
There are three kinds of van der Waals forces – 1. Keesom force (between two permanent
dipoles), 2. Debye force (between a permanent dipole and an induced dipole) 3. London
dispersion force (between two instantaneously induced dipoles).
Van der Waals forces are relatively weak compared to covalent bonds, but play a fundamental
role in fields as diverse as supramolecular chemistry, structural biology, polymer science,
nanotechnology, surface science, and condensed matter physics. Van der Waals forces define
many properties of organic compounds. In nature geckos and spiders utilize van der Waals
forces to climb and cling on to smooth surfaces (Fig. 2.2).

CRYSTAL STRUCTURE
Space lattice or crystal can be defined as any arrangement of atoms in space such that every
atom is situated similar to every atom. Space lattice may be the result of primary or secondary
bonds.
There are 14 possible lattice type forms, but many of the metals used in dentistry belong to
the cubic system. The simp­lest cubic space lattice is shown in Figs. 2.3A to C. The solid circles
represent the position of the atoms. Their positions are located at the points of intersection
of three sets of parallel planes, each set being perpendicular to other planes. These planes
are often refer­red to as crystal planes.

Simple cubic Body centered cubic Face centered cubic

A B C

Figure 2.2  Geckos can stick to walls and Figures 2.3A to C  Crystal structure.
ceilings because of van der Waals forces.
12  Part 1  Structure and Properties of Dental Materials
NONCRYSTALLINE STRUCTURE
In a crystalline structure, the arrangement of atoms in the lattice is orderly and follows a
particular pattern. In noncrystalline struc­tures or amorphous structures, e.g. waxes, the
arrangement of atoms in the lattice is disorderly and distributed at random.
There is, however, a tendency for the arrangement of atoms or molecules to be regular, for
example, glass is considered to be a noncrystalline solid, yet its atoms bind to form a short
range order rather than long range order lattice. In other words, the ordered arrangement of
glass is localized with large number of disordered units between the ordered units. Since such
an arrangement is also typical of liquids, such solids are, sometimes, called super­cooled liquids.

STRESS AND STRAIN

The distance between two atoms is known as interatomic dis­tance. This interatomic distance
depends upon the electrostatic fields of the electrons. If the atoms come too close to each
other, they are repelled from each other by their electrons charges. On the other hand, forces
of attraction keep them from separating. Thus the atoms are kept together at a position
where these forces of repulsion and attraction become equal in magnitude (but opposite in
direction). This is the normal equilibrium position of the atoms.
The normal position of the atoms can be changed by appli­cation of mechanical force. For
example, the interatomic distance can be increased by a force pulling them apart. If the displacing
force is measured across a given area it is known as a stress and the change in dimension is called
a strain. In simple words, stress is the force applied and strain is the resulting change in shape.
Theoretically, a stress and a strain exist whenever the interatomic distance is changed from
the equilibrium position. If the stress pulling the atoms apart exceeds the resultant force of
attraction, the atoms may separate completely, and the bonds holding them together are
broken.
Strain can also occur under compression. However, in this case, the strain produced is limited
because when the atoms come closer than their normal interatomic distance, a sudden
increase in energy is seen.

DIFFUSION
The diffusion of molecules in gases and liquids is well known. However, molecules or atoms
diffuse in the solid state as well. Diffusion rates depend mainly on the temperature. The higher
the temperature, the greater will be the rate of diffusion. The diffusion rate will, however, vary
with the atom size, interatomic or intermolecular bonding lattice imperfections. Thus every
material has its own diffusion rate. The diffusion rate in noncrystalline materials may occur
at a rapid rate and often may be seen.

SURFACE TENSION
Energy at the surface of a solid is greater than in its interior. For example, inside a lattice, all
the atoms are equally attracted to each other. The interatomic distances are equal, and energy
is minimal. However, at the surface of the lattice, the energy is greater because there are no
atoms on the outside. Hence there is only a force from the inside of the lattice pulling the
outermost atoms inwards. This creates a tension on the outer surface and energy is needed
to pull the outermost atoms away. The increase in energy per unit area of surface is referred
to as the surface energy or surface tension (Figs. 2.4A and B).
The surface atoms of a solid tend to form bonds to any atom that comes close to the surface
in order to reduce the surface energy of the solid. This attraction across the interface for unlike
 Structure and Properties of Dental Materials  Chapter 2  13

A B
Figures 2.4A and B  (A) Schematic representation of molecular view of surface tension. (B) Surface tension
causes a paper clip to float on water despite the fact that metal in the paper clip has a higher density than water.

molecules is called adhesion. In summary, the greater the surface energy, the greater will be
the capacity for adhesion.

WETTING
It is very difficult to force two solid surfaces to adhere. However smooth their surfaces may
appear, they are likely to be very rough at the atomic or molecular level. When they are placed
together, only the ‘hills’ or high spots are in contact. Since these areas form only a small
percentage of the total surface, no adhesion takes place. For proper adhesion, the distance
between the surface molecules should not be greater than 0.0007 micrometer or micron (µm).
One method of overcoming this difficulty is to use a fluid
that will flow into these irregularities and thus provide
contact over a great part of the surface of the solid. For A
example, when two glass plates are placed one on top of
the other, they do not usually adhere. However, if a film of
water is placed in between them, it becomes difficult to
separate the two plates.
B
To produce adhesion in this manner, the liquid must flow
easily over the entire surface and adhere to the solid. This
characteristic is referred to as wetting. The degree of wetting is
indicated by the contact angle of the adhesive to the adherend.

Contact angle
C
The contact angle is the angle formed by the adhesive
(e.g. water) and the adherend (e.g. glass) at their interface.
The extent to which an adhesive will wet the surface of an
adherend may be determined by measuring the contact
angle between the adhesive and the adherend.
Based on the contact angle there are four classes of wetting
(Figs. 2.5A to D): D
Contact Angle = 0 Perfect wetting Figures 2.5A to D  Four classes of
Contact Angle = 0 < <90° High wettability wetting based on the contact angles.
Contact Angle = 90° ≤< 180° low wettability
Contact Angle = 180° Perfect non-wetting
14  Part 1  Structure and Properties of Dental Materials
If the forces of adhesion are stronger than the cohesive forces holding the molecules of the
adhesive together, the liquid will spread completely over the surface of the solid and no
angle will be formed (e.g. water on a soapy surface (Fig. 2.5A). If the liquid remains as a drop
without spreading, the contact angle will be high (e.g. water on an oily surface, Fig. 2.5C).

Surfactant
Surfactants are compounds that lower the surface tension (or interfacial tension) between
two liquids or between a liquid and a solid. Surfactants may act as detergents, wetting agents,
emulsifiers, foaming agents, and dispersants. Surfactants are added to some dental materials
to improve wetting.

Significance
1. The mouth is a highly moist environment and impression materials used in the mouth
should be hydrophilic in order to record details even under moist conditions.
2. Good wettability is again desired in the laboratory for products contacting gypsum
products like dental stone and plaster which have a high moisture content. While
pouring casts the stone should be able to wet the impression well in order to minimize
voids.
3. Good wetting is important in soldering in order to produce a good strong joint.

PROPERTIES OF DENTAL MATERIALS

To select and use a dental material one must under­stand its properties. Knowledge of the
properties of the material predicts its behavior, functioning in the mouth and longevity.
Accordingly one can optimize design and techniques in order to get the best out of a particular
material.

Various properties important to dental materials are

1. Physical properties
2. Mechanical properties
3. Chemical properties
4. Thermal properties
5. Optical properties

Mechanical Properties
A mechanical property is the behavior of the material when it’s linked to the application of
force. The mechanical properties of a material describe how it will react to physical forces.

STRESS
When a force acts on the body, tending to produce deformation, a resistance is developed
within the body to this external force. The internal resistance of the body to the external
force is called stress. Stress is equal and opposite in direction to the force (external) applied.
This external force is also known as load. Since both applied force and internal resistance
(stress) are distributed over a given area of the body, the stress in a structure is designated
as a force per unit area.
Force F
Stress = =
Area A
 Structure and Properties of Dental Materials  Chapter 2  15
The internal resistance to force (stress) is impractical to measure. The convenient way is to
measure the external force applied to the cross-sectional area.
Area over which the force acts is an important factor especially in dental restorations in which
areas over which the forces applied often are extremely small. Stress at a constant force is
inversely proportional to the area—the smaller the area, the larger the stress and vice versa.

Types of Stresses
 Tensile stress
 Compressive stress
 Shear stress

Tensile stress
Results in a body when it is subjected to two sets of forces that are directed away from each
other in the same straight line. The load tends to stretch or elongate a body.

Compressive stress
Results when the body is subjected to two sets of forces in the same straight line but directed
towards each other. The load tends to or shortens a body.

Shear stress
Shear stress is a result of two forces directed parallel to each other. A stress that tends to resist a
twisting motion, or a sliding of one portion of a body over another is a shear or shearing stress.

Strain
If the stress (internal resistance) produced is not sufficient to withstand the external force
(load) the body undergoes a change in shape (deformation). Each type of stress is capable of
producing a corresponding deformation in the body. The defor­mation resulting from a tension,
or pulling force, produces an elongation of a body, whereas a compression, or pushing force,
causes com­pression or shortening of the body.
Deformation or change in length E
Strain = =
Original length L

Strain is expressed as change in length per unit length of the body when a stress is applied.
It is a dimensionless quantity and may be elastic or plastic or a combination of the two.

COMPLEX STRESSES
It is difficult to induce just a single type of stress in a body. Whenever force is applied over
a body, complex or multiple stres­ses are produced. These may be a combination of tensile,
shear or compressive stresses (Fig. 2.6). These multiple stresses are called com­plex stresses.
For example, when a wire is stretched, the predomi­nant stress is tensile, but shearing and
compressive stresses will also be present because the wire is getting thinner (compressed in
cross-section) as it elongates.

Figure 2.6 Complex stresses produced by a three-point

loading of a beam.
16  Part 1  Structure and Properties of Dental Materials
POISSON’S RATIO
If we take a cylinder and subject it to a tensile stress or compres­sive stress, there is simultaneous
axial and lateral strain. Within the elastic range, the ratio of the lateral to the axial strain is
called Poisson’s ratio.

PROPORTIONAL LIMIT
A tensile load is applied to a wire in small increments until it breaks. If each stress is plotted
on a vertical coordinate and the corresponding strain (change in length) is plotted on the
horizontal coordinate, a curve is obtained. This is known as stress-strain curve (Fig. 2.7). It is
useful to study some of the mechanical properties. The stress-strain curve is a straight line
up to point ‘P’ after which it curves.
The point ‘P’ is the proportional limit, i.e., up to point ‘P’ the stress is proportional to strain
(Hooke’s Law). Beyond ‘P’ the strain is no longer elastic and so stress is no longer proportional
to strain. Thus proportional stress can be defined as the greatest stress that may be produced
in a material such that the stress is directly proportional to strain.

ELASTIC LIMIT
Below the proportional limit (point ‘P’), a material is elastic in nature, that is, if the load is
removed, the material will return to its original shape. Thus elastic limit may be defined as
the maximum stress that a material will withstand without permanent defor­mation (change
in shape). For all practical purposes, the elastic limit and the proportional limit represent the
same stress. However the fundamental concept is different, one describes the elastic behavior
of the material whereas the other deals with proportionality of strain to stress in the structure.

YIELD STRENGTH
Very few materials follow Hooke’s law perfectly and some perma­nent change may be seen
in the tested material. A small amount of permanent strain is tolerable. The limit of tolerable
permanent strain is the yield strength. Thus yield strength is defined as the stress at which a
material exhibits a specified limiting deviation from proportionality of stress to strain.

Determination of yield strength

How much of permanent deformation can be tolerated? This varies from material to material
and is determined by selecting an offset. An offset is an arbitrary value put for a material. It
repre­sents the percent of total permanent deformation that is accept­able for the material. In

Figure 2.7  Stress-strain curve. P-proportional limit,

X-yield strength, S-offset.
 Structure and Properties of Dental Materials  Chapter 2  17
dentistry 0.1% (1% offset) and 0.2% (2% offset) are most commonly used. The yield strength
is determined by selecting the desired offset and drawing a line parallel to the linear region
of the stress-strain curve (Fig. 2.7). The point on the stress-strain curve where the offset meets
is the yield strength (point X).

MODULUS OF ELASTICITY
It is also referred to as ‘elastic modulus’ or ‘Young’s modulus’. It represents the relative stiffness
or rigidity of the material within the elastic range.
Young’s modulus is the ratio of stress to strain. Since stress is proportional to strain (up to the
proportional limit), the stress to strain ratio would be constant.
Modulus of elasticity
Stress F/A FL
or E= = =
Young’s modulus Strain E/ L EA

It, therefore, follows that the less the strain for a given stress, the greater will be the stiffness,
e.g. if a wire is difficult to bend, considerable stress must be placed before a notable strain or
deformation results. Such a material would possess a compara­tively high modulus of elasticity.

Application
The metal frame of a metal-ceramic bridge should have a high stiffness. If the metal flexes,
the porcelain veneer on it might crack or separate.

FLEXIBILITY
Generally in dental practice, the material used as a restoration should withstand high stresses
and show minimum deformation. However, there are instances where a large strain is needed
with a moderate or slight stress. For example, in an orthodontic appliance, a spring is often
bent at a large distance with a small stress. In such a case the material is said to be flexible.
The ‘maximal flexibility’ is defined as the strain that occurs when the material is stressed to its
proportional limit. The relation between the maximum flexibility, the proportional limit and
the modulus of elasticity may be expressed as
Proportional limit (P)
Maximum flexibility (EM) =
Modulus of elasticity (E)

Application
It is useful to know the flexibility of elastic impression materials to determine how easily they
may be withdrawn over undercuts in the mouth.

RESILIENCE
Popularly, the term resilience is associated with ‘springiness’. Resilience can be defined as the
amount of energy absorbed by a structure when it is stressed not to exceed its proportional
limit. For example, when an acrobat falls on a trapeze net the energy of his fall is absorbed
by the resilience of the net, and when this energy is released, the acrobat is again thrown
into the air.
The resilience of a material is measured in terms of its modulus of resilience, which is the amount
of energy stored in a body, when a unit volume of a material is stressed to its propor­tional
limit. It is expressed mathematically as
P2 (Proportional limit)
R (Modulus of Resilience) =
2E (Modulus of elasticity)
18  Part 1  Structure and Properties of Dental Materials
Resilience is also measured by the area under the
straight line portion of the stress-strain curve (Fig.
2.8).

IMPACT
It is the reaction of a stationary object to a collision
with a moving object. Depending upon the resilience
of the object, energy is stored in the body without
causing deformation or with deformation.
The ability of a body to resist impact without Figure 2.8  Area of resilience in a stress-
permanent defor­m ation is represented by the strain curve.
formula—KVR
where, K = Constant of proportionality
V = Volume
R = Modulus of resilience
But we know R = P2/2E
KVP2
Therefore, impact resistance =
2E
From the above formula, we can conclude
Impact resistance will be decreased with an increase in the modulus of elasticity, which means
that stiffer materials will have less impact resistance. Resilient materials will have better impact
resistance (however, a high stiffness is also necessary to provide rigidity to a material under
static loads, e.g. a cement base should be able to support an amalgam restoration). Increase
in volume leads to an increase in impact resistance.

IMPACT STRENGTH
It is the energy required to fracture a material under an impact force. A Charpy type impact
tester is used (Figs. 2.9A and B). It has a heavy pendu­lum which swings down to fracture the
specimen. Another instru­ment called Izod impact tester can also be used.

Figures 2.9A and B (A) Charpy’s

tester. (B) Diagrammatic representation
of Charpy’s tester.

A B
 Structure and Properties of Dental Materials  Chapter 2  19
Application
Dentures should have a high impact strength to prevent it from breaking if accidentally
dropped by the patient.

PERMANENT DEFORMATION
Once the elastic limit of a material is crossed by a specific amount of stress, the further increase
in strain is called permanent defor­mation, i.e., the resulting change in dimension is permanent.

Application
An elastic impression material deforms as it is removed from the mouth. However due to its
elastic nature, it recovers its shape and little permanent deformation occurs. Some materials
are more elastic than others. Thus permanent deformation is higher in hydrocolloids than in
elastomers.

STRENGTH
Strength of a material is its resistance to fracture. It is measured by measuring the maximal
stress required to fracture a structure.
The three types of strength are
 Tensile strength
 Compressive strength
 Shear strength

Tensile Strength
Tensile strength is determined by subjecting a rod, wire or dumbbell shaped specimen to a
tensile loading (a unilateral tension test). Tensile strength is defined as the maximal stress the
structure will withstand before rupture.

Tensile strength of brittle materials

Brittle materials are difficult to test using the
unilateral tension test. Instead, an indirect tensile
test called ‘diametral compression test’ (or Brazilian
test) is used (Fig. 2.10). In this method, a compressive
load is placed on the diameter of a short cylindrical
specimen. The tensile stress is directly propor­tional
to the load applied as shown in the formula.
2P (load)
Tensile-stress = =
π × D × T π(diameter × thickness)

Compressive Strength
Compressive strength or ‘crushing strength’ is
determined by subjecting a cylindrical specimen to
a compressive load. The strength value is obtained
from the cross-sectional area and force applied.
Though the load is compressive in nature, the
Figure 2.10  Diametral compression test.
failure is due to complex stresses.
20  Part 1  Structure and Properties of Dental Materials
Shear Strength
Shear strength is the maximum stress that a material can withstand before failure in a shear
mode of loading. It is tested using the punch or pushout method. The formula is as follows.
Where, F is the force
Shear Strength = F D is punch diameter
pDH H is the thickness of the specimen

Application
Used to study the interface between two materials, e.g. porcelain fused to metal.

Transverse or Flexural Strength

Transverse strength or modulus of rupture, or bend strength, or fracture strength is obtained
when a load is applied in the middle of a beam supported at each end.
Three types of flexural tests are used
1. Three-point flexural test
2. Four-point flexural test
3. Biaxial flexural test

Three-point flexural test

This test is also called a three-point bending test (3PB) (Figs. 2.11A to C).
The flexure strength may be represented by the formula below.
where, P = fracture load in Newtons
3PL
Flexural Strength af = L = distance between supports
2wt 2 w = width of the speciment
t = thickness of the specimen

B C
Figures 2.11A to C  Flexural testing. (A) Representation of 3-point flexure testing. (B) 3-point
flexure tester. (C) 4-point flexure tester.
 Structure and Properties of Dental Materials  Chapter 2  21

Figure 2.12  Biaxial flexural test.

Four-point flexural test

The addition of a 4th bearing brings a much larger portion of the beam to the maximum
stress, as opposed to only the material right under the central bearing. This difference is of
prime importance when studying brittle materials, where the number and severity of flaws
exposed to the maximum stress is directly related to the flexural strength and crack initiation.
Formula for the four-point flexural test is shown below.
3PL
Flexural Strength af =
4wt 2

Biaxial flexural test

This test is used to avoid the problem of edge fractures which can occur with the other
flexural tests. Disc-shaped specimens are used of 12 mm diameter and 1.2 mm thickness
(Fig. 2.12). The disc is supported by 3 balls (3.2 mm diameter). The load is applied by a round
ended piston.

Application
Used to test materials like porcelain.

Weibull statistics
Weibull analysis
Waloddi Weibull invented the Weibull distribution in 1937 and delivered his hallmark paper
on this subject in 1951. It is also known as ‘life data analysis’. The primary advantage of Weibull
analysis is the ability to provide reasonably accurate failure analysis and failure forecasts. Thus
it is used to estimate important life characteristics of a product such as reliability or probability
of failure at a specific time, the mean life for the product and failure rate.
Although manufacturers provide data on strength values. This typically represents the mean
value of a specific test. This may not correlate with its strength and survival probability under
clinical situations because in the mouth the restorations experience cyclic loading conditions.
It would be more useful to know the 95% stress level. This is the stress level below which
95% of the specimens would survive the stress test.

Dental application  Many restorative materials in dentistry are brittle materials like resins and
ceramics. These materials do not exhibit a normal or symmetric distribution of strength values.
22  Part 1  Structure and Properties of Dental Materials
The failure probability of brittle materials like resins and ceramics is best described using Weibull
analysis which is based on the concept of the weakest link.

Weibull modulus
The Weibull modulus represents the distribution of flaws in a brittle material or the distribution
of strength determined from the fracture probability versus failure test.

Significance
1. A low Weibull modulus indicates a material which is inconsistent in strength, has a wide
variation of fracture force and, therefore, has low reliability as a restorative material, e.g.
Weibull modulus for ceramics range from 5-15.
2. A higher Weibull modulus indicates a material with greater reliability as a structural
material, e.g. Metals which are ductile have Weibull modulus above 20.

Stress Concentration
A stress concentration (often called stress raisers) is a location in an object where stress is
concentrated.

Causes of stress concentration

Knowledge of the causes and effects of stress concentration is important in dental restorations
to prevent early failure.

Stress concentrations occur due to

1. Structural defects
2. Improper design
Structural defects  An object is strongest when force is evenly distributed over its area, so
a reduction in area, e.g. caused by a crack, results in a localized increase in stress. A material
can fail, via a propagating crack, when a concentrated stress exceeds the material’s theoretical
cohesive strength. The real fracture strength of a material is always lower than the theoretical
value because most materials contain small cracks or contaminants (especially foreign
particles) that concentrate stress.
Design defects  A structure should be designed in such a way that stress is evenly distributed.
An example of a stress concentration design is a narrow post with supporting a large core.
The weakest point of this structure is at the junction of the post and core. When occlusal
forces are applied stress concentration at this point can lead to a fracture. Slight alteration of
design can reduce stress concentration. In this case increasing the diameter of the post and
increasing the bulk of the metal at the junction of the post to the core so that the transition
is gradual rather than abrupt.

FATIGUE
A structure subjected to repeated or cyclic stresses below its proportional limit can produce
abrupt failure of the structure. This type of failure is called fatigue. Fatigue behavior is
determined by subjecting a material to a cyclic stress of a known value and determining the
number of cycles that are required to produce failure. The stresses used in fatigue testing are
usually very low. However, the repeated application causes failure.

Application
Restorations in the mouth are often subjected to cyclic forces of mastication. In order to last,
these restorations should be able to resist fatigue.
 Structure and Properties of Dental Materials  Chapter 2  23
Static Fatigue
It is a phenomenon exhibited by some ceramic materials. These materials support a high static
load for a long period of time and then fail abruptly. This type of failure occurs only when the
materials are stored in a wet environment and this property is related to the effect of water
on the highly stressed surface of the material.

TOUGHNESS
It is defined as the energy required to fracture a material.
It is a property of the material which describes how
difficult the material would be to break. Toughness is
also measured as the total area under the stress-strain
curve (Fig. 2.13).
Figure 2.13  Area of toughness in
BRITTLENESS the stress-strain curve.

A brittle material fractures at or near its proportional limit. Brittleness is the opposite of
toughness, e.g. glass is brittle at room temperature. It will not bend appre­ciably without
breaking. It should not be wrongly understood that a brittle material lacks strength.
From the above example of glass, we see that its shear strength is low, but its tensile
strength is very high. If glass is drawn into a fiber, its tensile strength may be as high
as 2800 MPa.

Application
Many dental materials are brittle, e.g. porcelain, cements, dental stone, etc.

DUCTILITY
It is the ability of a material to withstand permanent deformation under a tensile load without
rupture. A metal that can be drawn readily into a wire is said to be ductile. Ductility is dependent
on tensile strength. Ductility decreases as the temperature is raised.

Ductility may be measured by three methods

 By measuring the percentage elongation after fracture.
 By measuring reduction in cross-sectional area of fractured ends in comparison to the
original area of the wire or rod and the method is called reduction in area method.
 By using the cold bend test.

MALLEABILITY
It is the ability of the material to withstand rupture under compres­sion, as in hammering or
rolling into a sheet. It is not dependent on strength as is ductility. Malleability increases with
rise in tempe­rature.
Toughness of a material is dependent upon the ductility (or malleability) of the material than
upon the flexibility or elastic modulus.

Application of malleability and ductility

Gold is the most ductile and malleable metal. This property enables manufacturers to beat
it into thin foils. Silver is second. Among other metals, platinum ranks third in ductility and
copper ranks third in malleability.
24  Part 1  Structure and Properties of Dental Materials
HARDNESS
Hardness is difficult to define specifically. There are numerous factors which influence
the hardness of a material such as strength, proportional limit, ductility, malleability, etc.
In mineralogy the hardness is described as the ability of a material to resist scratching. In
metallurgy and in most other fields, the resistance to indentation is taken as the measure of
hardness. There are many surface hardness tests (Figs. 2.14A and B).

Brinell
The Brinell hardness scale was developed by a Swedish engineer named Johan August Brinell
in 1900. The Brinell test utilizes a 10 mm diameter steel ball as an indenter, applying a uniform
3000 kgf (29 kN) force. A smaller amount of force is used on softer materials and a tungsten
carbide ball is used for harder materials. The diameter of the indentation left in the test
material is measured with a low powered microscope. The load is divided by the area of the
surface of the indentation and the quotient is referred to as Brinell Hardness Number (BHN).

Application
Used for measuring hardness of metals and metallic materials.

Rockwell Hardness Number (RHN)

Like the BH test, a steel ball or a conical diamond point is used. However, instead of measuring
the diameter of the impres­sion, the depth is measured directly by a dial gauge on the instrument.

Application
The Rockwell test has a wider application for materials, since Brinell test is unsuitable for brittle
materials as well as plastic materials.

Vickers Hardness Test (VHN)

This is also similar to the Brinell test, however, instead of a steel ball, a diamond in the shape
of a square pyramid is used (Fig. 2.14A). Although the impression is square instead of round.
The load is divided by the area of indentation. The length of the diagonals of the indentation
(sides of the diamond) are measured and averaged.

Application
Vickers test is used in the ADA for dental casting golds. This test is suitable for brittle materials
and so is used for measuring hardness of tooth structure.

A B
Figrues 2.14A and B  (A) Knoop and Vickers hardness tester with microscope. (B) Various hardness tests.
 Structure and Properties of Dental Materials  Chapter 2  25
Knoop Hardness Test (KHN)
A diamond indenting tool (Fig. 2.14B) is used of a different shape from that of Vickers. The
indentation is more narrower and elongated. Knoop hardness value is independent of the
ductility of the material and values for both exceedingly hard and soft materials can be
obtained from this test.
The Knoop and Vickers tests are classified as microhardness tests. The Brinell and Rockwell
tests are classified as macrohardness tests.

The Shore and the Barcol

These are less sophisticated tests. They are compact portable units (Figs. 2.15A and B). A metal
indenter that is spring loaded is used. The hardness number is based on depth of penetration
and is read directly from a gauge.

Applications
Used for measuring the hardness of rubber and plastics.

ABRASION RESISTANCE
Like hardness, abrasion is influenced by a number of factors. Hardness has often been used
to indicate the ability of a material to resist abrasion.

Applications
It is useful for comparing materials in the same class, e.g. one brand of cement is compared
to another and their abrasion resistance is quoted in comparison to one another. However, it
may not be useful for comparing materials of different classes like metals and plastics.
The only reliable test for abrasion is a test procedure which simulates the condi­tions which
the material will eventually be subjected to, e.g. toothbrush abrasion tests.

RHEOLOGY
Rheology is the study of flow of matter. In dentistry, study of rheology is necessary because
many dental materials are liquids at some stage of their use, e.g. molten alloy and freshly
mixed impression materials and cements. Other materials appear to be solids but flow over
a period of time.

A B
Figures 2.15A and B  (A) Shore tester. (B) Barcol tester.
26  Part 1  Structure and Properties of Dental Materials
Terms and Properties in Rheology

Viscosity
Viscosity is the resistance offered by a liquid when placed in motion, e.g. honey is more viscous
than water. It is measured in poise or centipoise (1 cp = 100 p).

Creep
Time dependent plastic deformation or change of shape that occurs when a metal is subjected
to a constant load near its melting point is known as creep. This may be static or dynamic in
nature.
Static creep is a time dependent deformation produced in a completely set solid subjected
to a constant stress.
Dynamic creep produced when the applied stress is fluctuating, such as in fatigue type test.

Importance
Dental amalgam has components with melting points that are slightly above room temperature
and the creep produced can be very destructive to the restoration, e.g. glass tube fractures
under a sudden blow but bends gradually if leaned against a wall.

Flow
It is somewhat similar to creep. In dentistry, the term flow is used instead of creep to describe
rheology of amorphous substances, e.g. waxes. Although creep or flow may be measured
under any type of stress, compression is usually employed for testing of dental materials.

THIXOTROPIC
These materials exhibit a different viscosity after it is deformed, e.g. latex paints for ceilings
show lower viscosity after it is stirred vigorously. Zinc oxide eugenol cements show reduced
viscosity after vigorous mixing. Dental prophy paste is another example.

RELAXATION
Every element in nature makes an attempt to remain in a stable form. If an element is changed
from its equilibrium or stable form by either physical or chemical means, it tries to come back
to its original form.
When substances are deformed, internal stresses get trapped because of the displacement
of the atoms. The condition is unstable and the atoms try to return to their original positions.
This results in a change in shape or contour in the solid as atoms or molecules rearrange
themselves. This change in shape due to release of stresses is known as relaxation. The material
is said to warp or distort.
Examples, Waxes and other thermoplastic materials like com­pound undergo relaxation after
they are manipulated.

SHEAR STRESS AND SHEAR STRAIN RATE

A liquid is placed between two plates and the upper plate is moved to the right. The stress
required to move the plate is called shear stress (= F/A or force applied/ area of plate). The
change produced is called shear strain rate (= V/d or velocity of plate/distance covered).
 Structure and Properties of Dental Materials  Chapter 2  27
Newtonian
Shear stress and shear strain rate can be plotted.
An ideal fluid shows a shear strain rate that is
proportional to shear stress. This behavior is called
Newtonian (Fig. 2.16).

Pseudoplastic
If a material viscosity decreases with increase in shear
rate, it is said to exhibit pseudoplastic behavior, e.g.
elastomeric impression materials when loaded into
a tray shows a higher viscosity, whereas the same
material when extruded under pressure through a
syringe tip shows more fluidity (Fig. 2.16). Figure 2.16 Shear diagrams of pseudo­
plastic, Newtonian and dilatant liquids.

Dilatant
These are liquids that show higher viscosity as shear rate increases, e.g. fluid denture base
resins (Fig. 2.16).

Physical Properties
Physical properties can be observed or measured without changing the composition of
matter. Physical properties are used to observe and describe matter. Physical properties of
importance in dentistry include appearance, texture, color, optical properties, odor, glass
transition, temperature, melting point, boiling point, density, solubility, polarity, etc.

FORMS OF MATTER
Change of State
Matter exists in the forms—solid, liquid and gas (Fig. 2.17). The difference in form is mainly due
to difference in energy. Matter is made up of atoms and for these atoms to be held together
there must be a force, e.g. when 1 gram of water is to be changed into gaseous state at
100° C, 540 calories of heat are needed (known as heat of vaporization). Thus the gaseous
state has more energy than the liquid state. Although the molecules in a gas have a certain
amount of mutual attraction, they can diffuse readily and need to be confined in order to keep
the gas intact. Energy of the liquid is decreased by reducing the temperature sufficiently, a
second transformation in state occurs and energy is released in the form of heat (latent heat
of fusion). This decrease in energy state changes the liquid to a solid or freezes it.
The reverse is true when solid is changed to liquid, i.e., heat is required. The temperature at
which it occurs is called fusion temperature.

Figure 2.17  The 4 states of matter.

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28  Part 1  Structure and Properties of Dental Materials
Melting point
The melting point (or liquefaction point) of a solid is the temperature at which it changes
state from solid to liquid at atmospheric pressure. At the melting point the solid and liquid
phase exist in equilibrium.

Boiling point
The boiling point of a substance is the temperature at which the vapor pressure of the liquid
equals the pressure surrounding the liquid and the liquid changes into a vapor. The boiling
point of a liquid varies depending upon the surrounding environmental pressure.

Density
The density, or more precisely, the volumetric mass density, of a substance is its mass per
unit volume. The symbol most often used for density is ρ (the lower case Greek letter rho).
Mathematically, density is defined as mass divided by volume–
m
ρ=
V
where ρ is the density, m is the mass, and V is the volume.
In some cases (for instance, in the United States oil and gas industry), density is loosely defined
as its weight per unit volume, although this is scientifically inaccurate—this quantity is more
specifically called specific weight.
For a pure substance, the density has the same numerical value as its mass concentration.
Different materials usually have different densities. Osmium and iridium are the densest
known elements at standard conditions for temperature and pressure.
To simplify comparisons of density across different systems of units, it is sometimes replaced
by the dimensionless quantity “relative density” or “specific gravity”, i.e. the ratio of the density
of the material to that of a standard material, usually water. Thus a relative density less than
one means that the substance floats in water.
The density of a material varies with temperature and pressure. This variation is typically
small for solids and liquids but much greater for gases. Increasing the pressure on an
object decreases the volume of the object and thus increases its density. Increasing the
temperature of a substance (with a few exceptions) decreases its density by increasing
its volume.

Glass Transition Temperature (Tg)

The glass transition temperature (Tg) is the temperature at which an amorphous solid becomes
soft upon heating or brittle upon cooling. The Tg is one of the most important properties of
any epoxy and is the temperature region where the polymer transitions from a hard, glassy
material to a soft, rubbery material. The glass transition temperature is always lower than the
melting temperature (Tm) of the crystalline state of the material, if one exists.
Glass transition temperature is the most important property of a polymer. The value of the glass
transition temperature is directly related to the mechanical properties (strength, hardness,
brittleness, elongation, etc.).
The glass transition temperature is more important in plastics applications than is the melting
point, because it tells a lot about how the polymer behaves under ambient conditions. If a
polymer’s glass transition temperature is well above ambient room temperature, the material
behaves like a brittle glassy polymer (it is stiff with low impact resistance). Conversely, if the
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 Structure and Properties of Dental Materials  Chapter 2  29
Tg is well below room temperature, the material is what is commonly termed a rubber or
elastomer (soft and easily stretched). Those materials whose Tg is reasonably close to the
ambient temperature exhibit plastic material behavior (strong and tough with good impact
resistance). There are chemical compounds known as plasticizers that are used to decrease
the glass transition temperature.

Solubility
Solubility is the property of a solid, liquid, or gaseous chemical substance called solute to dissolve
in a solid, liquid, or gaseous solvent to form a homogeneous solution of the solute in the solvent.
Restorations placed in the oral cavity require to be insoluble in oral fluids. The tendency of
cements to dissolve in the oral fluids can lead to marginal ditching, microleakage, recurrent
caries, and ultimately failure of the restoration.

Thermal properties
Thermal properties are the response of a material to the application of heat.

Thermal conductivity
Thermal conductivity is defined as the property of a material that indicates its ability to
conduct heat through its body under a steady state condition. It is measured in watts per
meter per degree Kelvin (W/(mK)). In Imperial
units, thermal conductivity is measured in BTU/
(hr.ft.°F)
It is defined as the quantity of heat in calories
per second passing through a material 1 cm
thick with a cross-section of 1 cm 2 having
a temperature difference of 1 K (1°C) and is
measured under a steady-state condition in
which the temperature gradient does not
change.
Thermal conductivity depends on many
properties of a material, its structure and
temperature. The transfer of heat within a
material takes place by conduction; in this
process the materials do not move as a whole
but the energy flows through the body of
the material by the transfer of the molecular
kinetic energy. Various materials exhibit varying
degrees of thermal conductivity (Fig. 2.18).
The divided bar method (steady-state method)
is the most common way of measuring thermal
conductivity. The sample to be measured
is placed between two samples of known
Figure 2.18  Thermal conductivity of various materials.
conductivity (usually brass plates). The sample
is placed at the top of the vertical setup and the known conductivity brass bars are kept at
the bottom. To stop any convection within the sample, heat is supplied at the top and moved
downwards. After approximately 10 minutes, the measurements are taken after the whole
sample becomes equallyhttp://dentalebooks.com
hot.
30  Part 1  Structure and Properties of Dental Materials
Thermal diffusivity
Thermal diffusivity measures the ability of a material to conduct thermal energy relative to
its ability to store thermal energy. Thermal diffusivity is the thermal conductivity divided by
density and specific heat capacity at constant pressure. It has the SI unit of m²/s. Thermal
diffusivity is usually denoted by α but a, κ, K, and D are also used. The formula is
κ
α=
ρ × Cρ
κ is thermal conductivity (W/(mK))
ρ is density (kg/m³)
Cρ is specific heat capacity (J/(kgK))

THERMAL EXPANSION
Thermal energy is due to the kinetic energy (internal energy) of the atoms or molecules at
a given temperature. At temperatures above absolute zero, atoms are in a constant state of
vibration. The average amplitude of vibration depends upon the tempera­ture; the higher
the temperature, the greater will be the kinetic energy and amplitude of the atomic (or
molecular) vibration increases. As the amplitude and internal energy of the atoms increase,
the interatomic spacing increases as well. The gross effect is an expansion known as thermal
expansion. If the temperature continues to increase, the interatomic spac­ing will increase
and eventually a change of state will occur (e.g. solid to liquid).

Coefficient of Thermal Expansion (CTE)

When a substance is heated, the kinetic energy of its molecules increases. This usually results
in an expansion called thermal expansion.
The coefficient of thermal expansion describes how the size of an object changes with a change
in temperature. Specifically, it measures the fractional change in size per degree change in
temperature at a constant pressure.

Measurement of CTE
Several types of coefficients have been developed—volumetric, area, and linear. Which is
used depends on the particular application. For solids, one might only be concerned with the
change along a length, or area. The volumetric thermal expansion coefficient is commonly
used for fluids and gases. It is normally quoted in parts per million per degree Celsius rise in
temperature (ppm/K).
∆L
α=
L × ∆T
α (alpha) is CTE
L is original length of material
ΔL (delta L) is change in length
ΔT (delta T) is change in temperature

Negative thermal expansion

A number of materials contract on heating within certain temperature ranges; this is usually
called negative thermal expansion. For example, the coefficient of thermal expansion of water
drops to zero as it is cooled to 3.983°C and then becomes negative below this temperature;
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 Structure and Properties of Dental Materials  Chapter 2  31
this means that water has a maximum density at this temperature, and this leads to bodies of
water maintaining this temperature at their lower depths during extended periods of sub-zero
weather. Another example is pure silicon. It has a negative coefficient of thermal expansion
for temperatures between about 18 and 120 Kelvin.

Significance of CTE
1. The mismatch of thermal expansion and contraction between restorative materials and
tooth may cause stresses at their interface, which may lead to microleakage.
2. Metal ceramics restorations require a close match between the CTE of the alloy and
porcelain in order to reduce stresses in the porcelain. These stresses can cause immediate
or delayed cracking in the ceramic.
3. An inlay wax pattern created in the mouth may contract when transferred to the colder room.
4. Denture teeth set in wax may shift slightly when room temperature changes.

Optical properties and color

Light is a form of electromagnetic radiant energy within a certain portion of the electromagnetic
spectrum that can be detected by the human eye. The eye is sensitive to wavelengths
from approximately 400 nm (violet) to 700 nm (dark red). The combined intensities of the
wavelengths present in a beam of light determine the property called color.
In order for an object to be visible, either it must emit light or it must reflect or transmit light
falling upon it from an external source. Objects of dental interest generally transmit light. The
incident light is usually polychromatic (mixed light of various wave­lengths). The reaction of
an object to the incident light is to selec­tively absorb and/or scatter certain wavelengths. The
spectral distribution of the transmitted or reflected light will resemble that of the incident
light although certain wavelengths will be reduced in magnitude.
Cone-shaped cells in the retina are responsible for color vision in humans. The eye is most
sensitive to light in the green-yellow region and least sensitive at either extremes (i.e., red or blue).

Dimensions of Color
The three dimensions of color are — hue, value and chroma.

Hue
Refers to the basic color of an object, e.g. whether it is red, green or blue.

Value
Colors can be separated into ‘light’ and ‘dark’ shades. Value represents the amount of lightness
or darkness in the color. This lightness which can be measured independently of the hue is
called value.

Chroma
A particular color may be dull or more ‘vivid’, this difference in color intensity or strength is
called chroma. Chroma represents the degree of saturation of a particular hue (color). In other
words, the higher the chroma, the more intense is the color. Chroma cannot exist by itself
and is always associated with hue and value. The three dimensions of color is represented in
Figs. 2.19 and 2.20.
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32  Part 1  Structure and Properties of Dental Materials

Figure 2.19  Illustration representing the three Figure 2.20  Munsell color solid is also used
dimensions of color. to demonstrate the three dimensions of color.

Measurement of Color
One of the most commonly used method to define and measure color quantitatively is the
Munsell System. It is a coordinate sys­tem which can be viewed as a cylinder. The lines are
arranged sequentially around the perimeter of the cylinder, while the chroma increases along
a radius from the axis. The value co­ordinate varies along the length of the cylinder from black
at the bottom to neutral grey at the center to white at the top.

METAMERISM
The appearance of an object depends on the type of the light by which the object is viewed.
Daylight, incandescent lamps and fluorescent lamps are all common sources of light in the
dental operatory. Objects that appear to be color matched under one type of light may appear
very different under another light source. This phenomenon is called metamerism.

Tooth esthetics
Reproducing a tooth—both art and science. The esthetics of a dental restoration is determined by
1. Shape
2. Color
3. Texture
The shade and color of a tooth is a complex interplay of many factors. The color of the tooth
is determined by the shade, thickness and composition of the enamel and dentin, the pulp
chamber, extrinsic stains, color reflections from the gum and adjacent teeth and the incident
light itself. Light is a form of energy and must obey the basic law of conservation of energy
which states that energy cannot be created or destroyed but only changed from one form
into another or transferred from one object to another.

Light = Light + Light + Light + Light + Light + Light changed

Incident Reflected Scattered Transmitted Absorbed Fluoresced to heat

Transparence, Translucence, and opacity

A transparent object allows all the light to pass through an object, whereas a translucent
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object allows only partial passage of light. For example, plain glass is transparent, whereas
 Structure and Properties of Dental Materials  Chapter 2  33
frosted glass is translucent. An object which does not allow any passage of light is said to
be opaque.

Relevance
Teeth and oral tissue are translucent and allow passage of some of the incident light. In
some individuals, the enamel may be translucent or in rare circumstances transparent. This
may be particularly evident in the incisal edges of upper or lower incisors. Metal-ceramic
restorations are opaque unlike natural teeth which are translucent (Fig. 2.21). One of the
reasons for improved esthetics with all-ceramic restorations is the improved translucency.

FLUORESCENCE
Natural tooth structure also absorbs light of wavelengths which are too short to be visible to
the human eye. These wavelengths between 300 to 400 nm are referred as near ultraviolet.
Natural sunlight, photoflash lamps, certain types of vapor lamps and the ultraviolet lights used
in decorative lighting are all sources con­taining substantial amounts of near U-V radiation
and invisible U-V light (also called black light).
This energy that the tooth absorbs is converted into light with larger wavelengths, in which
case the tooth actually becomes a light source. The phenomenon is called fluorescence
(Fig. 2.22). The emitted light is primarily in 400-450 nm range, having blue white color.
Improved fluorescence adds esthetic value to artificial restorations.

Relevance
In UV light a natural tooth emits a weak whitish-blue fluorescence. This should be taken into
account when selecting restoratives. If restorative materials do not offer this property of
fluorescence, they will look dark in UV light (Fig. 2.23), and the restored tooth will stand out
against the other teeth in the mouth. Some patients want their restorations to match natural
tooth under fluorescent light conditions, e.g. in stage shows and discotheques. Some porcelain
restorations are able to match the natural teeth under fluorescent lighting.

Figure 2.21  Poor translucency exhibited by

the metal-ceramic restoration on the right when
compared to the natural teeth (left).

Figure 2.22  Composite restoration (on right central incisor) Figure 2.23 Artificial crown on left central appears dark
showing greater fluorescence. http://dentalebooks.com
under UV light because of insufficient fluorescence.
34  Part 1  Structure and Properties of Dental Materials
CLINICAL CONSIDERATIONS
Esthetics play a very important role in modern
dental treatment. The ideal restorative material
should match the color of the tooth it restores. In
maxillofacial prosthetics the color of the gums,
external skin and the eyes have to be duplicated.
Clinically in the operatory or dental lab, color
selection is usually done by the use of shade
guides (Fig. 2.24). These are used in much the
same way as paint chips are used to select the
color for house paint. The process of selection Figure 2.24  The Vitapan 3D Master is used as
a guide for selecting tooth color.
is described in (Figs. 2.25A to C).
Digital shade guides are also available (Figs. 2.26A to C). The probe is simply placed against
the tooth and on the press of a button the reading is displayed on the screen. The device is
also useful to measure the progress of bleaching.

Radiological properties

Radiopacity and Radiolucency

Radiopacity may be defined as the quality or property of a material to obstruct the passage
of radiant energy, such as X-rays. Thus materials that inhibit the passage of electromagnetic

B C

Figures 2.25A to C  Selecting the color using the Vitapan system. The color is determined in 3 steps. Step 1 determines
the value. Step 2 determines the chroma (basic saturation). Step 3 determines the hue (basic color). The figure shows step
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1. The guide is held along the patient’s face at arm’s length.
 Structure and Properties of Dental Materials  Chapter 2  35

A B C
Figures 2.26A to C  (A) Digital shade guide - VITA Easyshade Advance 4. (B) The shade is selected by placing the probe
against the tooth. (C) The reading is displayed on the screen.

radiation are called radiopaque. On the other hand those that allow radiation to pass more
freely are referred to as radiolucent.

Significance in dentistry
Radiography plays a significant role in dentistry. It is very useful as a diagnostic tool.
Radiographs help to detect problems within the restorations, teeth, bone, etc. Manufacturers
add certain elements in many dental materials in order to make them radiopaque. Commonly
used elements are heavy metal glasses (strontium or barium glasses) and compounds (barium
sulphate) and metal oxides (zirconium dioxide and ytterbium oxide. Pure polymers like acrylic
resins and bis-GMA are radiolucent. Composites, ceramics and metals are radiopaque, with
metals showing the highest radiopacity.

Measurement of radiopacity
Human tissues like teeth, bone and soft tissue have varying levels of radiopacity. Within the
tooth, the enamel is more radiopaque that dentin. Radiopacity similar to hard tissues of the
body provide an optimal contrast for diagnosis. If the radiopacity of material is too low, it
will not be visible. Generally, a restorative material should have radiopacity slightly greater
than that of enamel in order to present a contrast. The thickness of the material also affects
its radiographic properties. Radiopacity increases with increase in thickness.
Aluminum is used as a standard to measure radiopacity. The radiopacity of a material is
expressed as equivalent thickness of aluminum (millimetres of aluminum). Typically an
aluminum step wedge (Fig. 2.27A) is used for comparative studies. Specimens of specified
thickness are radiographed together with the step wedge for comparison (Fig. 2.27B).

Ingredient Al equivalent (mm) approx.

Enamel 4–4.3
Dentin 2.2–2.5
Composites 1.5–6.2
ZOE endodontic sealer (Kerr) 8.9
Pro-Root MTA 2.5
Compoglass 4
Zinc phosphate cement (Hoffman) 6.5
Zinc polycarboxylate cement (Hoffman) 3.6
Cercon (core ceramic) 8.73
Cercon ceram S (veneering ceramic) 1.71
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36  Part 1  Structure and Properties of Dental Materials

A B
Figures 2.27A and B  (A) Aluminum step wedge. (B) Radiograph of step wedge with specimens.

Magnetic properties of matter

Magnetism is a class of physical phenomena that are mediated by magnetic fields. Electric
currents and the fundamental magnetic moments of elementary particles give rise to a
magnetic field. All matter exhibits magnetic properties when placed in an external magnetic
field.
Aristotle attributed the first of what could be called a scientific discussion on magnetism to
Thales of Miletus, who lived from about 625 BCE to about 545 BCE. Around the same time,
in ancient India, the Indian surgeon, Sushruta, was the first to make use of the magnet for
surgical purposes. The Chinese were believed to be using the compass for navigation prior to
the Europeans. Alexander Neckam, by 1187, was the first in Europe to describe the compass
and its use for navigation.

Classification
Depending on whether there is an attraction or repulsion by the pole of a magnet, matter is
classified as being either
1. Paramagnetic—attracted to a magnetic field
2. Diamagnetic—repulsed by a magnetic field

Terms
Magnetic field  A magnetic field is the magnetic effect of electric currents and magnetic
materials (Fig. 2.28). The magnetic field at any given point is specified by both a direction
and a magnitude (or strength).

Figure 2.28  Representation of magnetic field.

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 Structure and Properties of Dental Materials  Chapter 2  37
Magnetic moment  The magnetic moment (or magnetic dipole moment) of an object is a
measure of the object’s tendency to align with a magnetic field. It is a vector quantity. The
object will tend to align itself so that its magnetic moment vector is parallel to the magnetic
field lines. Some materials like iron (ferromagnets) have permanent magnetic moments. Most
materials do not have permanent moments.
Ferromagnetism  It is the basic mechanism by which certain materials can retain their
magnetization when the external field is removed. Examples of ferromagnetic substances
include iron, nickel, cobalt and some of the rare earth elements, such as gadolinium and
dysprosium.
Nonmagnetic substances  Substances that are negligibly affected by magnetic fields are
known as nonmagnetic substances. They include copper, aluminium, gases, and plastic. Pure
oxygen exhibits magnetic properties when cooled to a liquid state.
Magnetocrystalline anisotropy  Magnets are capable of producing high forces relative to
their size due to the property of magnetocrystalline anisotropy. Samarium-cobalt (SmCo5)
and neodymium-iron-boron magnets (Nd2Fe14B) magnets not only have the property of
magnetocrystalline anisotropy, but they also have high coercivity.
Coercivity  It is the ability of the magnet to resist demagnetization. Materials with high
magnetic anisotropy usually have high coercivity.

Types
1. Ceramic magnets are used in refrigerators and elementary-school science experiments,
contain iron oxide in a ceramic composite. Most ceramic magnets, sometimes known as
ferric magnets, aren’t particularly strong.
2. Alnico magnets are made from aluminium, nickel and cobalt. They’re stronger than ceramic
magnets, but not as strong as the ones that incorporate a class of elements known as
rare-earth metals.
3. Neodymium magnets contain iron, boron and the rare-earth element neodymium.
Compared to other available magnets, neodymium magnets are the strongest permanent
magnets available. Today they are used in computer hard drives, speakers, electric motors,
wind turbines, etc.
4. Samarium cobalt magnets combine cobalt with the rare-earth element samarium.
5. Others In the past few years, scientists have also discovered magnetic polymers, or plastic
magnets. Some of these are flexible and mouldable. However, some work only at extremely
low temperatures, and others pick up only very lightweight materials, like iron filings.

Uses
Magnetic resonance imaging
Magnetic resonance imaging (MRI), nuclear magnetic resonance imaging (NMRI), or magnetic
resonance tomography (MRT) is a medical imaging technique used in radiology to investigate
the anatomy and physiology of the body in both health and disease. MRI scanners use strong
magnetic fields and radiowaves to form images of the body. The technique is widely used in
hospitals for medical diagnosis.

In dentistry
Magnets have generated great interest within dentistry. They have been used for various
applications in orthodontics and prosthodontics. Earlier use of magnets was limited due to
the unavailability of smallhttp://dentalebooks.com
size magnets, but after the introduction of rare earth magnets and
38  Part 1  Structure and Properties of Dental Materials

Figure 2.29  Dental magnet. Figure 2.30  Dental magnet.

their availability in smaller sizes, their use has increased considerably. They can be placed
within prostheses without being obtrusive.
In orthodontics  Their main use in orthodontics has been for tooth movement
In prosthodontics  They are primarily used as retentive aids in maxillofacial prosthesis and
in tooth and implant supported (Figs. 2.29 and 2.30).

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 3
Chapter

Structure and Properties

of Metals and Alloys
Chapter Outline
• Uses in Dentistry • Grains • Eutectic Alloys
• History of Metals • Crystallization Forms –– Equilibrium-Phase Diagrams
• Metallurgy –– Dendritic Microstructure of Ag-Cu
• Periodic Table –– Equiaxed Polycrystalline –– Hypoeutectic and
• General Properties of Metals Microstructure Hypereutectic Alloys
• Valence Electron –– Single Crystal • Peritectic Alloys
• Metallic Bonding • Grain Refinement and Size • Solid State Reactions
• Alloys • Grain Boundaries –– Gold-Copper Phase Diagram
–– Classification of Alloys • Time-Temperature Graph –– Heat Treatment of Gold
• Phase • Equilibrium Phase Diagrams Alloys
• Solid Solutions –– Homogenization Heat • Classification of Alloys
• Solidification and Microstructure Treatment - Microstructure • Functions of Alloying Elements

All matter can be classified as either metals, nonmetals or metalloids.

A metal can be defined as a substance with high thermal and electrical conductivity, lustre,
and malleability, which readily loses electrons to form positive ions (cations). They yield basic
oxides and hydroxides. Roughly 80 percent of the periodic table are metals (Fig. 3.1).
Metalloids are borderline elements showing both metallic and nonmetallic properties.
Examples are carbon and silica.

Uses in dentistry
Metals and their alloys are used extensively in dentistry. They are used in restorations,
prostheses, etc. They are used in orthodontics in the form of wires and various appliances for
the movement of teeth. Various instruments and appliances used in clinics and laboratory
dentistry are fabricated from metals.

In dentistry, metals or their alloys are used in three capacities

1. Dental restorations
a. Direct intracoronal restorations, e.g. direct filling gold (DFG)
b. Indirect (cast) coronal and extracoronal restorations like inlays and crowns, e.g. alloys
of gold, platinum, chrome, cobalt, etc.
2. Prosthetic uses, e.g. implants, intra and extraoral prostheses like dentures and maxillofacial
prostheses using cast alloy frames.
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40  Part 1  Structure and Properties of Dental Materials

Figure 3.1  Periodic table of elements.

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 Structure and Properties of Metals and Alloys  Chapter 3  41

Box 3.1    History of metals

Metallurgy is one of the oldest applied sciences. Its history can be traced back to 6000 BCE. The earliest metals known
to man were Gold (6000 BCE), Copper (4200 BC), Silver (4000 BCE), Lead 3500 BCE, Tin (1750 BCE), Iron 1500 (BCE) and
mercury 750 BCE. Collectively these were called the seven metals of antiquity. Over time more and more metals were
discovered, it greatly revolutionized human evolution and culture. Zinc was known to the Chinese in 1400s. Platinum
was discovered in Mexico by the Spaniards. Aluminium was first produced by Christian Oersted in 1825.

Indium

Molybdenum  Molybdenum
Tungsten  Pure tungsten has some is used in base metal casting
alloys. The Metalloids
unique properties including the
These exhibit both metallic and
highest melting point (3695 K),
nonmetallic properties.
lowest vapor pressure, and greatest
tensile strength out of all the metals.
For this reason it is commonly used
for light bulb filaments. Tungsten
carbide burs are used in dentistry.

Sodium metal Silicon

Copper  Natural Copper ore has a

blue-green hue.

Carbon

Copper coins from India - 1944

Burial site at Varna, Bulgaria, circa

4600 BCE, containing some of the
oldest sophisticated examples of
ancient copper and gold metallurgy.
Calcium metal (Courtesy: I, Yelkrokoyade.) Gold ore
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42  Part 1  Structure and Properties of Dental Materials
3. Functional appliances and splints, e.g.
a. Orthodontic therapy, e.g. wires and appliances for tooth movement
b. Surgical uses, e.g. titanium plates
4. Auxiliary uses, e.g. clinical and laboratory instruments and materials

Metallurgy
Metallurgy is the study of the physical and chemical behavior of metallic elements, their
intermetallic compounds, and their mixtures, which are called alloys.

Periodic table
Dmitri Mendeleev was the first scientist to create a periodic table of the elements (1869)
similar to the one we use today. This table showed that when the elements were ordered by
increasing atomic weight, a pattern appeared where properties of the elements repeated
periodically. Thus the periodic table is a chart that groups the elements according to their
similar properties.

Features
The periodic table helps predict some properties of the elements compared to each other.
Atom size decreases as you move from left to right across the table and increases as you move
down a column. Energy required to remove an electron from an atom increases as you move
from left to right and decreases as you move down a column. The ability to form a chemical
bond increases as you move from left to right and decreases as you move down a column.
There are 118 elements in the periodic table. Roughly 80 percent (94) of these elements are
classified as metals.

Groups
Columns of elements help define element groups. Elements within a group share several
common properties. Groups of elements have the same outer electron arrangement. The
outer electrons are called valence electrons. Because they have the same number of valence
electrons, elements in a group share similar chemical properties.

General Properties of metals

General properties of metals are
1. Most metals are solid except for hydrogen which is a gas, and mercury and gallium which
is liquid at room temperature.
2. Good thermal and electrical conductivity.
3. Hard, strong and dense.
4. Generally malleable and ductile, deforming under stress without cleaving.
5. Optical properties, metals are shiny and lustrous.
6. They make a metallic sound when struck.
7. Forms positive ions in solutions during electrolysis.

Valence electron
The outer-most electrons of the atom are known as valence electrons (Fig. 3.2). Metals have
outer valence electrons that are highly mobile. These are readily given up and are responsible
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for most of their properties.
 Structure and Properties of Metals and Alloys  Chapter 3  43
Valence electrons are such an essential part of the atom’s
stability. For the most part, eight valence electrons are
necessary for an atom to be stable. A valence electron
participates in the formation of a chemical bond with other
elements.

Metallic Bonding
Metals are tough because atoms of the metals are held
together by means of metallic bonds. Metallic bond is the
Figure 3.2 Valence electron of
bonding between molecules within metals (also called alkali the sodium atom.
reactive force).
In metals, valence electrons are shared by all the atoms of the metal and so are not
considered to be associated with any one atom. This is very different from ionic or covalent
bonds, where electrons are held by one or two atoms. The sea of shared ‘delocalised electrons’
amongst a lattice of positive ions acts as a kind of “electron glue” giving the substance a
definite structure.
The metallic bond is, therefore, strong and uniform. Since electrons are attracted to many
atoms, they have considerable mobility to be good conductors of heat and electricity.
Metallic bonds, though strong, also allow movement of the individual atoms. This property
allows metals to be hammered into sheets or drawn into wires.

Alloys
Most metals used in dentistry are used in the alloyed form. Examples of alloys in dentistry are
steel, chrome-cobalt, nickel-chrome, gold-palladium, etc.
One of the first alloys made by humans was bronze, which is made by mixing the metals tin
and copper.

Definition
An alloy is a material composed of two more elements; at least one of which should be a metal.
Thus an alloy is made by fusing two or more metals, or a metal and a nonmetal.
An alloy may be a solid solution of the elements (a single phase), a mixture of metallic phases
(two or more solutions) or an intermetallic compound with no distinct boundary between
the phases.
Solid solution alloys give a single solid phase microstructure, while partial solutions exhibit
two or more phases that may or may not be homogeneous in distribution, depending on the
thermal (heat treatment) history of the material. An inter-metallic compound has one other
alloy or pure metal embedded within another pure metal.
Alloys are used in some applications, where their properties are superior to those of the pure
component elements for a given application.

Why do we need to alloy?

An alloy has properties which are beneficial over that of the parent materials. A metal that
is normally very soft and malleable, such as aluminium, can be altered by alloying it with
another soft metal, like copper. Although both metals are very soft and ductile, the resulting
aluminium alloy will be much harder and stronger. Adding a small amount of nonmetallic
carbon to iron produces an alloy called steel. Due to its very-high strength and toughness
(which is much higher than pure iron), and its ability to be greatly altered by heat treatment,
steel is one of the mosthttp://dentalebooks.com
common alloys in modern use. By adding chromium to steel, its
44  Part 1  Structure and Properties of Dental Materials
resistance to corrosion can be enhanced, creating stainless steel, while adding silicon will
alter its electrical characteristics, producing silicon steel.

Classification of alloys
Alloys are usually classified as substitutional or interstitial alloys, depending on the atomic
arrangement that forms the alloy.

They can further be classified based on solubility as

1. Homogeneous (consisting of a single phase)
2. Heterogeneous (consisting of two or more phases)
3. Intermetallic (where there is no distinct boundary between phases)

During the fabrication of a restoration, the alloy is melted and the liquid metal forced into a
mold to create the particular restoration. Thus a knowledge of the behavior of alloys during
melting and solidification is beneficial.

Manufacture of alloys
Alloys may be prepared by different technological methods: melting, sintering of a powder
mixture, high temperature diffusion of an alloying element into the base metal, plasma and
vapor deposition of different elements, electroplating, etc.

Phase
A phase is a uniform part of an alloy, having a certain chemical composition and structure,
and which is separated from other alloy constituents by a phase boundary.
An alloy phase may be in the form of a compound (substance formed from two or more
elements), with a fixed ratio determining the composition) or in form of solid solution.

SOLID SOLUTIONS

Can one metal dissolve in another?

Two or more metals can dissolve to form solutions. This usually occurs at high temperatures and
the product formed is called an alloy. Some metals can also be dissolved at room temperatures,
e.g. mercury-tin (Box 3.2). This property is used in the creation of dental amalgam.

Solid solution
A solid solution is a solid-state solution of one or more solutes in a solvent. Such a
mixture is considered a solution rather than a compound when the crystal structure
of the solvent remains unchanged by addition of the solutes, and when the mixture
remains in a single homogeneous phase. This often happens when the two elements
(generally metals) involved are close together on the periodic table; conversely, a
chemical compound generally results when two metals involved are not near each
other on the periodic table.
The solid solution needs to be distinguished from a mechanical mixture of powdered solids
like two salts, sugar and salt, etc. The mechanical mixtures have total or partial miscibility
gap in solid state.
Examples of solid solutions include crystallized salts from their liquid mixture, metal alloys,
moist solids. In the case of metal alloys intermetallic compounds occur frequently.

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 Structure and Properties of Metals and Alloys  Chapter 3  45

Box 3.2   

Mercur y  M ercur y is the only

known metal which is liquid at room
temperature. Mercury dissolves many Gallium  Gallium melts at 29.76 °C
metals such as gold and silver to form which is near room temperature.
Mercury ore  Mercury ore is amalgams. This unique property is Thus one is able to melt a block
produced from its ore called used in dentistry to form the filling of Gallium simply by holding it in
Cinnabar. Cinnabar is a toxic material ‘Dental Amalgam’. Iron and one’s hands. Our body temperature
mercury sulfide mineral with a platinum are exceptions, and iron of 37 °C is sufficient for melting this
chemical composition of HgS. It flasks have been traditionally used to unique metal.
was used extensively as a pigment trade mercury. Other metals which
for thousands of years in many dissolve in mercury are manganese,
parts of the world. copper and zinc.

Types of solid solutions

Depending on the ratio of the solvent (matrix) metal atom size and solute element atom size,
two types of solid solutions may be formed.
1. Substitutional
2. Interstitial
Substitution solid solution
If the atoms of the solvent metal and solute element are of similar sizes (not more than
15% difference), they form substitution solid solution, where part of the solvent atoms are
substituted by atoms of the alloying element (Fig. 3.3).
Examples are brass (copper with zinc) and palladium-silver.

Interstitial solid solution

If the atoms of the alloying elements are considerably smaller than the atoms of the matrix
metal, interstitial solid solution forms, where the matrix solute atoms are located in the spaces
between large solvent atoms (Fig. 3.4).

Figure 3.3  Substitution solid solutions.

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46  Part 1  Structure and Properties of Dental Materials

Figure 3.4  Interstitial solid solutions.

Steel is an example of an interstitial alloy in which a relatively small number of carbon atoms
slip in the gaps between the huge iron atoms in a crystalline lattice of iron. Titanium (CPTi)
used in dental implants is another example (99% titanium with oxygen, carbon, nitrogen and
hydrogen as interstitial substitutes).

Dental Applications
Most noble alloys used in dentistry are based on solid solutions. In case of Pd-Ag both metals
are mutually soluble in each other in the solid state regardless of the proportion of each.

Solidification and microstructure of metals and alloys

Microstructure is defined as the structure of a prepared surface or thin foil of material as
revealed by a microscope. The microstructure of a material can strongly influence physical
properties such as strength, toughness, ductility, hardness, corrosion resistance, high/low
temperature behavior, wear resistance, and so on, which in turn, govern the application of
these materials in laboratory and clinical practice. Microstructure at scales smaller than can
be viewed with optical microscopes is often called ultrastructure or nanostructure.

Grains
Solidification occurs by a process of crystallization (Fig. 3.5). Crystallization begins around
a nucleus. Crystals are also known as grains as they seldom show the customary crystal
shapes because of interference from
neighboring crystals. Crystallization
process results in various types of
microstructures depending on the type
of metal or alloy and the cooling process.
The crystals are otherwise known as
grains since they seldom exhibit the
customary geometric forms due to
interference from adjacent crystals
during the change of state.

Nuclei of crystallization
Surface tension of liquid metal is 10
times higher than that of water. When
molten alloy cools, the solidification
process begins with the formation of
atom clusters called ‘embryos’ or ‘nuclei
of crystallization’. http://dentalebooks.com
Figure 3.5  Illustration of grain growth and solidification.
 Structure and Properties of Metals and Alloys  Chapter 3  47

Figure 3.6  Photomicrograph showing

dendritic structure.

Crystallization forms
Metals solidify in roughly three predominant
crystal forms (Figs. 3.6 and 3.7)
1. Dendritic microstructure
2. Polycrystalline microstructure
a. Equiaxed grains
b. Columnar grains
3. Monocrystalline or Single crystal A B C

Dendritic microstructure Figures 3.7A to C Illustration of different grain

In the dendritic form, the crystals that form in structures in a turbine blade. (A) Equiaxed grains. (B)
Columnar grains. (C) Monocrystalline or Single crystal.
the liquid during freezing generally follow a
pattern consisting of a main branch with many appendages. A crystal with this morphology
slightly resembles a pine tree and is called a dendrite, which means branching. The formation of
dendrites occurs because crystals grow in defined planes due to the crystal lattice they create.
Secondary dendrite arms branch off the primary arm, and tertiary arms off the secondary
arms, etc., resulting in a three-dimensional dendritic structure (Fig. 3.6).
Dental base metal alloys and titanium based casting alloys in which nickel (N), cobalt (Co), iron
(Fe), and titanium (Ti) are the main elements generally have a dendritic as cast microstructure.

Equiaxed polycrystalline microstructure

Equiaxed grains (Figs. 3.7A and 3.8) are crystals that have axes of approximately the same
length. The crystal grows from multiple nucleation points. The expanding crystals continue
to grow until they impinge on adjacent growing crystals at grain boundaries. The final sizes of
the individual crystals depend on the number of nucleation points. Most noble metal casting
alloys solidify with this type of microstructure.
Dental noble metal alloys generally have equiaxed fine-grain microstructures because of
certain grain refining elements added into the composition.

Columnar polycrystalline alloys

Columnar grain structured castings (Figs. 3.7B and 3.9) are created using a special casting
technique called ‘directional solidification’. They have grains parallel to the major stress axes. They
are less prone to creep deformation compared to equiaxed grain structured metal components.

Single crystal
Normally when a material begins to solidify, multiple crystals begin to grow in the
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liquid and a polycrystalline (more than one crystal) solid forms. However, it is possible
48  Part 1  Structure and Properties of Dental Materials
to produce a single large crystal, so there are
no grain boundaries in the material (Fig. 3.7
C). Single crystals are produced under carefully
controlled conditions. The expense of producing
single crystal materials is only justified for special
applications, such as turbine engine blades, solar
cells, and piezoelectric materials.
Jet engine turbine blades must endure tremendous
forces at extremely high temperatures for
prolonged periods of time. Under such conditions,
metals with a grain structure tend to “creep,” or
slowly deform, along grain boundaries. Because
single-crystal alloy parts have no grain boundaries
they are highly resistant to creep.
Figure 3.8  Photomicrograph of aluminium alloy (Al-Mg-Fe-Si
containing < 1 wt.% of each solute) showing equiaxed grain Forming single-crystal metal objects requires
structure. Addition of TiB2 particles facilitates fine, equiaxed both special alloys and special casting
grain structure. (Specimen was electrolytically etched using techniques (modified version of the directional
Barker’s reagent and photographed under cross-polarised light
microscopy. (Courtesy: Department of Materials Science and
solidification technique). The alloys are almost
Metallurgy, University of Cambridge). always nickel-based, with as many as nine minor
metal components including chromium, cobalt,
tungsten, tantalum, aluminium, and/or rhenium.

Grain Boundaries
As mentioned previously, the grains meet at
grain boundaries (Fig. 3.8) which are regions of
transition between differently oriented crystals.
These are regions of importance
1. Less resistance to corrosion
2. High internal energy
3. Collection of impurities
Figure 3.9  Columnar grained ingot through directional
solidification. 4. Barriers for dislocations

Grain refinement and Grain size

Control of grain morphology and size are important in order to predict the properties of the cast
metal. Generally alloys with fine grains have superior properties including corrosion resistance.

Control of Grain Size

Grain size can be controlled by
1. Addition of small quantities of grain refining elements like iridium (Ir), ruthenium ((Ru),
rhenium ((Re), etc.
2. Use of different casting techniques.
3. Heat treatment, namely annealing.

Time-temperature graph
In order to understand the solidification of alloys, one has to understand the solidification
of a pure metal. This can be understood by melting a pure metal and then cooling it back to
room temperature. As it cools, a time-temperature graph is plotted (Fig. 3.10).
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 Structure and Properties of Metals and Alloys  Chapter 3  49

Figure 3.10  A time temperature

cooling curve for a pure metal.

The molten metal starts cooling from A to point B1, this is called supercooling. During the
supercooling process crystals of metal begin to form. Crystallization releases latent heat of
fusion causing a rise in temperature (B1 to B).
Completion of crystallization occurs at point C. Between B and C the metal has both liquid
and solid phases. The temperature remains steady (plateau) until crystallization is completed.
Point D indicates cooling to room temperature.

Equilibrium Phase Diagrams

A phase diagram is also known as a constitutional diagram. It helps to identify the phases
present in an alloy at different compositions and temperatures. The phase diagram may be
explained using the example of the palladium-silver alloy. The two metals exhibit complete
solubility in liquid and solid states. The equilibrium phase diagram of Pd-Ag at a composition
of 65% Pd and 35% Ag is presented in Figure 3.11.

Homogenization Heat Treatment - microstructure

From the phase diagram of the palladium-silver alloy, it is evident that the composition of
the structure is not uniform. The grains that form early on during solidification have a higher
palladium content compared to the layers that solidify later. Thus the core contains dendrites
of varying or nonuniform composition.
Heat treatments can be used to homogenize cast metal alloys to improve their hot workability,
to soften metals prior to, and during hot and cold processing operations, or to alter their
microstructure in such a way as to achieve the desired mechanical properties.

Definition
Homogenization heat treatment can be defined as a combination of heating and cooling
operations applied to a metal or alloy in its solid state to eliminate as cast nonuniform
compositional variations (coring effect) to a more uniform equiaxed grain structure through
atomic diffusion.

Procedure
The heat treatment of metals involves raising the temperature of an alloy to a defined
temperature, usually nearhttp://dentalebooks.com
its solidus. The material is then held at this temperature for a period
50  Part 1  Structure and Properties of Dental Materials

Equilibrium Phase Diagrams 

Consider the cooling of Pd-Ag alloy at 65% and 35% composition respectively. This is represented by the line PO. At ‘P’
the alloy is in liquid state. At ‘R’ the alloy begins to solidify. However the first crystals have a higher Pd content than the
expected 65 %. To determine the exact percentage composition of the first crystals a line is extended from ‘R’ to ‘M’ on
the solidus line. Point ‘M’ determines the composition of the first solids which is 77% Pd. At ‘S’ it is midway through its
solidification. Here the composition of the solid is determined as 71% Pd (Point W). The liquid composition is 57% Pd
(Point Y). As it cools to the solidus line (1340 °C) Point ‘T’ the solid phase has 65 % palladium and the remainder of the
liquid solidifies at a composition of only 52% Pd. Thus it can be seen from this phase diagram that grains have a varied
composition within the structure, though the overall composition is 65% palladium

Figure 3.11  Equilibrium phase diagram for the palladium-silver system.

of time (up to 6 hours) before being cooled either at a prescribed rate or under rapid quenching
conditions to a fixed temperature. Heat treatment is carried out in furnaces and ovens.

Eutectic Alloys
Eutectic is a ‘term’ used to describe two components which are ‘completely soluble’ in each
other in the liquid or molten state, but only partially soluble in the solid state. Therefore these
alloys do not form solid solutions. Rather, eutectic alloys upon cooling, convert from liquids
to intimately mixed solids.
In an eutectic system, the “eutectic alloy” composition has the lowest melting point in the
system. It is lower than the melting points of either of the pure components.

Applications
1. Pb-Sn alloy is a good example of an eutectic alloy system.
2. In Dentistry, the Au-Cu eutectic alloy is used in the silver amalgam system.
3. Gold-iridium system is eutectic at iridium concentration of 0.005%.

Equilibrium-phase diagrams of Ag-Cu

In the phase diagram (Fig. 3.12), at three different concentrations, the material will be solid
until it is heated to its melting point, and then (after adding the heat of fusion) becomes
liquid at that same temperature.
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 Structure and Properties of Metals and Alloys  Chapter 3  51

Figure 3.12  Equilibrium phase

diagram for the silver-copper system
α - Silver-rich substitutional solid
solution
β - Copper-rich substitutional solid
solution
L - Liquid phase
AED - Liquidus line
ABEGD - Solidus line
Solidus and Liquidus lines meet
at E rather than at the pure metal
composition seen in the earlier phase
diagram. This composition of 72% Ag
and 28% Cu is called as the Eutectic.
Eutectic means lowest melting. The
Eutectic composition melts at a
temperature of 779 °C which is lower
than either of the pure parent metals.

1. The unalloyed extreme left

2. The unalloyed extreme right
3. The dip in the center E (the eutectic composition).
At other compositions, the material will enter a mushy or pasty phase until it warms up to
its melting temperature.
The mixture at the dip point (E) of the diagram is called an eutectic alloy.

Features of the eutectic system

1. The eutectic composition melts at a temperature of 779 °C which is lower than either of
the pure parent metals. This property is useful in solders.
2. Solidus and liquidus lines meet at the Eutectic temperature. Thus there is no solidification
range at the eutectic temperature of 779 °C.

Hypoeutectic and hypereutectic alloys

Alloys with compositions less than that of the eutectic are called hypoeutectic alloys and those
with a composition greater than the eutectic are known as hypereutectic alloys.

Peritectic Alloys
Peritectic transformations are also similar to eutectic reactions. Here, a liquid and solid phase
of fixed proportions react at a fixed temperature to yield a single solid phase (Fig. 3.13).
The peritectic reaction during the cooling phase can be written as
Liquid + β Solid solution → α Solid solution

Peritectic alloys are susceptible to coring during rapid cooling. This cored structure is more
brittle and has lower corrosion resistance than a homogeneous solid solution.

Examples
1. The dental amalgam alloy silver-tin is based on the peritectic system.
2. Dental casting alloy gold-platinum.
3. Palladium-ruthenium alloy at 16.5% has a peritectic reaction.
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52  Part 1  Structure and Properties of Dental Materials

Figure 3.13 Equilibrium phase diagram for the platinum-silver system demonstrating

peritectic reaction
α - Silver rich phase
β - Platinum rich phase
P - Peritectic transformation point
A - Platinum melting point (1768 °C)
H - Silver melting point (961.8 °C)
A peritectic reaction is a reaction where a solid phase (β) and liquid phase will together form
a second solid phase (α) at a particular temperature and composition.
In this case, it occurs at a composition of 56% Pt.

Solid state reactions

Knowledge of solid-state reactions is important to understand strengthening mechanisms in
Type III and IV gold alloys like age hardening. Solid state reactions can be explained through
the gold-copper phase diagram.

Gold-Copper phase diagram

Gold and copper are completely soluble in each other in the liquid state. The gold-copper
equilibrium phase diagram is presented in (Fig. 3.14). The difference between the liquidus
and solidus is small at all compositions. The two curves meet at 80.1%. This composition marks
the lowest temperature at which a gold-copper alloy can melt. At temperatures between
the solidus and 410 oC the gold and copper are mutually soluble and form a disordered solid
solution (α). The atoms are in random arrangement in an FCC structure. However, as the alloy
cools down further, certain solid state transformations are seen. The various phases on cooling
at various compositions are summed up in Table 3.1.
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 Structure and Properties of Metals and Alloys  Chapter 3  53

Figure 3.14  Equilibrium phase diagram for the gold-copper system.

Table 3.1  Phases formed at various temperature and composition range

Phase Temperature Composition range
Disordered α phase (Au-Cu) Between solidus and 410 °C 40–65%
Ordered α’ phase (Au-Cu3) Below 390 °C 40–65%
Ordered α’’2 phase (Au-Cu II) Below 410 °C 65–85%
Ordered α’’1 phase (Au-Cu I) Below 410 °C 65–85%

Heat treatment of Gold alloys

The ordered phases (α’, α’’2 , and α’’1) have superior mechanical properties. The disordered
phase (α phase) on the other hand is relatively soft and ductile. This soft ductile phase is
convenient for laboratory finishing and grinding procedures. The disordered phase which
exists at the higher temperatures can be preserved by rapid quenching. Rapid cooling prevents
atomic movement to the more ordered lower temperature phases. Following adjustments
of the crown, the alloy is again age hardened by holding it at specified temperature for a
specified period. This permits the solid state reactions to take place (through atomic fusion)
and convert the alloy to its mechanically superior ordered phases (α’, α’’2 , and α’’1). The alloys
can be restored to its softened condition by again raising it to a temperature just below its
solidus (700 oC) and holding it at this temperature for 10 minutes and then rapidly quenching.
Thus essentially, gold alloys can be both softened and hardened through heat treatment.

Types of Heat treatment

From the above, it is clear that a variety of heat treatments are available for various purposes.
The various heat treatments are summarized below.
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54  Part 1  Structure and Properties of Dental Materials
Homogenization
This treatment is used prior to hot working processes and is performed to equalize
temperatures throughout an alloy or to reduce the coring effect caused by the nonuniform
chemical composition.

Softening heat treatment

Synonyms  Solution heat treatment, annealing.
Softening heat treatment covers a variety of heat treatment processes used to soften alloys
and increase their ductility as an aid to cold working. It is also performed to remove internal
stresses within components following cold working, welding, casting or rapid cooling.

Hardening heat treatment

Synonyms  Precipitation hardening, age hardening
Hardening heat treatment is a heat treatment technique used to increase the strength of
malleable materials, including most structural alloys of nickel, titanium, and some stainless steels.

Classification of alloys
Dental alloys can be classified in many ways.
1. Based on the number of alloying elements
a. Binary (two constituents)
b. Ternary (three constituents)
c. Quaternary (four constituents)
d. Quinary (five constituents)
2. Based on noble metal content
a. High Noble
b. Noble
c. Predominantly base

Functions of alloying elements

Elements are added into the alloy in various proportions to modify its properties. Most
elements affect the properties of the metal in multiple ways. The various properties and the
effect of the modifiers are described.

Grain refinement
Grain refinement is the process by which the grain size is restricted during solidification.
Smaller grain sizes block dislocation movements within the structure. This improves the yield
strength of the alloy.

Metals that refine grain sizes are

 Iridium
 Rhenium
 Ruthenium

Mechanical properties
Alloys like palladium, platinum, copper and iron improve mechanical properties like strength,
hardness and modulus of elasticity in gold-based alloys.
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 Structure and Properties of Metals and Alloys  Chapter 3  55
Color modification
The alloying metals have varying effects on the color of the alloy. Metals like gold and copper
impart a gold and reddish hue to the alloy. White metals like palladium and silver tend to
whiten the alloy. Silver-rich alloys tend to have a greening hue.

CTE (TEC) modification

The thermal expansion coefficient (TEC) (also called coefficient of thermal expansion-
CTE) of an alloy used to construct porcelain-fused to metal crowns (PFM) requires to be
closely matched to that of the veneering porcelain. TEC mismatch can cause fracture or
separation of the veneer from the metal. Silver increases CTE whereas palladium lowers
the CTE in the alloy.

Melting range modification

Generally metals with higher melting points raise the melting range, whereas metals with
lower melting point tend to lower the melting range of the corresponding alloys. Example,
silver reduces the melting range of palladium and gold alloys. Palladium and platinum raise
the melting range of gold-based alloys.

Castability
The castability of a material is the ease with which a casting can be produced with minimal
energy and defects. Generally castability is related to the density of a material. Denser
metals improve the castability of the alloy. Noble alloys are generally more easy to cast
because of their greater density when compared to base metal alloys like cobalt-chromium.

Oxygen scavenger
Zinc is added to remove oxygen during the casting process, thereby reducing porosity.

Tarnish and corrosion resistance

Tarnish and corrosion resistance is a desirable property especially in the oral environment.
Improving the concentration of noble metals improve the tarnish and corrosion resistance
of an alloy.
In base metal alloys, the mechanism for tarnish and corrosion resistance is different. In chrome-
based alloys, a surface oxide is readily formed. The surface oxide forms a protective layer which
protects the metal from further corrosion. This property is called ‘passivation’. Other metals
which use a similar mechanism is stainless steel and titanium.

Density and specific gravity

In certain instances like large cast removable partial dentures, a light weight framework is
preferable to a more heavier frame in terms of patient comfort and appliance retention. Base
metal alloys are popular as RPD alloys because of their low density. Palladium being lighter
than gold lowers the density and weight of gold-palladium-based alloys. The density of a
palladium based alloy is midway between that of base metal and of high noble alloys.

Oxide formation
Metals used for porcelain fused to metal restorations have the additional requirement of
facilitating porcelain attachment. Porcelain does not bond readily to noble metal alloys.
Certain elements like tin, indium and iron oxide are added to noble metal alloys to form
oxides which aid in the bonding of porcelain to the alloy. Base metal alloys form oxides
quickly. http://dentalebooks.com
 4
Chapter

Electrochemical
Properties of Materials
Chapter Outline
• Definitions –– Electromotive Force Series –– Electrolyte Concentration
–– Tarnish (Emf) Cell
–– Passivation • Types of Electrolytic Corrosion • Protection Against Corrosion
–– Corrosion –– Galvanic Corrosion –– Passivation
• Classification of Corrosion –– Heterogeneous Compositions –– Increasing Noble Metal
–– Chemical or Dry Corrosion –– Stress Corrosion Content
–– Electrolytic or Electrochemical –– Concentration Cell Corrosion –– Polishing
or Wet Corrosion or Crevice Corrosion –– Other Methods

Except for a few, pure metals do not occur naturally. They occur in the form of minerals such
as oxides and sulfides and these have to be refined to produce the pure metal. Most pure
metals attempt to reconvert to the combined state. The process by which this takes place is
called corrosion.
One of the primary requisites of any metal that is to be used in the mouth is that it must
not produce corrosion products that will be harmful to the body. The mouth is moist and
continually subjec­ted to fluctuations in temperature. The foods and liquids ingested have
wide range of pH. All these factors make the mouth an extremely favorable environment for
corrosion.

DEFINITIONS
Tarnish
Tarnish is a surface discoloration on a metal or even a slight loss or alteration of the surface
finish or lustre.

Tarnish generally occurs in the oral cavity due to

1. Formation of hard and soft deposits on the surface of the restoration, e.g. calculus, mucin
and plaque.
2. Pigment producing bacteria, produce stains.
3. Formation of thin films of oxides, sulfides or chlorides.
Tarnish is often the forerunner of corrosion.

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 Electrochemical Properties of Materials  Chapter 4  57
Passivation
In certain cases, the oxide film can also be protective in nature. For example, chromium alloys
(used in dental castings) are protected from corrosion by the formation of an oxide layer on its
surface which protects the metal against any further corrosion. This is known as passivation.
Another example is titanium.

Corrosion
It is not a surface discoloration but actual deterioration of a metal by reaction with the
environment. It can be defined as the deterioration of metals by chemical interaction with
their environment.
Most metals exist in their stable oxide state in nature except for some of the noble metals
like gold. Metals are refined from these natural ores to produce the pure metals and alloys.
However, the pure state of metals is unstable. Corrosion is a natural process, which converts
refined metal to their more stable forms.
In the most common use of the word, this means electrochemical oxidation of metal in
reaction with an oxidant such as oxygen. Rusting, the formation of iron oxides, is a well-known
example of electrochemical corrosion. This type of damage typically produces oxides or salts
of the original metal.
However element other than oxygen also can cause corrosion particularly in the oral
environment. Water, oxygen, chloride ions, sulfides like hydrogen sulfide or ammonium sulfide
contribute to corrosion attack in the oral cavity. Various acids such as phosphoric, acetic and
lactic are also present. Among the specific ions responsible for corrosion, oxygen and chloride
have been implicated in amalgam corro­sion both at the tooth interface and within the body
of amalgam. Sulfide has been implicated in the corrosion of silver containing casting alloys.
Corrosion degrades the useful properties of materials and structures including strength and
appearance. In due course, it may lead to rapid mechanical failure of the structure.

Electromotive Force Series (EMF)

The EMF series is a classification of elements in the order of their dissolution tendencies. That is,
if two metals are immersed in an electrolyte and are connected by an electrical conductor, an
electric couple is formed. The metal that gives up its electrons and ionizes is called the anode.
In the EMF series, hydrogen has been used as the standard electrode to which other metals
have been compared. Hydrogen has been given the value zero in the EMF series (Table 4.1).

Table 4.1  Electromotive force values

Metal Ion Electrode potential
Gold Au + 1.50
Platinum Pt + 0.86
Silver Ag + 0.88
Copper Cu + 0.47
Hydrogen H +
0.00
Cobalt Co –0.28
Iron Fe –0.44
Zinc Zn –0.76

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58  Part 1  Structure and Properties of Dental Materials
The metal with lowest electrode potential corrodes. Also the more active metal corrodes
(anode) and the more noble metal becomes the cathode.

CLASSIFICATION OF CORROSION
Corrosion can be classified as
1. Chemical or dry corrosion
2. Electrochemical or wet corrosion

Chemical or Dry Corrosion

The metal reacts to form oxides and sulfides in the absence of electrolytes.
Example Formation of Ag2S in dental alloys containing silver.
Oxidation of alloy particles in dental amalgam.

Electrolytic or Electrochemical or Wet Corrosion

This requires the presence of water or other fluid electrolytes. There is formation of free
electrons and the electrolyte provides the pathway for the transport of electrons. An
electrolytic cell is as follows:

M0 → M+ + e–

The anode is the surface where positive ions are formed. This metal surface corrodes since
there is loss of electrons. This reac­tion is sometimes referred to as oxidation reaction.

M+ + e– → M0
2H+ + 2e– → H2
2H2O + O2 + 4e– → 4(OH)¯
At the cathode a reaction must occur that will consume the free electrons produced at the
anode. The reactions 2, 3 and 4 occur at the cathode and are referred to as reduction reactions.
Hence, the anode loses electrons and the cathode consumes. The surface of the anode corrodes
due to loss of electrons.

TYPES OF ELECTROLYTIC CORROSION

Galvanic Corrosion
Saliva with its salts provides a weak electrolyte. Galvanic corro­sion occurs when dissimilar
metals lie in direct physical contact with each other (Fig. 4.1).
If a gold restoration comes in contact with an amalgam resto­r ation, the amalgam
forms the anode and starts corroding. The electric couple (500 millivolts) created when
the two restorations touch, causes sharp pain called ‘galvanic shock’. It usually occurs
immediately after insertion and can be minimized by painting a varnish on the surface
of the amalgam restoration. However, the best precaution is to avoid dissimilar metals
in contact. Another variation of galvanic corrosion can occur even in a lone standing
restoration (Fig. 4.2).

Note  Seldom there is any one type of corrosion found alone, generally two or more act
simultaneously and thus aggra­vate the problem.

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 Electrochemical Properties of Materials  Chapter 4  59

Figure 4.2  A current pathway may exist even in a single

metallic restoration. In this case the tissue fluid behaves like
Figure 4.1 Potential galvanic current pathway when a cathode (because of the higher concentration of Cl– ions
dissimilar metals contact. The tissue fluid and saliva in tissue fluid when compared to saliva) whereas saliva
behaves like an electrolyte. behaves like an anode. This current is usually less intense.

Heterogeneous Compositions
This kind of corrosion occurs within the structure of the restoration itself. Heterogeneous
(mixed) compositions can cause galvanic corrosion.
 When an alloy containing eutectic is immersed in an electrolyte the metallic grains with
the lower electrode potential are attac­ked and corrosion results.
 In a cored structure differences in the composition within the alloy grains are found.
Thus a part of a grain can be anode and a part, cathode. Homogeni­zation improves the
corrosion resis­tance of the alloy.
 In metals or alloys the grain boundaries may act as anodes and the interior of the grain as
the cathode.
 Solder joints may also corrode due to the nonhomogeneous composition.
 Impurities in any alloy enhance corrosion.

Stress Corrosion
A metal which has been stressed by cold working, becomes more reactive at the site of maximum
stress. If stressed and unstressed metals are in contact in an electrolyte, the stressed metal will
become the anode of a galvanic cell and will corrode. For example, if an orthodontic wire has
been cold worked, stress corrosion may occur and cause the wire to break.

Concentration Cell Corrosion or Crevice Corrosion (Fig. 4.3)

 Electrolyte concentration cell  In a metallic restoration which is partly covered by food
debris, the composition of the electro­lyte under the debris will differ from that of saliva
and this can contribute to the corrosion of the restoration.

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60  Part 1  Structure and Properties of Dental Materials

Figure 4.3  Different types of corrosion.

 Oxygen concentration cell  Differences in oxygen tension in between parts of the same
restoration causes corrosion of the restoration. Greater corrosion occurs in the part of the
restora­tion having a lower concentration of oxygen.

Factors affecting corrosion of restorations in the mouth

Corrosion of dental restorations in the mouth is influenced by
1. Diet
2. Drug
3. Smoking
4. Bacterial activity
5. Oral hygiene and habits

PROTECTION AGAINST CORROSION

Passivation
Certain metals readily form strong adherent oxide film on their surface which protects them
from corrosion. Such metals are said to be passive. Chromium, titanium, and aluminium are
exam­ples of such metals.
Adding more than 12% Cr to iron or cobalt produces a chromic oxide layer on the surface of
stainless steel or cobalt chromium alloys which is highly corrosion resis­tant. Since this film is
passive to oxidative chemical attack, their formation is called passivation.

Increasing Noble Metal Content

Alloys with a noble metal content below 65% may tarnish. So it has been suggested that
at least 50% of the atoms in a dental alloy should be gold, platinum or palladium to ensure
against corro­sion. Noble metals resist corrosion because their EMF is positive with regard to
any of the common reduction reactions found in the oral environment.

Polishing
Polishing metallic restorations like amalgam and cast metal to a high luster minimizes
corrosion. The patient should also maintain good oral hygiene.

Other Methods
Dissimilar metal restorations should be avoided. Avoid using a high mercury con­taining
amalgam as it is more susceptible to corrosion. Mercury tarnishes gold, thus, care must be
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taken to protect gold ornaments worn by the operator, assistant or patient.
 5
Chapter

Biological Properties
of Dental Materials
Chapter Outline
• Biological Requirements of • Physical Factors Affecting Pulp • Therapeutic Effects of Dental
Dental Materials Health Materials
• Classification of Materials –– Microleakage • Osseointegration
from a Biological –– Thermal Change • Effect of Pressure on Tissues
Perspective –– Galvanism • Effect of Pontic Design
• Biohazards Related to the • Classification of Adverse • Effect of Material - Porcelain
Dental materials Reactions from Dental Materials Versus Resin
• Biological considerations of • Toxicity Evaluation • Infection Control
restoration Design –– Level I Tests (Screening Tests) –– Infection Routes
–– Biotraps in the Oral –– Level II (Usage Tests) –– Disinfection of Dental
Environment –– Level III (Human Trials) Materials

The science of dental materials must include a knowledge and appreciation of the biological
considerations that are associated with selection and use of materials designed for the oral
cavity. Strength and resistance to corrosion are unimportant if the material irritates or injures
the pulp or soft tissue. The biological charac­teristics of dental materials cannot be isolated
from their physical properties. In the early days of dentistry, the patient’s mouth was often
the testing ground of dental materials. Modern dentistry, however, involves extensive testing
before the material is certified for human use.

Biomaterials
Many materials used in the mouth are classed as ‘biomaterials’.
A biomaterial can be defined as any substance other than a drug that can be used for any
period of time as a part of a system that treats, augments, or replaces any tissue, organ or
function of the body.

Biological Requirements of Dental Materials

A dental material should
1. Be nontoxic to the body
2. Be nonirritant to the oral or other tissues
3. Not produce allergic reactions
4. Not be mutagenic or carcinogenic
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62  Part 1  Structure and Properties of Dental Materials
Classification of Materials from a Biological Perspective
A. Those which contact the soft tissues within the mouth
B. Those which could affect the health of the dental pulp, e.g. restorative materials and
luting cements.
C. Those which could affect the periapical areas of the tooth such as root-canal medicaments,
filling materials, etc.
D. Those which affect the hard tissues of the teeth.
E. Those used in the dental clinics and laboratory which when handled may be accidentally
ingested or inhaled, e.g. alginate dust, mercury vapors, alloy dust containing beryllium
formed while cutting metal.

Biohazards related to the Dental materials

 Some dental cements are acidic and may cause pulp irritation.
 Polymer based filling materials may contain irritating chemicals such as unreacted
monomers, which can irritate the pulp.
 Phosphoric acid is used as an etchant for enamel.
 Mercury is used in dental amalgam, mercury vapor is toxic.
 Dust from alginate impression materials may be inhaled, some products contain lead
compounds.
 Monomer in denture base materials is a potential irritant.
 Some people are allergic to alloys containing nickel (Fig. 5.1). Dental applications of nickel
alloys include orthodontic wires, fixed and removable partial dentures, etc. Allergies are
confirmed using the patch test (Figs. 5.6A and B).
 The frequency of titanium allergy seems
to be very rare. Titanium allergies are
similar to other metal allergies. They show
symptoms adjacent to the area where it
is placed (Fig. 5.2). Some patients report
worsening of health after placement of
titanium implants.
 During grinding of beryllium containing
casting alloys, inhalation of beryllium dust
can cause berylliosis.
 Some dental porcelain powders contain Figure 5.1  Nickel allergy from a necklace.
uranium.
 Metallic compounds (e.g. of lead, tin etc.)
are used in elastomeric materials.
 Eugenol in materials like restorations
and impressions can cause irritation and
burning in some patients.
 Laboratory materials have their hazards,
such as cyanide solution for electro­
plating, vapors from low fusing metal dies,
siliceous particles in investment materials,
fluxes containing fluorides asbestos, etc.
Figure 5.2  Titanium allergy. The shin of a woman
 Some periodontal dressing materials have with dermatitis adjacent to implanted titanium
contained asbestos http://dentalebooks.com
fibers. orthopedic device.
 Biological Properties of Dental Materials  Chapter 5  63
Biological considerations of restoration Design
Besides material considerations, the design of the restoration plays an important part in
biological response and function. Faulty design is a major cause of recurrent caries, gingival
inflammation, periodontal disease and tooth loss or damage. Every year countless restorations
and teeth are lost due to faulty design (Fig. 5.3A).

Biological requirements of restoration design

The restoration should be designed such that
1. It should not impede natural cleansing mechanisms of the mouth (crevicular fluid
(Fig. 5.4) and saliva).
2. It does not provide a habitat for bacterial colonization.
3. It should not trap food (Fig. 5.5B).
4. It should not trap defoliating epithelial cells lining the gingival sulcus.
In short, a restoration design should avoid ‘biotraps’ and allow natural cleansing mechanisms.

Biotraps in the oral environment

Many restorations serve as biotraps because of improper design or poor clinical skills.
1. Amalgams overhang in the proximal regions (Fig. 5.5A).
2. Overhanging crown margins especially those which are subgingival or in close proximity
to the biological width.

A B
Figures 5.3A and B  (A) Every year hundreds of crowns fail due to various reasons including poor
technique and material selection. (B) Microleakage under a crown.

Figure 5.4  Biotraps in

the gingival sulcus can trap
defoliated epithelial cells
and degradation products
by preventing the natural
exit and cleansing activity
of the crevicular fluid.
Biotraps provide a habitat
for bacterial colonization
and potential infection.

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64  Part 1  Structure and Properties of Dental Materials
3. Microleakage due to improper restoration
adaptation or bonding (Fig. 5.3B).
4. Cracked teeth or roots.
5. Cracked restorations in the interproximal
or subgingival zone.
6. Porosity within restorations contacting
tissue.
7. Uneven or rough surfaces in restorations
or prostheses contacting tissue.
8. Bridge pontics with saddle or ridge lap A
designs.
9. Biotraps in the root canal system resulting
from incomplete obturation of the root
canal system.

PHYSICAL FACTORS AFFECTING PULP HEALTH

Microleakage
A great deficiency of materials used for
restoring teeth is that, they do not adhere to
tooth structure and preexisting restorative
materials already on the tooth (except those
systems based upon polyacrylic acid and
certain dentin-bonding agents). Thus a
microscopic space always exists between the B
restoration and the prepared cavity. The use of Figures 5.5A and B  Examples of biotraps.
radioisotope tracers, dyes, scanning electron (A) Amalgam overhangs. (B) Saddle pontics are
microscope and other techniques have clearly contraindicated because of biotraps.
shown that fluids, micro­organisms and oral debris can penetrate freely along the interface
between the restoration and the tooth and progress down the walls of the cavity preparation.
This phenomenon is referred to as microleakage.

Microleakage can result in

1. Recurrent or secondary caries  The seepage of acids and microorganisms could initiate
caries around the margins of the restoration (Fig. 5.3B). Recurrent caries if left unchecked
can lead to loss of the restoration and destruction of tooth structure.
2. Stain or discoloration can also develop.
3. Sensitivity  Sometimes because of microleakage the tooth remains sensitive even after
placement of the filling. If the leakage is severe, bacterial growth occurs between the
resto­ration and the cavity and even into the dentinal tubules. Toxic products liberated
by such microorganisms produce irritation to the pulp.
4. Pulpitis from continued thermal and bacterial irritation.
5. Foul smell from trapped and decaying organic matter.
6. Inflammation of adjacent tissue caused by microorganisms or their byproducts.

Thermal Change
Tooth structure and dental restorations are continually exposed to hot and cold beverages and
foods. Instantaneous temperature fluctuation during the course of an average meal may be
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 Biological Properties of Dental Materials  Chapter 5  65
as great as 85 °C. The temperature fluctuations can crack the restorative mate­rials or produce
undesirable dimensional changes in them because of thermal expansion and contraction.
Many restorative materials are composed of metals. Metals conduct heat and cold rapidly.
Patients may often complain of sensitivity in a tooth with a metallic restoration when they
are eating hot or cold foods. The problem is more in a very large restoration, where the layer
of dentin remaining at the floor of the cavity may be so thin that it is not adequate to insulate
the pulp against the temperature shock.

Protection from thermal changes  The dentist must place a layer of insulating cement
(called base) under the restoration.

Galvanism
Another cause for sensitivity is the small currents created whenever two different metals are
present in the oral cavity. The presence of metallic restorations in the mouth may cause a
phenomenon called galvanic action or galvanism. This results from a difference in potential
between dissimilar fillings in opposing or adjacent teeth. These fillings in conjunction with
saliva as electrolyte make up an electric cell. When two opposing fillings contact each other,
the cell is short-circuited and the patient experiences pain. A similar effect may occur when
a restoration is touched by the edge of a metal fork.
Studies have shown that relatively large currents can flow. The current rapidly drops if
the fillings are maintained in contact, probably as a result of polarization of the cell. The
magnitude of the voltage is not of primary importance, but the sensitivity of the patient to
the current has a greater influence on whether he will feel pain. Some patients may feel pain
at 10 µ amp and other at 110 µ amp (average: 20 to 50 µ amp). That is why some patients
are bothered by galvanic action and others are not despite similar conditions in the mouth.
The galvanic current magnitude depends on the composition and surface area of the metals.
Stainless steel develops a higher current density than either gold or cobalt chromium alloys
when in contact with an amalgam restoration. As the size of the cathode (e.g. a gold alloy)
increases relative to that of the anode (e.g. amalgam), the current density may increase. The
larger cathode can enhance the corrosion of the smaller anode. Current densities associated
with non γ2-containing amalgams appear to be less than those associated with γ2-containing
amalgam.

Classification of adverse reactions from dental MATERIALS

A number of biological responses are possible from materials. However, they may be broadly
grouped into
1. Toxic
2. Inflammatory
3. Allergic
4. Mutagenic
Fortunately, most materials are screened very early on for toxicity and mutagenicity, therefore,
most of the possible responses if any to dental materials usually fall in the inflammatory or
allergic category.

Adverse effects may also be classified as

1. Local
2. Systemic

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66  Part 1  Structure and Properties of Dental Materials

B
Figures 5.6A and B  (A) Patch test. (B) Possible reactions to the patch test.

A local effect is a result of the direct contact of the material to the regions immediately adjacent
to the material. Example of a local reaction is the allergic response of the oral mucosa to the
denture seen in some individuals.
A systemic reaction is caused by the absorption of the material into the body through local
absorption, ingestion or inhalation.

Toxicity Evaluation
Toxicity tests are classified as
1. Level I tests (screening tests)
2. Level II tests (usage tests)
3. Level III tests (human trials)

Level I Tests (Screening Tests)

The material is first checked for acute systemic toxicity and for its cytotoxic, irritational, allergic
and carcinogenic potentials.
 Acute systemic toxicity test  is conducted by administering the material orally to laboratory
animals. If more than 50% of the animals survive, the material is safe.
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 Biological Properties of Dental Materials  Chapter 5  67
 Cytotoxic screening  may be done in vivo or in vitro. In vitro tests are conducted on cultured
cells like mouse L-929 fibroblasts and human Hela cells. There are many in vitro tests.
Example, Agar overlay technique; Agar is spread over a layer of culture cells in a culture
plate. The test material is then placed on it and incubated. A toxic material will show a
clear zone of dead cells.
 Irritational properties are checked by placing the material beneath the skin in rats or
intramuscularly in rabbits. The animals are killed at different time intervals. The tissue
response is then examined and compared.
 Allergic potential  The material is first placed inside the skin of guinea pigs. Later the material
is placed on the skin surface. Erythema and swelling at the site show allergic reaction.
 Carcinogenic potential  (i) In vivo tests  A material is placed beneath the skin
(subcutaneously) of mice. They are then killed after 1 and 2 years and examined for tumors
(ii) In vitro tests  Include Ames test. Here the material is tested with the help of mutant
histidine dependent bacteria.

Level II (Usage Tests)

The material is tested in experimental animals similar to how it is used in humans, e.g. pulp
reaction is studied by placing the material into class V cavities in teeth of primates (apes or
monkeys). The teeth are then extracted periodically and compared with negative controls
(ZOE cement) and positive controls (silicate cement).

Level III (Human Trials)

Once the material has passed screening and usage tests in animals, it is ready for trials in
humans. The reactions and performance under clinical conditions are studied.

Therapeutic effects of dental materials

Certain dental materials are utilized for their beneficial biological effects. For example, zinc
oxide eugenol cement has a pain relieving effect on irritated pulp. Calcium hydroxide pulp
capping agent promotes the formation of secondary dentin and helps repair dentinal tissue.

Osseointegration
The osseointegration potential of titanium has been well-documented in the literature. It is this
property which allowed the successful use of materials like titanium as an implant material.
The surface of titanium forms a very thin layer of oxide which promotes osseointegration.
Materials that allow osseointe­gration have a very low degradation rate. Osseointegration with
intervening connective tissue is called fibrous osseointegration and is generally considered
a failure. When the bone closely approximates the implant without intervening connective
tissue, it is called osseointegration. If the bone actually fuses with the implant, it is called
biointegration (refer chapter on Implants).

Effect of pressure on tissues

It was once believed that pressure from the pontic of a fixed dental prosthesis on the ridge
resulted in permanent inflammation based on an article by Stein in 1966 (Pontic-residual
ridge relationship: A research report, JPD 1966). With the increasing popularity of the ovate
pontic it is now known that pressure results in remodelling of the tissues and does not
invariably lead to permanent inflammation. Pressure from the pontic may result in short-
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68  Part 1  Structure and Properties of Dental Materials
term injury and inflammation as a result of tissue response to trauma. The tissues usually
recover in 10 to 12 days. Porcelain restorations were relative uncommon prior to the 1960’s.
Acrylic was commonly used for masking the metal for bridges and saddle pontics were
widely used. Both saddle pontics and acrylic have been implicated in ridge inflammation
and thus the inflammation reported by Stein may have been related to the pontic design
or material (Figs. 5.7A and B).

Effect of Pontic design

Saddle or ridge lap pontics designs usually result in inflammation as they act as biotraps. Ovate
pontics on the other hand present a convex interface (Fig. 5.8A) with the tissues with little
or no biotrap. It has a biocleansing effect on the tissues. Relatively little inflammation is seen
underneath a porcelain ovate pontic even when the patient has not performed subpontic
flossing (Fig. 5.8B).

Effect of material – Porcelain versus resin

In a fixed dental prostheses, the pontic is often in continuos contact with the tissue. Among
the various materials polished or glazed, porcelain is the most inert. However, the pontic
design must be taken into consideration. Except for saddle design, long-term contact with
porcelain shows little or no inflammation (Fig. 5.8B). On the other hand long-term contact with
resin pontics can result in inflammation of tissues regardless of the design (Figs. 5.7A and B).

A B
Figures 5.7A and B  Tissue response to 2-year old temporary resin bridge. (A) 2-year old temporary
bridge with ovate pontic design made from resin based composite (Protemp 2). (B) Inflamed tissue is
evident on removal of the bridge.

A B
Figures 5.8A and B  Tissue response to 3-year old porcelain fused to metal bridge. (A) 3-year PFM
bridge with ovate pontic requiring replacement due to ceramic chipping. (B) Tissues show little or no
inflammation in spite of the patient not having flossed for 3 years.

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 Biological Properties of Dental Materials  Chapter 5  69
INFECTION CONTROL
There is increased interest in expanding infection control measures to the dental laboratory.
Concern over possible cross-contamination to dental office personnel by microorganisms,
including hepatitis-B virus and human immunodeficiency virus (HIV), through dental
impressions has promoted the study of the effect of disinfecting techniques on dental
materials.

Infection Routes
There are many ways by which microorganisms can spread.
1. Contaminated instruments and needles.
2. Direct splashing of saliva and blood into the mouth or onto wounds.
3. Breathing of contaminated aerosol from the air-rotor handpiece.
4. Through contaminated dental materials.
Except for contamination occurring through dental materials, the other routes are beyond
the scope of this book.

Disinfection of Dental Materias

Impressions
Impressions are the main source of spread of infection among the dental materials. However,
disinfecting impression materials is more complex. The disinfectant must not affect its
properties and accuracy. If the impression has not been disinfected, we must disinfect the cast.
Materials may be disinfected by
1. Immersion in a disinfectant.
2. Spraying with a disinfectant.
3. Incorporating the disinfectant into the material as part of its composition.
Immersion in a disinfectant is the most common method of disinfection in the dental office
as well as laboratory. However, certain materials like alginates may be affected if immersed
beyond the recommended period. Alginates imbibe water and swell thereby affecting its
accuracy.

Contaminated restorations and prostheses

Crowns, dentures and other prostheses that have been tried in the mouth are also a possible
source of contamination. After the try-in many of these are returned to the laboratory
without disinfection. These contaminate the polishing lathe and the pumice powder used
for polishing which in turn cross-contaminate other restorations and prostheses. Studies
have shown complete dentures are massively contaminated with microorganisms and
can serve as the primary source in the cycle of cross infection within dental laboratories.
The polishing of dentures without previous disinfection leads to a high level of transfer of
microorganisms.
Infection control measures such as the use of barriers during polishing, the disinfection
of dentures before being sent to the laboratory and upon return to the dental clinic, the
disposal or sterilization of the cone after each use, as well as the addition of disinfectants to
pumice and unit doses of pumice should be adopted with the objective of reducing the risk
of cross-infection.

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Section-2

Direct Restorative Materials

Chapter 6 Introduction to Restorations, Luting and Pulp Therapy,  73
Chapter 7 Cavity Liners and Varnish,  80
Chapter 8 Dental Cements,  84
Chapter 9 Dental Amalgam,  128
Chapter 10 Direct Filling Gold,  156
Chapter 11 Resin-based Composites and Bonding Agents,  167

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 6
CHAPTER

Introduction to Restorations,
Luting and Pulp Therapy
Chapter Outline
• Restorations • Types • Types
• Types of Restorations –– Temporary Cementation –– High Strength Bases
–– Temporary Restorations –– Permanent Cementation –– Low Strength Bases
–– Intermediate Restorations • General Requirements of Luting • Properties
• Requirements of a Materials –– Thermal Properties
Temporary Filling • Pulp Capping –– Protection Against Chemical
Material • Criteria for Pulp Capping Insults
• Permanent • Types of Pulp Capping –– Therapeutic Effect
• Direct and Indirect –– Direct Pulp Capping –– Strength
Restorations –– Indirect Pulp Capping • Clinical Considerations
• Esthetic and Nonesthetic –– Indications • Liners and Varnish
• Luting • Bases

This chapter serves as an introduction to restorative dentistry, including cements, liners and
varnish. An emphasis is also placed on the effect of these materials on the pulp.

RESTORATIONS
Tooth material is often lost as a result of caries and trauma. A restoration is a material which
substitutes the missing tooth structure and restores the form and function of the tooth (Fig. 6.1).

TYPES OF RESTORATIONS
Restorations may be classified in a number of different ways.
1. Temporary, intermediate and permanent
2. Direct and indirect
3. Esthetic and nonesthetic

TEMPORARY RESTORATIONS
Temporary restorations are often required
before the placement of a permanent
restoration. Materials used for temporary
restora­tions are expected to last for only a
short period of time, a few days or a few weeks FIGURE 6.1  Restoration of a tooth.
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74  PART 2  Direct Restorative Materials
at most. They serve as an interim restoration while the pulp heals; and/or till the permanent
restoration can be fabri­cated and inserted. At one time gutta-percha (temporary stopping),
a thermoplastic gum that is used to fill root canals was popular for this purpose. However, it
did not adapt well to the cavity walls, microleakage ensued and sensitivity was a common
occurrence.
Because of its excellent initial sealing ability and kind pulpal response, zinc oxide eugenol (ZOE)
is the cement of choice for temporary restorations. This material is particularly useful when
a sedative treatment is required until the pulp has healed well enough for the permanent
restoration to be placed. The Type I ZOE is very popular for sedative treatment, temporary
coverage and temporary cementation. Type III ZOE is used for temporary restorations.

INTERMEDIATE RESTORATIONS
Intermediate or holding type of restoration is particularly used in pedodontics. For example,
in rampant caries, it is desirable to remove all the caries quickly in order to change the oral
health and arrest the caries process. Once the initial ‘clean up’ has been done, the dentist can
proceed with placement of the permanent restorations. The interval be­tween removal of the
caries and completion of final restorative work may take several months. During this time
teeth are protected with a desirable intermediate restoration.
Conventional zinc-eugenol cements used as temporary resto­rations are deficient in toughness.
They have inadequate strength and abrasion resistance to serve for a longer period. As a
result polymer reinforced cement (IRM) is used. Earlier Type II zinc phosphate and Type II or
Type III zinc silicophosphate cements were used. However, these materials were irritating to
the pulp and required more pre­cise cavity preparation and placement time. They are now
replaced by improved ZOE formulations. The combination of sur­face treatment and polymer
reinforcement results in good strength, improved abrasion resistance and toughness. They
can last for a period of one year or more.

REQUIREMENTS OF A TEMPORARY FILLING MATERIAL

1. It should have adequate strength to last a few weeks, but weak enough to be dislodged
easily.
2. It should be easy to insert and remove.
3. It should have adequate seal.
4. It should have antibacterial properties.
5. It should have a therapeutic effect (pain relief, healing, etc.) on the pulp.
6. It should have cariostatic properties.

PERMANENT
The term permanent is not an absolute term. However, it obviously serves to denote
any material that is expected to last much longer than the temporary and inter­mediate
restorations. Therefore, it is expected to have improved properties than the temporary and
intermediate restorations. Examples of permanent restorative materials are direct filling gold,
amalgam (Fig. 6.1), composite resins, glass ionomer cement, as well as porcelain, composite
and cast metal inlays and onlays.
The length of time each material lasts varies on the technical skills of the operator, the material
itself and other patient related factors. A well-made amalgam restoration would probably last
a lifetime or more. On the other hand the composite restoration might have to be replaced
much earlier as a result of wear, fracture or discoloration.
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 Introduction to Restorations, Luting and Pulp Therapy  CHAPTER 6  75
DIRECT AND INDIRECT RESTORATIONS
Direct restorations  These are materials used to build and restore the tooth structure
directly in the mouth. They are usually placed in increments. They are usually soft and plastic
when initially placed and harden later with time. Examples are amalgam, direct filling gold,
composite (can be used both directly and indirectly) and glass ionomer.
Indirect restorations  These are usually fabricated outside the mouth on models of the tooth
and then cemented into place in the mouth. Examples of indirect restorations are porcelain,
composite and cast metal inlays and onlays.

ESTHETIC AND NONESTHETIC

The terms esthetic and nonesthetic are again relative.
Esthetic  An esthetic material is obviously something which is pleasing to an individual.
At one time gold fillings and crowns were considered esthetic. Today, however, an esthetic
material implies any material that is capable of reproducing the color and appearance of a
natural tooth. Examples are resin-based composites, glass ionomer and porcelain restorations.
Nonesthetic  Currently, it denotes any material that is not tooth colored. This includes
amalgam, direct filling gold and metal inlays and onlays.

LUTING
Synonyms  Bonding, cementing
Luting or cementation (Fig. 6.2) is the
process by which crowns, restorations and
other devices are fixed or attached to tooth
structure using an intermediate material
called cement. Cements have multiple uses.
For example, glass ionomer can be used
as a base, luting agent and as a restorative
material. Besides attaching the restoration
a luting agent must also seal the space
between the restoration and the tooth
structure to prevent caries and chemical and FIGURE 6.2  The luting agent attaches as well as seals
bacterial irritation of the tooth and pulp. the space between the restoration and tooth structure.

TYPES
1. Temporary cementation
2. Permanent cementation

TEMPORARY CEMENTATION
Temporary cementation of crowns and fixed partial dentures (FDP) are often required.
Temporary crowns and FDPs are required to stay in place only until the permanent structure
is ready. Therefore, it must be weak enough to be easily removed when the permanent
structure is ready for cementation. In addition, this cement should have some soothing effect
on the pulp of the freshly, prepared vital tooth, which would have been traumatized during
the preparation. Permanent structures (e.g. crowns or FDPs) are also sometimes cemented
temporarily. This allows the patient to take it for a home trial or to observe the pulpal response.
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Once the patient and dentist are satisfied with the results, the restoration is removed and
76  PART 2  Direct Restorative Materials
cemented permanently. An example of such a temporary bonding cement is a zinc oxide
eugenol-based cement (Temp Bond).

PERMANENT CEMENTATION
A permanent cementing material on the other hand should be strong and insoluble in oral
fluids. It would also be advantageous if it had some chemical bonding to the tooth structure.
In addition, it should be fluid enough to flow well to ensure the complete seating of the
restoration.
Examples of permanent cementing materials are zinc phosphate cement, glass ionomer
cement, resin cement, polycarboxylate cement, etc.

GENERAL REQUIREMENTS OF LUTING MATERIALS

1. They should be nontoxic and nonirritant to pulp and tissues.
2. They should be insoluble in saliva and liquids taken into the mouth.
3. Mechanical properties: These must meet the requirements for their particular applications,
e.g. a cement base should develop sufficient strength rapidly to enable a filling material
to be packed on it.
4. Protection of the pulp from insults.
–– Thermal insulation, a cement used under a large metallic restoration should protect
the pulp from temperature changes.
–– Chemical protection, should be able to prevent penetration into the pulp of harmful
chemicals from the restorative material.
–– Electrical insulation under a metallic restoration to reduce galvanic shock.
5. Optical properties: For cementation of a translucent restorations (e.g. porcelain) the
cement should match the color and translucency of tooth substance.
6. Dental cements should ideally be adhesive to both tooth structure and restorative material
(gold alloys, porcelain, etc.), but not to dental instruments.
7. They should be bacteriostatic in a cavity with residual caries.
8. They should have an obtundent (soothing) effect on the pulp.
9. Rheological properties: A luting cement should have sufficiently low viscosity to give a
low film thickness.

PULP CAPPING
Pulp capping is the process of placing a specialized agent in contact with or in close proximity
to the pulp with the intention of encouraging formation of new dentin (secondary dentin)
and promote the healing of the pulp. Prior to the discovery of pulp capping agents, a pulp
exposure often led to irreversible pulpitis or pulpal infection and ultimately pulp necrosis.
Thanks to these pulp capping agents, it became possible to treat pulpal tissue which otherwise
would have had to undergo root canal therapy. Example of a pulp capping agent is calcium
hydroxide cement.

CRITERIA FOR PULP CAPPING

Are all exposed pulps suitable for pulp capping therapy? The answer is obviously no. The
dentist has to apply certain criteria and select his cases carefully.
1. The pulp should be http://dentalebooks.com
healthy and noninfected.
 Introduction to Restorations, Luting and Pulp Therapy  CHAPTER 6  77
2. The area of exposure should be no more than 0.5 mm.
3. Following exposure the dentist should make all attempts to immediately isolate the tooth
and prevent contamination.

TYPES OF PULP CAPPING

A. Direct pulp capping
B. Indirect pulp capping

DIRECT PULP CAPPING

Direct pulp capping is the placement of the agent directly on the exposed pulp (Figs 6.3A
and B). Such a situation is often encountered during
1. The excavation of deep carious lesions when the dentist accidentally exposes the pulp.
2. Traumatic fractures of the tooth.
3. Iatrogenic (caused by treatment) exposure during cavity preparation.
4. Iatrogenic exposure during crown preparation.

INDIRECT PULP CAPPING

Secondary dentin formation can be induced even when the pulp is not exposed but is near
exposure. When the calcium hydroxide is placed in the region of the near exposure, it can still
induce new dentin formation. This is known as indirect pulp capping.

Indications
1. Deep carious lesions close to the pulp.
2. During excessive crown preparation the pulp is often visible through the remaining dentin
as a pinkish or reddish spot or area.
3. Similar near exposures may be seen in cases of traumatic tooth fracture.

BASES
A base is a layer of cement placed beneath a permanent resto­ration to encourage recovery
of the injured pulp and to protect it against numerous types of insults to which it may
be subjected. The type of insults depends upon the particular restorative material. It may
be thermal or chemical or galvanic. The base serves as replacement or substitute for the
protective dentin, that has been destroyed by caries or cavity preparation. Nonvital teeth do
not require a base.

A B
FIGURES 6.3A AND B  (A) Pulp exposure. (B) Direct pulp capping and subsequent secondary dentin
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78  PART 2  Direct Restorative Materials
TYPES
They belong to two categories.

High strength bases

These are used to provide thermal protection for the pulp, as well as mechanical support for
the restoration.
Examples of high strength bases: Zinc phosphate, Zinc polycarboxylate, glass ionomer and
reinforced ZOE cements.
Some important properties of cements used as high strength bases are strength, modulus
of elasticity and thermal conductivity.

Low strength bases

Low strength bases have minimum strength and low rigidity. Their main function is to act as
a barrier to irritating chemicals and to provide therapeutic benefit to the pulp. Examples are:
calcium hydroxide and zinc oxide eugenol.

PROPERTIES

Thermal properties
The base must provide thermal protection to the pulp. This pro­perty is important especially
when the tooth is restored with metallic restorations.
The thermal conductivity of most cement bases is similar to tooth structure and is in the range
of recognized insulators such as cork and asbestos.
For effective thermal protection the base should have minimal thickness of 0.75 mm. A
thin wash of cement would not offer protection against thermal insults through metallic
restorations.

Protection against chemical insults

The cement base also serves as a barrier against penetration of irritating constituents (e.g.
acids, monomer, etc.) from restorative materials. Calcium hydroxide and zinc oxide eugenol
are most effective for this especially in deep (close to the pulp) cavities. Polycarboxylate and
glass ionomer bases are also used as chemical barriers in more moderate cavities.

Therapeutic effect
Some bases are used for their therapeutic benefit to the pulp. For example, calcium hydroxide
acts as a pulp capping agent and promotes the formation of secondary dentin. Zinc oxide
eugenol has an obtundent effect on the pulp.

Strength
The cement base must have sufficient strength to
 Withstand the forces of condensation. Fracture or displace­ment of the base permits the
amalgam to penetrate the base and contact the dentin. Likewise, in deep cavities the
amal­gam may be forced into the pulp through microscopic expo­sures in the dentin.
 Withstand fracture or distortion under masticatory stresses transmitted to it through the
permanent restoration.

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 Introduction to Restorations, Luting and Pulp Therapy  CHAPTER 6  79
Also the cement base should develop sufficient strength rapi­dly in order to allow early
condensation of amalgam. The mini­mum strength requirement of a base is between 0.5 and
1.2 MPa.

CLINICAL CONSIDERATIONS
The base is selected according to
 Design of the cavity
 Type of permanent restorative material used
 Proximity of the pulp to the cavity walls.
With amalgam, calcium hydroxide or zinc oxide eugenol cement is usually sufficient.
In case of direct filling gold where the condensation pressure is higher, a stronger cement is
indicated as base.
With resin restorations, calcium hydroxide is the material of choice, as zinc oxide eugenol
cements interfere with its poly­merization. Glass ionomer cement can also be used as base.

LINERS AND VARNISH

Liners and varnishes are agents in a volatile solvent which when applied to a surface evaporates
leaving behind a thin film. This film acts as a barrier which has different functions depending
on the circumstance and the location where it is applied. These materials are discussed in
more detail in the subsequent chapter.
 7
Chapter

Cavity Liners and Varnish

Chapter Outline
• Cavity Liners • Cavity Varnish –– Precautions
–– Supplied as –– Application –– Clinical Considerations
–– Composition –– Supplied as • Fluoride Varnishes
–– Properties –– Composition –– Composition
–– Manipulation –– Properties –– Manipulation
–– Other Liners –– Manipulation –– Contraindications

CAVITY LINERS
A cavity liner is used like a cavity varnish to provide a barrier against the passage of irritants
from cements or other restorative materials and to reduce the sensitivity of freshly cut dentin.
They are usually suspensions of calcium hydroxide in a volatile solvent. Upon the evaporation
of the volatile solvent, the liner forms a thin film on the prepared tooth surface.

SUPPLIED AS
 Solutions in bottles
 Powder and liquid
 Paste in tubes

Composition
Suspension of calcium hydroxide in an
organic liquid (Fig. 7.1) such as methyl
ethyl ketone or ethyl alcohol. Acrylic
polymer beads or barium sulphate
calcium monofluoro­phosphate.

Properties
Like varnishes, cavity liners neither Figure 7.1 Calcium hydroxide suspension used for cavity
possess mechanical strength nor lining.
provide any significant thermal
insulation. The calcium hydroxide liners are soluble and should not be applied at the
margins of restorations. Fluoride compounds are added to some cavity liners in an
 Cavity Liners and Varnish  Chapter 7  81
attempt to reduce the possibility of secondary caries around permanent restorations or
to reduce sensitivity.

Manipulation
Cavity liners are fluid in consistency and can be easily flowed or painted over dentinal surfaces.
The solvents evaporate to leave a thin film residue that protects the pulp. The paste form is
applied in the cavity and then light cured.

Other Liners
Some other materials have been claimed as liners. These include Type III glass ionomer and ZOE.

CAVITY VARNISH
Cavity varnish is a solution of one or more resins which when applied onto the cavity walls, evaporates
leaving a thin resin film, that serves as a barrier between the restoration and the dentinal tubules.

APPLICATION
1. It reduces microleakage around the margins of newly placed amalgam restorations,
thereby reducing, postoperative sensi­tivity.
2. It reduces passage of irritants into the dentinal tubules from the overlying restoration
or base, e.g. silicate.
3. In amalgam restorations, they also prevent penetration of corrosion products into the
dentinal tubules, thus, minimizing tooth discoloration.
4. Varnish may be used as a surface coating over certain resto­rations to protect them from
dehydration or contact with oral fluids, e.g. silicate and glass ionomer restorations.
5. Varnish may be applied on the surface of metallic restoration as a temporary protection
in cases of galvanic shock.
6. When electrosurgery is to be done adjacent to metallic restorations, varnish applied over
the metallic restor­ations serves as a temporary electrical insulator.
7. Fluoride containing varnishes release fluoride.

SUPPLIED AS
Liquid in regular or-dark colored bottles (Fig. 7.2).
Commercial Names Harvard lac, Chem Varnish, Secura, Fuji Varnish (GC)

COMPOSITION
Natural gum such as copal, resin or synthetic resin dissolved in an organic solvent like alcohol,
acetone, or ether. Medicinal agents such as chlorobutanol, thymol and eugenol may be added.
Some varnishes also contain fluorides.

PROPERTIES
Varnishes neither possess mechanical strength nor provide ther­mal insulation because of
the thin film thickness. The film thick­ness ranges from 2 to 400 µm. The solubility of dental
varnishes is low; they are virtually insoluble in water.
82  Part 2  Direct Restorative Materials

Figure 7.2  Some of the various commercially available varnishes.

MANIPULATION
The varnish may be applied by using a brush, wire loop or a small pledget of cotton. Several
thin layers are applied. Each layer is allowed to dry before applying the next one. When the
first layer dries, small pinholes develop. These voids are filled in by the succeeding varnish
applications. The main objective is to attain a uniform and continuous coating.

PRECAUTIONS
1. Varnish solutions should be tightly capped immediately after use to prevent loss of
solvent by evaporation.
2. It should be applied in a thin consistency. Viscous varnish does not wet the cavity walls
properly. It should be thinned with an appropriate solvent.
3. Excess varnish should not be left on the margins of the resto­rations as it prevents proper
finishing of the margins of the restorations.

CLINICAL CONSIDERATIONS
When placing a silicate restoration, the varnish should be confined to the dentin. Varnish
applied on the enamel inhibits the uptake of fluoride by the enamel.

Contraindications
 Composite resins  The solvent in the varnish may react with the resin.
 Glass ionomer  Varnish eliminates the potential for adhe­sion, if applied between glass
ionomer cement (GIC) and the cavity.
 When therapeutic action is expected from the overlying cement, e.g. zinc oxide eugenol
and calcium hydroxide.

Fluoride varnishes
Fluoride varnishes are used to prevent or arrest tooth decay in smooth surfaces in young
children, especially when applied before age three as their teeth erupt. The taste does not
appear to be offensive so is considered acceptable to young children. The technique is well
accepted by parents. It hardens on contact with saliva and stays in contact with the teeth for
 Cavity Liners and Varnish  Chapter 7  83

A B
Figures 7.3A and B  Two commercially available fluoride varnishes. (A) Duraphat. (B) Fluor Protector.

several hours or days, but is not meant to adhere permanently. Families should be told that
their child can eat and drink afterward but they should not brush the teeth until the next day,
or at least 12 hours later, as it may remove some of the varnish. Most protocols suggest two
applications per year, although some recommend up to four, with the first ones occurring
fairly close together or in the first 1–2 weeks.

Trade names
Commonly used varnishes are Duraphat (Figs. 7.3A and B) (Colgate-Oral Pharma­ceuticals,
Inc), Duraflor (Pharmascience, Inc.), Fluor Protector (Ivoclar-Vivadent) and Cavity Shield (OMNII
- Oral Pharmaceuticals).

Composition
Composition varies depending on the particular brand. It contains concentrated fluoride
dissolved in an organic solvent. One varnish (Colgate Duraphat) contains 22,600 ppm (5%)
sodium fluoride. Another product Fluor Protector (Ivoclar-Vivadent) contains 0.1% fluoride
(Fluorsilane) in ethyl acetate (65%), isoamyl-propionate (21%) and polyisocyanate (12%).

Manipulation
Fluoride varnishes are painted on to the teeth
using a special tiny brush. The teeth are cleaned
with a toothbrush first and then dried with a
gauze square; professional tooth cleaning
with prophylactic paste is not indicated. Some
varnishes are colored for visualization during
placement (Fig. 7.4).

Contraindications
Varnishes should not be used in cavitated
carious lesions because the caries may spread
to other portions of the tooth, but can be used
Figure 7.4  Application of Duraphat varnish.
to remineralize white spot lesions.
 8
CHAPTER

Dental Cements

Chapter Outline
• Classification of Cements Zinc Oxide Eugenol Cement –– Fissure Sealing
–– ISO Standards –– Polymer Reinforced Zinc • Modified Glass Ionomers
–– ISO Classifica­tion Oxide Eugenol Cement –– Metal Modified Gic
• General Structure –– Special Zinc Oxide Eugenol –– Resin-Modified Glass
–– According to Setting Products Ionomer
Reaction –– Endodontic Sealers • Calcium Hydroxide Cement
• Uses of Cements • Zinc Oxide/Zinc Sulphate –– Light Activated Calcium
• General Properties of Cements Hydroxide Cement
Cements • Glass Ionomer Cements –– Calcium Hydroxide Root
• Silicate Cements –– Packable Glass Ionomer for Canal Sealing Pastes
• Zinc Phosphate Cement Posterior Restorations • Resin Cements
• Copper Cements –– Atraumatic Restorative • Compomer
• Zinc Polycarboxylate Dentistry (Art)

Dental cements are materials of multiple uses including restorations, luting and therapeutic.
They are generally materials of comparatively low strength, but have extensive use in
dentistry. The first dental cement is said to have been introduced in 1785 by Sorel who
created the ‘zinc-oxide-chloric-cement’. Nearly a hundred years later Rostain and then Fleck
developed and introduced the zinc phosphate cement. Around the same period silicates
were also developed.
Cements have come a long way since then. Many of them have been improved considerably,
while some like the silicate cements have been discontinued. Some like the glass ionomers
and the polycarboxylate have adhesive properties and form a chemical bond to dentin and
enamel. Regardless of some inferior properties, they possess so many desirable features that
they are widely used in dentistry.

CLASSIFICATION
Cements have a wide variety of uses, properties and reaction mechanisms. This makes them
generally difficult to classify.

ISO standards covering cements

ISO 9917-1:2007 Water-based cements–Part 1: Powder/liquid acid-based cements
ISO 9917-2:2010 Water-based cements–Part 2: Light-activated cements
 Dental Cements  CHAPTER 8  85
ISO 3107:2011 Zinc oxide/eugenol and zinc oxide/noneugenol cements
ISO 4049:2009 Polymer-based filling, restorative and luting materials

ISO classifica­tion
Water-based cements  Zinc phos­phate, glass iono­mer, etc.
Oil-based cements  ZOE and noneugenol cements
Resin or polymer-based cements  Resin cements, compomer, etc.
According to setting reaction
The materials may be classified as
 Acid-base reaction cements
 Polymerizing cements
 Dual cure cements
 Tricure cements
Acid-base reaction cements  They are formulated as powder and liquid. The liquid acts as
the acid and the powder as the base. On mixing the two an acid-base reaction takes placing
resulting in a viscous paste, which hardens to a solid mass.
Polymerizing cements  These cements set by polymerizing reaction which may be light
activated or chemically activated, e.g. resin cements.
Dual and tricure cements  Dual cure cements set by acid base and any one of the
polymerization (light activated or chemically activated) mechanisms. Tricure cements utilize
all three mechanisms for hardening.

Classification of cements based on application (ISO 9917-1:2007)*

a. Luting
b. Bases or lining
c. Restoration

GENERAL STRUCTURE
On mixing the powder and liquid, only a part of the powder reacts with the liquid and the
final set material is composed of
 A core of unreacted powder, surrounded by
 A matrix formed by the reaction product of the powder and the liquid.

USES OF CEMENTS
Cements have a wide variety of usage in dentistry.

Function Cement used

Final cementation Zinc phosphate, zinc silicophosphate, EBA cement, zinc polycarboxylate, glass ionomer,
resin cement
Temporary cementation Zinc oxide eugenol, noneugenol zinc oxide
Bases Zinc phosphate, reinforced zinc oxide eugenol, zinc polycarboxy­late, glass ionomer, zinc
oxide eugenol, calcium hydroxide
(Contd...)
* Current ISO specifications no longer classify cements as Type 1, 2 or 3. The prefix ‘Type’ has been discontinued. Only a single type of luting cement
with a maximum film thickness of 25 μm is described. Medium grain (film thickness 40 μm) from previous editions have been discontinued.
Similarly, only a single class of restorative cement is described; sub-classification (a) esthetic restorative and (b) reinforced restorative cements
have been discontinued.
86  PART 2  Direct Restorative Materials
(Contd...)
Function Cement used
Long-term restorations Glass ionomer, compomer, metal modified GIC
Temporary and intermediate Zinc oxide eugenol, reinforced zinc oxide eugenol, zinc polycarboxylate, glass ionomer
restorations
Pulp therapy Calcium hydroxide
Obtundant (pain relief ) Zinc oxide eugenol
Liners Calcium hydroxide in a suspension
Root canal sealer Zinc oxide eugenol, zinc polycarboxylate

GENERAL PROPERTIES OF CEMENTS

Though cements are formulated to serve a variety of functions, the two most common
applications of dental cements are luting and restorations. Some of the minimum requirements
for water based dental cements are presented in Table 8.1.

NET SETTING TIME

Net setting time is the period of time, measured from the end of mixing, until the material
has set (as per ISO criteria).

STRENGTH
Most cements are comparatively weak when compared to restorative materials like amalgam
and composites. The strength required depends on the application. For example, a cement
used as a base under amalgam should have sufficient strength to withstand condensation
forces. Many dental cements as well as restorative materials continue to gain strength with
time. For this reason patients are often advised to wait at least 2 hours before any food is
placed in the mouth. In addition the side in which the restoration has been placed is avoided
for a further 24 hours period.

MODULUS OF ELASTICITY (MOE)

This is a measure of the stiffness of the cement. Cements under ceramic crowns should have
sufficient stiffness to withstand masticatory loads. A low MOE can result in flexing of the
restoration resulting in fracture.

SOLUBILITY AND DISINTEGRATION

This is an important property as it can determine the long-term survivability of restorations
(Figs. 8.1, 8.2A and B). Solubility and disintegration of the cement at the margins can
eventually lead to problems like inflammation, caries, sensitivity, etc. Most cements exhibit
varying degrees of solubility. ISO specification No. 99171:2007 uses in vitro testing with 0.1
mol/L lactic acid with pH of 2.74. However, a more reliable test would be an in vivo test as
conditions in the mouth are far more complex. Solubility and disintegration can be reduced
by proper manipulation, minimizing the exposure of the cement to the oral environment and
protecting of the cement during setting and the initial 24 hours period.

FILM THICKNESS
Film thickness is an important property especially for luting cements. A thinner film is more
advantageous for luting.
 Dental Cements  CHAPTER 8  87

FIGURE 8.1  One cannot rely entirely on the cement for sealing an open margin. Most cements slowly dissolve and disintegrate
in the oral cavity leading to microleakage and subsequent failure. A good marginal fit of the crown is therefore essential.

A B
FIGURES 8.2A AND B  Cement dissolution. (A) Area of inflammation in relation to the leaking margin (arrow). (B) On removing
the crown, area of cement dissolution is clearly visible (arrows).

1. It improves the seating of the restoration.

2. It helps in greater flow and wetting of the tooth and restoration surface, thus improving
bonding.
3. It minimizes the air spaces and structural defects present in the bulk of the cement.
Film thickness is measured in µm. ISO 9917-1:2007 specifies maximum film thickness for
luting cements as 25 μm.

BIOLOGICAL PROPERTIES
Most cements are placed within the dentin and in many instances in close proximity to the
pulp. Thus it is important that the cement should not be irritant or toxic to the pulp.
PH of the cement  Most cements are acidic. The exceptions are zinc oxide eugenol, calcium
hydroxide and resin cements. The acidity of cements is higher at the time of placement but
gradually decrease with time.
Pulpal response  The pulp response may be classified as mild, moderate or severe. Originally
silicate cement was used as a reference to compare the pulpal response to various cements.
Because of its high acidity, silicates were classed as severe irritant. High acidity can irritate
and sometimes lead to irreversible pulpal damage. In some patients it can cause severe pain
and sensitivity. Monomer present in resin-based cements is also a potential irritant.
Pulp protection  In case of deep cavities and where the cement is classed as an irritant
measures to protect the pulp are indicated.
1. Avoid thin mixes.
2. Pulp protection should be carried out in deep cavities through the use of an intervening
liner or base.
88  PART 2  Direct Restorative Materials

BOX 8.1 

Cements manu­fac­­tured for various appli­ca­tions would have been modi­fied slightly to suit the particular application. For
example, glass ionomer manu­fac­tured for luting may be slightly different from glass ionomer used for restora­tions. Luting
cements are usually more fine grained and have a different powder-liquid ratio. Restora­tive GIC has better translucency
and esthetics when com­pa­red to the luting GIC which may be more opaque.

FLUORIDE RELEASE
Many cements contain fluoride which is gradually released over a period of time to impart
adjacent teeth structure with caries resistance. Glass ionomer is an example of a fluoride
releasing cement.

Fluoride recharging
The process by which a restorative material, specifically glass ionomer cement, absorbs fluoride
from a solution with a high fluoride concentration.

SILICATE CEMENTS
Silicate cements (Fig. 8.3) are said to have been introduced in
1873 by Fletcher as an anterior esthetic filling material. They
were translucent and resembled porcelain in appearance.
Though the initial esthetics was satisfactory, over a period
of time silicates degraded and stained. Leakage around the
margins result in dark margins. Silicates are attacked by oral
fluids and in time degrade.
The average life of a silicate restoration is four years. Some
may last as long as 25 years, others may require replace­ment
FIGURE 8.3  Silicate cement. in a year or even less.
The incidence of secondary caries is markedly less around sili­cate restorations. This is surprising
when considering that severe leakage takes place at its margins. Also the incidence of contact
caries is less when compared to amalgam restorations (contact caries is the term applied
to caries occurring on the proximal surface of the tooth adjacent to the restoration). The
anticariogenic property is due to presence of 15% fluoride. Fluoride release is slow and occurs
throughout the life of the restoration. Silicate cements were classed as a severe irritant to the
pulp because of its low pH (acidic). For many years silicate served as a standard for comparing
the pulpal response to other material. In deep cavities the pulp had to be protected with
varnish or calcium hydroxide.
With the development of better alternate materials like composite resin and glass ionomer
cements, silicates gradually fell out of favor. By the 1980s and 1990s they were gradually
phased out of the market and are rarely used. However, silicate cements are of historical
interest as they were the first tooth colored filling materials. It also forms the basis for the
glass ionomer system.

ZINC PHOSPHATE CEMENT

Zinc phosphate is the oldest of the luting cements and thus serves as a standard with which
newer cements can be compa­red. The terms ‘Crown and Bridge’ and ‘Zinc Oxyphosphate’ have
also been used for this cement.
 Dental Cements  CHAPTER 8  89
APPLICATIONS
1. Luting of restorations (inlays, crowns, fixed dental prostheses, etc.)
2. High strength bases.
3. Temporary restorations.
4. Luting of orthodontic bands and brackets.

CLASSIFICATION
ISO 9917-1:2007 designates them as
a. Luting (Maximum film thickness—25 μm)
b. Bases and lining

AVAILABLE AS
 Powder and liquid system.
 Capsules of preproportioned powder and liquid.
Supplied in shades of yellow, gray, golden brown, pink and white.

Representative commercial products  Confit, Harvard, Zinc cement (DPI), Modern Tenacin,
Poscal (VOCO), De Trey Zinc (Dentsply), Hy Bond, etc. Some representative products are shown
in Figure 8.4.

COMPOSITION

Powder
Ingredient Weight (%) Function
Zinc oxide 90.2 Principal constituent
Magnesium oxide 8.2 Aids in sintering
Other oxides (like bismuth trioxide, calcium 0.2 Improves smoothness of mix
oxide, barium oxide, etc.)
Silica 1.4 Filler, aids in sintering

FIGURE 8.4  Three representative zinc phosphate cements.

90  PART 2  Direct Restorative Materials
Liquid
Ingredient Weight (%) Function
Phosphoric acid 38.2 Reacts with zinc oxide
Water 36.0 Controls rate of reaction
Aluminum phosphate or sometimes zinc phosphate 16.2 Buffers, to reduce rate of reaction
Aluminum 2.5
Zinc 7.1

MANUFACTURE
The ingredients are mixed and heated at temperatures between 1,000 °C and 1,400 °C
(sintering). After sintering, the cake formed is cooled quickly. This causes the material to crack
which helps in grinding of the material to a fine powder. This process is known as fritting.
The liquid is produced by adding aluminum and sometimes zinc or their compounds into
orthophosphoric acid solution.

SETTING REACTION
When the powder is mixed with liquid, phosphoric acid attacks the surface of the particles
and releases zinc ions.
The aluminum in the liquid is essential for cement formation. The aluminum complexes with
the phosphoric acid and the zinc ions to form a zinc aluminophosphate gel. The reaction is
exothermic.

STRUCTURE OF SET CEMENT

The set cement has a cored structure consisting primarily of unreacted zinc oxide particles
embedded in a matrix of zinc aluminophosphate.

BOX 8.2 
NET SETTING TIME
The setting time of cements in general vary
According to ISO 9917-1:2007, the net setting
widely. The set­ting time varies between different
time can vary from 2.5 to 8 minutes for luting manufacturers. Climatic condi­tions too have a
and 2.5 to 6 for base and lining type (Box 8.2). significant effect. Warm humid climatic condi­tions
accelerate the set­ting. The portion of the material
Control of setting time placed in the mouth sets faster than that on the
table. This is because of the warm and moist con­
Manufacturing process di­tions in the mouth.
1. Sintering temperature  The higher the
temperature, the more slowly the cement sets.
2. Particle size  Finer particles react more quickly as a greater surface area is exposed to
the liquid.
3. Water content of liquid  Presence of excess water accelerates, whereas insufficient water
retards the reaction.
4. Buffering agents  When added slow down the reaction.

Factors under control of operator

1. Temperature  Higher temperatures accelerate the reaction. Cooling the mixing slab is
an effective way of slowing the reaction and prolonging the working time.
 Dental Cements  CHAPTER 8  91

BOX 8.3 

When used as a base for an amal­gam or a DFG restoration, the operator must allow the cement to gain sufficient strength
before proceeding with the condensa­tion.

2. Powder-liquid ratio  More the liquid, slower the reaction.

3. Rate of addition of powder to liquid  The reaction is slower if the powder is incorporated
slowly.
4. Mixing time  The longer the mixing time (within practical limits), the slower is the rate
of reaction.

PROPERTIES

COMPRESSIVE STRENGTH
The fully set zinc phosphate cement has a relatively high compressive strength ranging from
104 to 119 MPa. The set cement gains approximately 70% of its maximum strength in the
first 30 minutes. The strength continues to rise with time and maximum strength is attained
at the end of 24 hours (Box 8.3).
The strength of zinc phosphate cement is sufficient when used as a base or luting agent. However,
when it is exposed to the oral environment, e.g. temporary restorations, its brittleness and low
strength causes it to fracture and disintegrate. Also, the prolonged contact with the oral fluids
or water gradually reduces its strength. This may be due to the slow dissolution of the cement.

Factors affecting strength

1. Powder-liquid ratio  More the powder, greater the strength.
2. Water content of the liquid  Both loss or gain, reduces the strength.

TENSILE STRENGTH
The set cement is weaker in tension (5.5 MPa), thus making it brittle.

MODULUS OF ELASTICITY (STIFFNESS)

It is comparatively high (13.7 GPa). This makes it stiff and resis­tant to elastic deformation. This is
beneficial when it is used to cement restorations that are subjected to high masticatory stresses.

SOLUBILITY AND DISINTEGRATION

This property is important for cements used for permanent cementation. When tested
according to ISO specification, maximum solubility permitted is 0.3 (Table 8.1).
However, in the mouth they show greater disintegration over a period of time. This shows that
other factors are involved (like wear, abrasion, chemical attacks by products from decaying
food, etc.). The solubility is greater in dilute organic acids like lactic, acetic and especially
citric acids, all of which are present in the human diet. Thus it is important to minimize the
exposure of the cement in the mouth by having minimum gaps at the margins of restorations.

Factors affecting solubility

1. Powder-liquid ratio  Thicker mixes show less solubility.
2. Water content of liquid  Any change in the water content is accompanied by increased
solubility.
92  PART 2  Direct Restorative Materials
3. Effect of moisture contamination  Premature contact of the incompletely set cement with
water results in the dissolu­tion and leaching of the surface. Varnish application over the
exposed cement margin is beneficial.

FILM THICKNESS
The smaller the particle size, less is the film thickness. The thickness is lesser than the size of
the particles because, during mixing the particles are crushed and dissolved. The thickness
can also be reduced by applying pressure on the casting during seating.

THERMAL PROPERTIES
Zinc phosphate cements are good thermal insulators and may be effective in reducing
galvanic effects.

ADHESION PROPERTY
The primary retentive mechanism of zinc phosphate is micromechanical. The cemented
restoration is held by mechanical interlock­ing of the set cement with surface roughness on
the tooth and restoration.

BIOLOGICAL PROPERTIES
pH of the cement  The acidity is high at the time of insertion due to phosphoric acid. At the
time of cementation, the pH is 2 (approx.). As time passes the acidity reduces. By the end of
24 hours the pH is 5.5, which is still in the acidic range (neutral value is 7).
Pulpal response  The pulp response may be classified as moderate.
Pulp protection  A thickness of dentin as great as 1.5 mm can be penetrated by the acid of
the cement. If dentin is not protected against infiltration of this acid, pulpal injury may occur,
especially during the first few hours.
1. Avoid thin mixes.
2. Pulp protection should be carried out in deep cavities through the use of an intervening
liner or base
–– Zinc oxide eugenol
–– Calcium hydroxide
–– Cavity varnish
3. Some patients are extremely sensitive to the acid. Cementation of a restoration such as a
crown or FDP on to vital teeth can cause severe sensitivity or pain. An anesthesia should
be used in these instances.

OPTICAL PROPERTIES
The set cement is opaque.

MANIPULATION
Spatula used  Stainless steel.
Mixing time  1 min. 15 seconds.
Powder to liquid ratio 1.4 g/0.5 mL
A cool glass slab is used in order to delay the setting and allow more powder to be incorporated
before the matrix formation occurs. The liquid should be dispensed just before mixing.
 Dental Cements  CHAPTER 8  93
Procedure
The powder is added in small increments. Mixing is done with stainless spatula using brisk
circular motion. Each increment is mixed for 15 to 20 seconds. A large area is covered during
mixing in order to dissipate the exothermic heat (Figs. 8.5A and B). Maximum amount of
powder should be incorporated in the liquid to ensure minimum solubility and maximum
strength. Note: An appropriate consistency is attained by addition of more powder to the
liquid and not by allowing a thin mix to thicken.

Insertion
The crown should be seated immediately and held under pressure till set. Field of operation
should be dry. Varnish is applied at the margins, where the cement is exposed.

ADVANTAGES AND DISADVANTAGES OF ZINC PHOSPHATE

Advantages
1. Long track record with proven reliability.
2. Good compressive strength.

Disadvantages
1. No chemical adhesion. Not indicated if the retention is poor.
2. No anticariogenic property.
3. Pulp irritation.
4. Poor esthetics; cannot be used with translucent (all ceramic) restorations like crowns
and veneers.

COPPER CEMENTS
Copper cements are basically modified zinc phosphate cements. Silver salts or copper
oxide are sometimes added to the powders of the zinc phosphate cements to increase their
‘antibacterial’ properties. Copper cements gradually fell out of favor because of their poor
biological properties. It was highly acidic and the copper was considered toxic to the cell.
This may have been due to the extremely high copper content (97%) in certain cements
(Ames). There has been a renewed interest in copper cements recently. New formulations
have come out with lower copper content (2%). It is claimed that these new generation
copper cements are safe and is especially recommended for indirect pulp capping and
where there is active caries.

A B
FIGURES 8.5A AND B  Manipulation of zinc phosphate. (A) The cement is mixed over a large
area to dissipate heat. (B) Luting consistency.
94  PART 2  Direct Restorative Materials
APPLICATIONS
1. Temporary fillings in children.
2. Intermediate restorations.
3. For retention of silver cap splints in oral surgery.
4. Indirect pulp capping.
5. As base beneath composite restorations.

CLASSIFICATION
Classified according to the percentage of the copper oxide that is used as a replacement for
the zinc oxide.
Commercial examples  Ames copper (discontinued), Doc’s best red and white copper kit
(Fig. 8.6).

COMPOSITION
 Copper oxide (if cuprous oxide is used—cement is red, if cupric oxide is used, the cement
is black)
 Zinc oxide
 Liquid used is clear phosphoric acid

PROPERTIES
1. Biological properties: They have poor biological properties. Because its pH is 5.3, it is
irritant to the pulp.
2. They are bactericidal or bacteriostatic.

MANIPULATION
The chemistry of the copper cements is very similar to that of the zinc phosphate cements
and they are manipulated in the same manner.

ZINC POLYCARBOXYLATE CEMENT

Canadian biochemist Smith developed the first polycarboxylate cement in 1968 by substituting
the phosphoric acid of zinc phosphate cement with polyacrylic acid. Polycarboxylate became
the first cement system developed with potential for adhesion to tooth structure.

FIGURE 8.6  White and red copper cements.

 Dental Cements  CHAPTER 8  95
APPLICATIONS
1. Primarily for luting permanent restorations.
2. As bases and liners.
3. Used in orthodontics for cementation of bands.
4. Also used as root canal fillings in endodontics.

AVAILABLE AS
 Powder and liquid in bottles (Fig. 8.7A)
 Water settable cements (Fig. 8.7B)
 As precapsulated powder/liquid system

Commercial Examples  Poly F (Dentsply), Durelon and Durelon Maxicap (encapsulated) (3M
ESPE), Carboco (Voco), Imibond P (Imicryl), Hy Bond polycarboxylate (Shofu).

Water settable cements

In these cement the polyacid is freeze dried and added to the cement powder. Water is used
as the liquid. When the powder is mixed with water, the polyacrylic acid goes into the solution
and the reaction proceeds as described for the conventional cements.

COMPOSITION
Powder
Ingredient Function
Zinc oxide Basic ingredient
Magnesium oxide Principal modifier and also aids in sintering
Oxides of bismuth and aluminum Small amounts
Stannous fluoride Increases strength, modifies setting time and imparts anti-
cariogenic properties

Liquid
Aqueous solution of polyacrylic acid or copolymer of acrylic acid with other unsaturated
carboxylic acids, i.e. itaconic, maleic, or tricarballylic acid.

A B
FIGURES 8.7A AND B  (A) Representative zinc polycarboxylate cement products. (B) A water settable cement.
96  PART 2  Direct Restorative Materials
MANUFACTURE
The powder mixture is sintered at high temperature in order to reduce the reactivity and then
ground into fine particles.

SETTING REACTION
When the powder and liquid are mixed, the surface of powder particles are attacked by the acid,
releasing zinc, magnesium and tin ions. These ions bind to the polymer chain via the carboxyl
groups. They also react with carboxyl groups of adjacent polyacid chains to form cross-linked salts.

Structure of set cement

The hardened cement consists of an amorphous gel matrix of zinc polyacrylate in which
unreacted powder particles are disper­sed.

PROPERTIES
Mechanical properties
Compressive strength  ISO requires a minimum compressive strength of 50 MPa for this cement
(Table 8.1). Polycarboxylate cement is inferior to zinc phosphate cement in this respect.
Tensile strength  6.2 MPa. Its tensile strength is slightly higher than that of zinc phosphate cement.
The strength of the cement depends on
 Increase in P/L ratio increases strength.
 Molecular weight of polyacrylic acid also affects strength. A mix from a lower viscosity
liquid is weaker.

Solubility and disintegration

It tends to absorb water and is slightly more soluble (0.6% wt) than zinc phosphate. Thus the
marginal dissolution is more when used for cementing. It is more soluble in organic acids
like lactic acid. Low P/L ratio results in a significantly higher solubility and disintegration in
the oral cavity.

Biocompatibility
Pulpal response is classified as mild. Despite the initial acidic nature of polycarboxylate cement,
the pH of the liquid is 1.0–1.7 and that of freshly mixed cement is 3.0–4.0. After 24 hours, pH
of the cement is 5.0-6.0.
They are less irritant than zinc phosphate cement because:
 The liquid is rapidly neutralized by the powder. The pH of polycarboxylate cement rises
more rapidly than that of zinc phosphate.
 Penetration of polyacrylic acid into the dentinal tubules is less because of its higher
molecular weight and larger size. The histological reactions are similar to zinc oxide
eugenol cements but more reparative dentine is observed with polycarboxylate.

Adhesion
An outstanding characteristic of zinc polycarboxylate cement is that the cement bonds
chemically with the tooth structure. The carboxyl group in the polymer molecules chelates
with calcium in the tooth structure.
Bond strength to enamel is 3.4–13.1 MPa and to dentine 2.07 MPa.
 Dental Cements  CHAPTER 8  97

TABLE 8.1  Requirements for water based dental cements (ISO 9917-1:2007)
Chemical type Application Film Net setting Com- Acid Opacity Acid- Acid
thickness time pressive erosion C0,70 soluble soluble
mm min strength mm As Pb
MPa content content
mg/kg mg/kg
max. min. min. max. min. max. max. max.
Zinc Luting 25 2.5 8 50 0.30 2 100
phosphate
Zinc polycarboxylate Luting 25 2.5 8 50 0.40 2 100
Glass polyalkenoate Luting 25 1.5 8 50 0.17 100

Zinc Base/lining 2 6 50 0.30 2 100

phosphate
Zinc polycarboxylate Base/lining 2 6 50 0.40 2 100
Glass polyalkenoate Base/lining 1.5 6 50 0.17 100

Glass polyalkenoate Restoration 1.5 6 100 0.17 0.35 0.90 100

Factors affecting bond

1. A clean dry tooth surface improves bonding.
2. If the inside surface of the metal crown is not clean, the cement cannot bond with the
metal. So to improve the mechanical bond, the surface should be carefully abraded with
a small stone or with airborne abrasives.
3. The presence of saliva reduces bond strength.
4. Unlike zinc phosphate cements, the adhesion is better to a smooth surface than to a
rough surface.
5. Does not adhere to gold or porcelain.
6. Adhesion to stainless steel is excellent. Thus it is used in orthodontics.

Optical properties
They are very opaque due to large quantities of unreacted zinc oxide.

Anticariogenic properties
Some manufacturers have attempted to incorporate fluoride within the cement. However,
the fluoride release is limited when compared to glass ionomer cement.

Thermal properties
They are good thermal insulators.

MANIPULATION
CONDITIONING
The tooth structure should be meticulously clean for proper bond­ing. To clean the surface,
10% polyacrylic acid solution followed by rinsing with water, or 1 to 3% hydrogen peroxide
may be used. Then dry and isolate the tooth.
98  PART 2  Direct Restorative Materials
PROPORTIONING
1.5 parts of powder to 1 part of liquid by weight.

PROCEDURE
The powder and liquid are taken on a cooled glass slab. The liquid is dispensed just prior to
the mixing, otherwise its viscosity increases. The powder is incorporated into the liquid in bulk
(90%) with a stiff cement spatula and remaining powder is added to adjust consistency. The mix
appears quite thick, but this cement will flow readily into a thin film when seated under pressure.

MIXING TIME AND SETTING TIMES

Mixing time ranges from 30 to 40 seconds. Setting time can be from 7 to 9 minutes (The setting
time can be increased by cooling the glass slab. It also depends on method of manufacture
of powder and liquid).

Points to note
 The cement should be used while the surface is still glossy. Loss of lustre indicates that
the setting reaction has progres­sed to an extent that proper wetting of the tooth surface
by the mix is no longer possible. If the surface is not creamy and shiny and is matted and
tends to form cobwebs, the mix should be discarded.
 After insertion the excess is not removed immediately as it passes through a rubbery stage,
it tends to get lifted from the cavity. Remove excess cement only when it has hardened
and breaks off.
 The powder may be cooled, but the liquid should not be cooled since the viscosity of
the liquid increases.
Polycarboxylate cement adheres to instruments
 Use alcohol as release agent for mixing spatula.
 Instruments should be cleaned before the cement sets.
 Excess cement from the spatula can be chipped off. Any remaining material is removed
by boiling in sodium hydroxide solution.

ADVANTAGES AND DISADVANTAGES

Advantages
1. Comparatively less irritating to the pulp.
2. Chemical bond to tooth structure.

Disadvantages
Limited fluoride release when compared to GIC.

ZINC OXIDE EUGENOL CEMENT

These cements have been used extensively in dentistry since the 1890s. Depending on their
use they vary widely in their proper­ties. In general, they are cements of low strength. They
are the least irritating of all dental cements and are known to have an obtundant (sedative)
effect on exposed dentin.
 Dental Cements  CHAPTER 8  99

B C
FIGURES 8.8A TO C  (A) Type I zinc oxide eugenol for temporary cementation. (B) Type II zinc oxide eugenol
cement for temporary restorations. (C) Type II zinc oxide eugenol—cavity liner (was previously Type IV).

To improve the strength many modified zinc oxide eugenol cements have been introduced,
e.g. EBA—alumina modified and polymer—reinforced zinc oxide eugenol cements non-
eugenol zinc oxide cements are also available. They are suitable for patients sensitive to eugenol.

CLASSIFICATION (ISO 3107:2011)*

Type I—for temporary cementation
Type II —for bases and temporary restorations
The previous version of this classification (ISO 3107:2004) * listing 4 classes, has been replaced
by ISO 3107:2011, in which only 2 classes are described. (See also foot note **)
Type I cements are meant for short term luting (1 to 6 weeks—Fig. 8.8A). They are used to
cement provisional restorations for the period it takes to make the definitive restoration.
Permanent restorations are also sometimes cemented for a short period for the patient to
try it. They have low strength which allows easy removal of the restoration without damage
to the restoration or the tooth.
Type II cements are used for the interim period (few weeks to few months) when a tooth is
undergoing treatment or until it is ready for a permanent restoration. They can also be used
as bases under non-resin based permanent restorations.

AVAILABLE AS
 Powder and liquid (Fig. 8.8B)
 Two paste system (Fig. 8.8C)

* ISO 3107:2004: Type I ZOE — Temporary cementation: Class I — Setting cement, Class II — non-setting cement; Type II ZOE — Permanent
cementation; Type III ZOE — Bases and temporary restorations;Type IV ZOE — Cavity liners
** A version of this classification in a popular US reference book described as ISO 3107 (Type I to Type IV with Type IV listed as intermediate filling),
could not be verified in any of the original ISO sources.
100  PART 2  Direct Restorative Materials
Representative commercial names
Unmodified EBA modified Polymer modified Noneugenol
Type I TempBond TempBond clear Nogenol, Zone Freegenol
TempBond NE
Type II DPI zinc oxide SuperEBA IRM, Kalzinol
Cavitec (Kerr)

COMPOSITION
Powder
Ingredient Weight (%) Function
Zinc oxide 69.0 Principal ingredient
White rosin 29.3 To reduce brittleness of set cement
Zinc stearate 1.0 Accelerator, plasticizer
Zinc acetate 0.7 Accelerator, improves strength
Magnesium oxide Is added in some powders, acts with eugenol in a similar manner as
zinc oxide

Liquid
Ingredient Weight (%) Function
Eugenol 85.0 Reacts with zinc oxide
Olive oil 15.0 Plasticizer
*Some powders may contain arsenic. ISO 3107 specifies maximum permissible arsenic content of 2 mg/kg.

SETTING REACTION
The setting reaction and microstructure are the same as that of the zinc oxide eugenol
impression pastes.
In the first reaction hydrolysis of zinc oxide takes place. Water is essential for the reaction
(dehydrated zinc oxide will not react with dehydrated eugenol).
ZnO + H2O → Zn(OH)2
The reaction proceeds as a typical acid-base reaction.
Zn(OH)2 + 2HE → ZnE2    +   2H2O
Base Acid Salt
(Zinc hydroxide) (Eugenol) (Zinc eugenolate)
The chelate formed is an amorphous gel that tends to crys­tallize imparting strength to the set mass.

Structure of set cement

Thus, the set cement consists of particles of zinc oxide embedded in a matrix of zinc
eugenolate.

TABLE 8.2  Requirements of ZOE cement as per ISO 3107:2011

Type Setting time at 37 °C Compressive strength at 24/h Film thickness Acid-soluble arsenic mass fraction
min MPa μm mg/kga
min. max. min. max. max. max.
Type I 1,5 10 35 25 2
Type II 1,5 10 5 N/A 2
 Dental Cements  CHAPTER 8  101
GENERAL PROPERTIES OF ZINC OXIDE EUGENOL CEMENTS
Mechanical properties
Compressive strength  They are relatively weak cements. The strength depends on what it
is used for, e.g. cements intended for temporary purposes like temporary restorations and
cementation will have a lower strength. The compressive strength, therefore, ranges from a
low of 5 to 55 MPa. Minimum requirements are presented in Table 8.2.
Type I 6 to 28 MPa (ISO—maximum of 35 MPa)
Type II 45 to 55 MPa (ISO—minimum of 5 MPa)
Particle size affects the strength. In general the smaller the particle size, the stronger the
cement. The strength can also be increased by reinforcing with alumina-EBA or polymers (see
EBA and polymer modified ZOE cements).
Tensile strength  Ranges from 0.32 to 5.3 MPa.
Modulus of elasticity (0.22 to 5.4 GPa)  This is an important property for those cements
intended for use as bases.

Thermal properties
Thermal conductivity  3.98 [Cal. Sec-1 cm-2 (°C/cm)-1] × 10–4. Their thermal insulating
properties are excellent and are approximately the same as for human dentin. The thermal
conductivity of zinc oxide eugenol is in the range of insulators like cork and asbestos.
Coefficient of thermal expansion  35 × 10–6/°C.

Solubility and disintegration

The solubility of the set cement is highest among the cements (0.4 to 1.5 % wt). They
disintegrate in oral fluids. This break down is due to hydrolysis of the zinc eugenolate matrix
to form zinc hydroxide and eugenol. Solubility is reduced by increasing the powder/liquid
(P/L) ratio.

Film thickness
This property is important for those cements (Type I) used for luting of restorations. The film
thickness of zinc oxide eugenol cements (ISO maximum of 25 µm) is generally higher than
other cements.

Adhesion
They do not adhere well to enamel or dentin. This is one reason why they are not often used
for final cementation of crowns and other fixed dental prosthesis. The other reasons are low
strength and high solubility.

Biological properties
1. pH and effect on pulp (pH is 6.6 to 8.0): They are the least irritating of all cements. Pulpal
response—classified as mild.
2. Bacteriostatic and obtundent properties: They inhibit the growth of bacteria and have
an anodyne or soothing effect (obtundent) on the pulp in deep cavities, reducing pain.
3. Eugenol is irritating to skin and eyes. Repeated contact may cause allergic dermatitis.

Optical properties
The set cement is opaque.
102  PART 2  Direct Restorative Materials
Material interactions
Eugenol interferes with the hardening/and or cause softening of resin based restorations and
are therefore contraindicated as a base under these restorations.

MANIPULATION
Powder/liquid system
Powder/liquid ratio  4:1 to 6:1 by weight.
The bottles are shaken gently. Measured quantity of powder and liquid is dispensed onto
a cool glass slab. The bulk of the powder is incorporated into the liquid and spatulated
thoroughly in a circular motion with a stiff bladed stainless steel spatula. Zinc oxide eugenol
exhibits pseudothickening. Although it appears to thicken early during spatulation. Further
vigorous spatulation or stropping loosens the mix. Smaller increments are then added until
the mix is complete.
For temporary restorations a thick putty-like consistency is recommended.
Oil of orange is used to clean eugenol cement from instruments.

Two paste system

Equal lengths of each paste are dispersed and mixed until a uniform color is observed.

Setting time
4–10 minutes.
ZOE cements set quicker in the mouth due to moisture and heat.

Factors affecting setting time

The complete reaction between zinc oxide and eugenol takes about 12 hours. This is too slow
for clinical convenience.
1. Manufacture The most active zinc oxide powders are those formed from zinc salts like
zinc hydroxide and zinc carbonate by heating at 3,000 °C.
2. Particle size Smaller zinc oxide particles set faster.
3. Accelerators Alcohol, glacial acetic acid and water.
4. Heat Cooling the glass slab, slows the reaction.
5. Retarders The set can be retarded with glycol and glycerine
6. Powder to liquid ratio Higher the ratio, faster the set.

MODIFIED ZINC OXIDE EUGENOL CEMENTS

These were introduced to improve some of the shortcomings of the regular unmodified zinc
oxide eugenol. The modified ZOE cements are
 EBA-Alumina modified cements
 Polymer reinforced

EBA-ALUMINA MODIFIED CEMENTS

These are modified ZOE cements (Fig. 8.9). It is available as a white powder and a pinkish liquid.
Its greater strength allows its use as an intermediate filling material and as a base. A part of
the liquid is substituted by orthoethoxy benzoic acid. Alumina is added to the powder. These
 Dental Cements  CHAPTER 8  103
cements are increasing in popularity as a retrograde
filling material because of the high cost of MTA.

USES
1. Long-term cementation.
2. Temporary and intermediate restorations.
3. Root end filling material. FIGURE 8.9  EBA cement.

COMPOSITION
Powder Liquid
Ingredient Weight (%) Ingredient Weight (%)
Zinc oxide 60–75 EBA
(orthoethoxy benzoic acid) 62.5
Fused Quartz or Alumina 0–35 Eugenol 37.5
Hydrogenated Rosin 6

PROPERTIES
Their properties are better than that of unmodified ZOE. They are more easier to handle and
have improved carvability.
1. Compressive strength is higher—55 to 60 MPa (8000 psi)
2. Tensile strength—4.1 MPa (600 psi)
3. Modulus of elasticity—2.5 GPa (0.36 psi × 106)
4. Film thickness—25 µm
5. Solubility and disintegration in water—0.05% wt. Despite their low solubility, these
cements disintegrated and wore more quickly clinically when compared to the polymer
modified zinc oxide cements.
6. Effect on pulp—these cements are relatively mild to the pulp.
7. Adhesion—these materials adhere well to tooth structure.

MANIPULATION
A glass slab is recommended for EBA-alumina modified cements. After dispensing, the
powder is incorporated into the liquid in bulk, kneaded for 30 seconds and then stropped for

FIGURE 8.10  IRM and Kalzinol are two popular resin modified zinc oxide cements for
intermediate restorations (Type II).
104  PART 2  Direct Restorative Materials
an additional 60 seconds with broad strokes of the spatula to obtain a creamy consistency.
They have long working times.

Setting time
9.5 minutes.

POLYMER REINFORCED ZINC OXIDE EUGENOL CEMENT

The modifications take the form of resins added to the powder or the liquid. The aim is to
improve the strength and reduce the solubility of the cement. Resin-modified cements are
among the strongest of the zinc oxide eugenol based cements. Their high strength and low
wear make them ideal intermediate restorative materials that can last as long as 1 year.

USES
1. Luting agent
2. As base
3. As temporary filling material
Available as  1. Powder and liquid. 2. Capsule for mechanical mixing.
Commercial Names  IRM (Dentsply) and Kalzinol (DPI) (Fig. 8.10).

COMPOSITION
Powder Liquid
Ingredient Weight (%) Ingredient Weight (%)
Zinc oxide 80 Eugenol
Finely divided natural or synthetic resins 20 Acetic acid Accelerator
Thymol Antimicrobial

The zinc oxide powder is surface treated. The combination of surface treatment and polymer
reinforcement results in good strength, improved abrasion resistance and toughness.

SETTING REACTION
The setting reaction is similar to zinc oxide eugenol cements. Acidic resins if present, may
react with zinc oxide, strengthening the matrix.

PROPERTIES
These cements have improved mechanical properties.
 Compressive strength: 48 MPa (7000 psi)
 Tensile strength: 4.1 MPa (600 psi)
 Modulus of elasticity: 2.5 GPa
 Film thickness: 32 µm
 Solubility and disintegration: 0.03% wt
 Material interactions: Similar to ZOE these materials interfere with the hardening/ and or
cause softening of composites and are therefore contraindicated as a base under resin
based restorations.
 Pulp response: Classified as moderate which is similar to unmodified ZOE.
 Improved abrasion resistance and toughness.
 Dental Cements  CHAPTER 8  105
MANIPULATION
The proper powder/liquid is dispensed on a dry glass slab. 50 percent of the powder is mixed
into the liquid and the remainder in small portions with vigorous spatulation or stropping.
The mix will appear quite stiff, however continued stropping for an additional 5 to 10 seconds
improves plasticity (known as shear thinning effect).
After mixing, the plastic zinc oxide eugenol is swiped into the tooth cavity and condensed
using a moist cotton pellet.
Working time  These cements have a long working time.
Setting time  6 to 10 minutes. Heat and moisture in the mouth cause it to set faster than
on the mixing pad.

Factors affecting setting time

1. Low powder-liquid ratio increases setting time
2. Moisture accelerates setting time.
3. Cooling the glass slab slows the setting.

OTHER ZINC OXIDE EUGENOL PRODUCTS

ENDODONTIC SEALERS
Zinc oxide eugenol is very popular as an endodontic sealer. Two traditional formulations—
Rickert’s formula and Grossman’s formula are very popular. Along with gutta-percha, these
materials are used in endodontic therapy to seal the canals. Some materials are used as
therapeutic sealers and are formulated with ingredients such as iodoform, paraformaldehyde or
trioxymethylene which have therapeutic value. Others contain antibiotics such as tetracyclines
and steroids as anti-inflammatory agents. Some formulations can also be used for pulp capping.
Endodontic sealers also contain radiopaque materials such as barium sulphate, bismuth salts
or silver powder. These products are discussed in further detail in a subsequent section.

ZINC OXIDE/ZINC SULPHATE CEMENTS

These are single component temporary filling materials. Their main advantage is their ease
of placement.

SUPPLIED AS
As putty in small tubes, syringes or plastic containers (Fig. 8.11).
Representative products  Cavit (ESPE), Caviton (GC), Coltosol (Coltene).

FIGURE 8.11  Various zinc oxide/

sulphate temporary restorations.
106  PART 2  Direct Restorative Materials
USE
Short-term restorations after caries excavation, root canal therapy, etc.

COMPOSITION
 Zinc oxide 40–60 %
 Zinc sulphate-1-hydrate 1–20 %
 Calcium sulphate-hemihydrate 15–35 %
 Ethylene bis (oxyethylene) diacetate - 15–35 %
 Barium sulphate 0–20 %
 Poly (vinyl acetate)
 Diatomaceous earth

SETTING REACTION
The material sets by reacting with water which it absorbs from the mouth or from the cavity.
The setting occurs slowly. It expands on setting.

PROPERTIES
It may be white or pink colored putty-consistency material. It has good initial sealing. Since
it expands on setting (up to 18%), the marginal seal is further improved. The seal gradually
decreases with time as it disintegrates. Unfortunately, the strength is low and its life is short.
The material should be used for not more than 1 to 2 weeks. It slowly disintegrates with time
and is therefore not indicated for any longer term temporary restorations. The material is
radiopaque. Short-term pain may be experienced because of dehydration of the cavity.

MANIPULATION
The material is dispensed and inserted into the cavity using a cement carrier. The container
should be closed immediately. It is condensed into the cavity using a plastic filling instrument
(condenser). Since it sets by hydration, the cavity should not be fully dried before placing the
material.

Setting time
The surface hardens in about 20 to 30 minutes. Complete hardening takes place in 2 to 3
hours.

GLASS IONOMER CEMENTS

Glass ionomer cements are adhesive tooth-colored anticariogenic restorative materials which
were originally used for restorations of eroded areas. Current glass ionomers have been
modified to allow a wider application. These cements evolved from a general dissatisfaction
with silicate cements. The first usable glass ionomer system was formulated in 1972 by Wilson
and Kent and was known as ASPA. Subsequently great improvements were made and today
these materials are very popular and widely used.
It was named glass ionomer because, the powder is a type of glass and the setting reaction and
adhesive bonding to tooth structure is due to ionic bond. Unlike other restorative materials,
this cement requires mini­mal cavity preparation as it bonds adhesively to tooth structure.
Compared to composite resin they are less technique sensitive. Glass ionomer cement is often
 Dental Cements  CHAPTER 8  107
known as a biomimetic material, because of its similar mechanical
properties to dentine. For this reason it is one of the most popular
cements in dentistry.
Synonyms
 Poly (alkenoate) cement
 GIC (glass ionomer cement)
 ASPA (alumino silicate polyacrylic acid)

APPLICATION
1. Anterior esthetic restorative material for Class III cavities.
2. Restorative material for eroded areas and Class V restorations
FIGURE 8.12  A four-
(Fig. 8.12). year-old glass ionomer
3. As a luting agent for restorations and orthodontic brackets. restoration.
4. As liners and bases.
5. For core build up.
6. To a limited extent as pit and fissure sealants.
7. Intermediate restorative material.
8. Atraumatic restorative treatment (ART) technique.
Glass ionomer cements are not recommended for Class II and Class VI restorations, since they
lack fracture toughness and are susceptible to wear.

CLASSIFICATION
The general ISO classification of cements apply to glass ionomer (ISO 9917-1:2007)*
a. Luting
b. Bases and liners
c. Restorations
Difference between various types
The various types of GIC cements are chemically identical. They vary primarily in the powder/
liquid ratio and particle size. The GICs used for luting have a lower powder/liquid ratio and
a smaller particle size when compared to the restorative variety. These features enable the
luting GIC to have a thinner film and better flow.
They may also be classified as
1. Conventional GIC
2. Resin-modified GIC
3. Metal-modified GIC
Representative commercial products
Aquacem, Fuji I — Luting
Ketac bond — Bases and liners
Chem Fil, Fuji II — Restorations
Vitra bond — Light cure GIC

AVAILABLE AS
1. Powder/liquid in bottles (Figs. 8.13 and 8.14)
* see footnotes on page 85
108  PART 2  Direct Restorative Materials

FIGURE 8.13  Representative glass ionomer luting cements (Type I).

2. Preproportioned powder/liquid in capsules

3. Light cure system
4. Powder/distilled water (water settable type)

COMPOSITION
Powder
The powder is an acid-soluble calcium fluoroaluminosilicate glass. It is similar to that of silicate,
but has a higher alumina-silica ratio. This increases its reactivity with liquid.
Ingredient Weight (%)
Silica (SiO)2 41.9
Alumina (Al2O3) 28.6
Aluminum fluoride (AlF3) 1.6
Calcium fluoride (CaF2) 15.7
Sodium fluoride (NaF) 9.3
Aluminum phosphate (AlPO4) 3.8

The fluoride component acts as a ‘ceramic flux’. Lanthanum, strontium, barium or zinc oxide
additions provide radiopacity.

Liquid
Originally the liquid was a 50% aqueous solution of polyacrylic acid. It was very viscous and
had a tendency to gel. Modern glass ionomer liquids are in the form of copolymers.
Component Function
Polyacrylic acid in the form of copolymer Copolymerizing with itaconic, maleic acid, etc. tends to
with itaconic acid, maleic acid and increase reactivity of the liquid, decrease viscosity and
tricarballylic acid reduce tendency for gelation.
Tartaric acid Improves the handling characteristics, increases working time
and shortens setting time.
Water Water is the most important constituent of the cement liquid,
it is the medium of reaction and it hydrates the reaction
products. The amount of water in the liquid is critical. Too
much water results in a weak cement. Too little water impairs
the reaction and subsequent hydration.
 Dental Cements  CHAPTER 8  109
Water settable cements
The polyacrylic acid copolymer is freeze dried and then added
to the glass ionomer powder. The liquid is water or water with
tartaric acid. An example of a water settable cement is shown
in Figure 8.14.
When the powder is mixed with water, the polyacrylic acid
powder goes into solution to form liquid acid. Then the chemical
reaction takes place as in the conventional powder and liquid
systems. These cements are known as water settable cements
FIGURE 8.14  Water settable
and they set faster than those with polyacrylic acid. glass ionomer luting cement.

MANUFACTURE
The components are sintered at 1100 °C to 1500 °C. The glass is then ground to particle sizes
ranging from 15 to 50 um.

SETTING REACTION
Leaching  When the powder and liquid are mixed together, the acid attacks the glass particles.
Thus calcium, aluminum, sodium and fluoride ions leach out into the aqueous medium.
Calcium cross-links  The initial set occurs when the calcium ions cross-links (binds) the
polyacrylic acid chains. This forms a solid mass.
Aluminum cross-links  In the next phase, the aluminum also begins to cross-link with
polyacrylic acid chains.
Sodium and fluorine ions  These ions do not take part in the cross-linking. Some of the sodium
ions may replace the hydrogen ions in the carboxylic groups. The rest combine with fluorine
to form sodium fluoride which is uniformly distributed within the cement.
Hydration  Water plays a very important role in the cement. Initially it serves as the medium.
Later it slowly hydrates the matrix, adding to the strength of the cement (maturation process).
Silica gel sheath  The unreacted glass (powder) particle is sheathed (covered) by a silica gel.
It is formed by the leaching of the ions (Ca²+, Al³+, Na+, F¯) from the outer portion of the glass
particle.

Structure of set cement

The set cement (Fig. 8.15) consists of
agglomeration of unreacted powder
particles surrounded by a silica gel sheath
and embedded in an matrix of hydrated
calcium and aluminum cross-linked
polyacrylic gel.

Sensitivity to air and moisture

Exposure of the cement to water before FIGURE 8.15 Representation of structure of set glass
the hardening reaction is complete, leads ionomer.
to loss of cations and anions which form
the matrix as they can be dissolved. Thus it is very important to protect the cement surface
(by applying varnish, etc.) after it is placed in the mouth.
110  PART 2  Direct Restorative Materials
PROPERTIES
Some of minimum requirements for the different types of GI cements are presented in Table 8.1.

Mechanical properties
Compressive strength  Because of differences in the powder-liquid ratio GIC used for different
applications show variations in their physical properties. Restorative GIC has a compressive
strength of 150 MPa. The luting GIC has a lower compressive strength of about 85 MPa.
Tensile strength Luting type—6.2 MPa
Restorative type—6.6 MPa
Hardness (49 KHN)  Less harder than silicates. The hardness is also far lower when compared
to composites.
Fracture toughness  A measure of energy required to produce fracture. Type II GIC’s are far
inferior to composites in this respect.
Elastic modulus (7.3 GPa)  It is a measure of their stiffness. The MOE is half that of zinc
phosphate cement.
Wear resistance  They are more susceptible to tooth brush abrasion and occlusal wear when
compared to composites.

Solubility and disintegration

The initial solubility is high due to leaching of intermediate products. The complete setting
reaction takes place in 24 hours; therefore, the cement should be protected from saliva in the
mouth during this period. Glass ionomer cements are more resistant to attack by organic acids.
 Solubility in water for Luting type—1.25% wt.
 Solubility in water for Restorative type—0.4% wt.

Adhesion
It adheres well to enamel and dentin. Shear bond strength ranges from 3–5 MPa.
Mechanism of adhesion Glass ionomer bonds chemically to tooth structure. The exact
mechanism has not been fully understood. The bonding is due to the reaction between the
carboxyl groups of the polyacids and the calcium in the enamel and dentin. The bond to
enamel is always higher than that to dentin, probably due to the greater inorganic content
of enamel and its greater homogeneity.

Esthetics
Esthetically they are inferior to silicates and composites. They lack translucency and have a
rough surface texture. They may stain with time. The restorative GICs are available in different
shades. The esthetics are sufficient for restoring cervical lesions and minor defects in nonesthetic
zones. The luting cement is more opaque than the restorative cement.

Biocompatibility
Pulpal response to GIC is classified as mild.
Type II glass ionomers are relatively biocompatible. The pulpal reaction is greater than that
from zinc oxide eugenol cements but less than that produced by zinc phosphate cement.
Polyacids are relatively weak acids.
The water settable cements show higher acidity. Luting type GIC is more acidic than
Restorative type because of the lower powder/liquid ratio. Occasionally sensitive patients
show a painful response to GIC luting cement.
 Dental Cements  CHAPTER 8  111
Pulp protection  In deep cavities, the smear layer should not be removed as it acts as a barrier
to acid penetration. Deep areas are protected by a thin layer of calcium hydroxide cement.

Anticariogenic properties
Type II glass ionomer releases fluoride in amounts comparable to silicate cements initially
and continue to do so over an extended period of time.
In addition, due to its adhesive effect they have the potential for reducing infiltration of oral
fluids at the cement-tooth interface, thereby preventing secondary caries.

MANIPULATION
 Conditioning of tooth surface.
 Proper manipulation.
 Protection of cement during setting.
 Finishing.

PREPARATION OF TOOTH SURFACE

The tooth should be clean for effective adhesion of cement. The smear layer present after
cavity preparation tends to block off the tooth surface and so should be removed to achieve
adhesive bonding.

This is achieved by
 Rubbing with a cotton pellet and pumice slurry
 Etching with 10% polyacrylic acid or 37% phosphoric acid.
(The objective is to remove the smear layer but still leave the collagenous plug in place. The
plug acts as a barrier to the penetration of acid from the cement).
Conditioning  This is achieved with 10% polyacrylic acid or 37% phosphoric acid for about
10 to 20 seconds. Next rinse with water for 20 seconds. Very deep areas of the preparation
should be protected by a dab of calcium hydroxide.
After conditioning and rinsing, the surface is dried but not desiccated. It should be kept free
of saliva or blood as these will interfere with bonding. If contaminated the whole procedure
is repeated.

PROPORTIONING AND MIXING

Powder/liquid ratio
Powder/liquid ratio varies according to the type of GIC and intended use.
Most manufacturers provide a plastic scoop which is useful for measuring. The manufacturers
recommended ratio should be followed. Low P/L ratio reduces mechanical properties and increase
the chances of cement degradation. Moisture contamination alters the acid-water balance.
Spatula used  Stiff plastic or metal spatula.

Mixing
Manual mixing  The powder bottle is tumbled gently. The powder and liquid is dispensed
just prior to mixing. A nonabsorbent paper pad or a cool and dry glass slab may be used.
The powder is divided into two or more increments (Figs. 8.16A to C). The first increment
is incorporated rapidly into the mix with a stiff bladed spatula in about 5–10 seconds. The
112  PART 2  Direct Restorative Materials
material should not be spread over a large area. Subsequent increments are incorporated
and mixed using a swiping and folding technique. The material is collected and folded on to
itself. Total mixing time should not exceed 30–40 seconds.
A good mix should have a glossy surface (Fig. 8.17A). This indicates the presence of residual
polyacid (which has not been used up in the setting reaction) and ensures proper bonding
to the tooth. A mix with dull surface (Fig. 8.17B) is discarded as it indicates prolonged mixing
and reduces the adhesion.
Mixing time  45 seconds.
Insertion  The mix is packed into the cavity without delay using a plastic filling instrument.
If the mix loses its gloss or forms a skin it should be discarded.
Mechanical mixing  GIC supplied in capsule form containing preproportioned powder and
liquid is mixed in an amalgam triturator. The capsule has a nozzle and so the mix can be
injected directly into the cavity or crown (Figs. 8.18A and B).

A B C
FIGURES 8.16A TO C  (A) Dispensed powder and liquid. (B) Mixing of glass ionomer. (C) Mixed glass ionomer showing
right consistency for luting.

A B
FIGURES 8.17A AND B  (A) A good mix should have a glossy surface. This indicates the presence of residual polyacid and
ensures proper bonding to the tooth. (B) A mix with dull surface (right) is discarded.

A B
FIGURES 8.18A AND B  (A) Glass ionomer in capsule form. Mixing is done in a triturator (similar to an amalgam triturator).
(B) The cement is expressed through the nozzle with the help of a special gun.
 Dental Cements  CHAPTER 8  113
Consistency after mixing
This varies according to the type of GIC and its intended use. For example, restorative
consistency differs from luting consistency. For luting the material should have sufficient flow
to ensure complete seating. Care should be taken not to make it too fluid as it can reduce
strength. For restorations, a thicker consistency is required to provide sufficient body for
manipulation and placement into the cavity. In the ART (atraumatic restorative treatment)
technique the material has a very heavy or putty like consistency for improved packability.

Advantages
1. Better properties due to controlled P/L ratio.
2. Less mixing time required.
3. Convenient delivery system.

Disadvantages
1. Cement quantity limited by the manufacturer.
2. Shade selection is limited, colors cannot be blended.

Setting time
Luting type — 7 minutes
Restorative type — 4 to 5 minutes

PROTECTION AND SHAPING OF CEMENT DURING SETTING

Glass ionomer cement is sensitive to air and water during setting. It should be protected from
moisture contamination as well as drying during setting and for a few days after setting. After
placement into the cavity, a preshaped matrix (Figs. 8.19A and B) may be applied to
1. Protect the cement from the environment while setting.
2. Provide maximum contour so that minimal finishing is required.
3. Ensure adequate adaptation on to the walls of the cavity.

PROTECTION OF CEMENT AFTER SETTING

The matrix is removed after complete set. Immediately after removal, the cement surface is
again protected from drying with
1. A special varnish supplied by manufacturer, or
2. An unfilled light cured resin bonding agent, or
3. Cocoa butter or petroleum jelly

A B
FIGURES 8.19A AND B  (A) Commercially available cervical matrixes. (B) Demonstration of matrix application.
114  PART 2  Direct Restorative Materials
This protects the cement from drying while the dentist proceeds with the finishing. Failure to
protect the cement surface from contact with air results in a chalky or crazed surface.
The causes for chalky or crazed surface are
 Inadequate protection of freshly set cement (from air)
 Low powder/liquid ratio
 Improper manipulation

FINISHING
Excess material is trimmed from the margins. Hand instruments are preferred to rotary tools
to avoid ditching. Further finishing if required is done after 24 hours.
Before dismissing the patient, the restoration is again coated with the protective agent to
protect the trimmed areas. Failure to protect the cement from saliva for the first 24 hours can
weaken the cement.

Precautions
1. If the liquid contains polyacids, it should not be placed in a refrigerator as it becomes
very viscous.
2. The restorations must be protected from drying at all times, even when other dental
procedures are to be carried out later.
3. The glass slab should not be below dew point, as moisture may condense on the slab
and change the acid-water balance.

PACKABLE GLASS IONOMER FOR POSTERIOR RESTORATIONS

A packable GIC (Fuji VIII for anterior teeth and Fuji IX or posterior teeth—Figs. 8.20A and B) with
a dough like consistency is available as a cheaper alternative to compomers and composites
for posterior restorations.

Indications for packable GIC

1. Pediatric and geriatric restorations.
2. Intermediate restorative material.
3. Permanent restorative material in non-stress zones.
4. As a core material.

Advantages
1. Higher wear resistance than conventional GICs.
2. Packable and pressable.
3. Fluoride release.
4. Simple to place (single step).
5. Less technique sensitive

ATRAUMATIC RESTORATIVE DENTISTRY (ART)

In areas with no access to electricity or equipment, patients may be treated using the ART
concept which involves hand excavation of caries. Since hand excavation is often incomplete,
one has to rely on a materials that bonds adhesively to enamel and release fluoride in order
to protect teeth under adverse conditions. The material of choice in this case is packable GIC
(Figs 8.20A and B).
 Dental Cements  CHAPTER 8  115

A B
FIGURES 8.20A AND B  High viscosity GIC. (A) Fuji VIII for anterior. (B) Fuji IX for posterior.

FISSURE SEALING (SPECIAL APPLICATIONS)

The traditional glass ionomer cement is somewhat viscous, which prevents penetration to the
depth of the fissure. Thus the fissure orifice in general must exceed 100 um in width. Fissures
or pits that are smaller are better treated with acid etching and light cured resin sealants. The
use of glass ionomer in sealant therapy will increase as formulations are developed that are
less viscous (e.g. light cured) and have good wear resistance.

MODIFIED GLASS IONOMERS

Over the years glass ionomer has been modified by manufacturers in order to compensate for
some of their deficiencies. This has resulted in new products. The modified glass ionomers are:
1. Metal modified GIC
2. Resin modified GIC

METAL MODIFIED GLASS IONOMER CEMENT

Metal-reinforced glass ionomer cements were first introduced in 1977 to improve the strength,
fracture toughness and resistance to wear and yet maintain the potential for adhesion and
anticariogenic property. The addition of silver-amalgam alloy powder to conventional materials
also provided radiodensity. Subsequently, silver particles were sintered onto the glass and
a new product called cermet was launched. These materials are currently considered old-
fashioned, as the conventional glass ionomer cements have comparable physical properties
and far better esthetics.

TYPES
Two methods are employed
1. Silver alloy admixed  Spherical amalgam alloy powder is mixed with restorative type GIC
powder (Miracle Mix—Fig. 8.21).
2. Cermet  Silver particles are bonded to glass particles. This is done by sintering a mixture
of the two powders at a high temperature (Ketac-Silver) (Fig. 8.22).

USES
1. Restoration of small Class I cavities as an alternative to amal­gam or composite resins.
They are particularly useful in young patients who are prone to caries.
2. For core-build up of grossly destructed teeth.
116  PART 2  Direct Restorative Materials

FIGURE 8.21  Miracle Mix. The bottle in the center contains the silver alloy. FIGURE 8.22  Ketac-Silver.

PROPERTIES
Mechanical properties
1. The strength of either type of metal modified cement (150 MPa) is not greatly improved
over that of conventional cement.
2. Diametral tensile strength of the cement is similar to conventional GIC.
3. The fracture toughness of metal modified GIC is similar to that of conventional GIC.
4. In the mouth both metal modified and conventional GIC appear to have similar wear rates.
From the above properties it is clear that there is no appreciable advantage of using metal
modified GIC over conventional GIC. The clinical performance of cermet cements is considered
to be inferior to other restorative materials, so much so that their use is now discouraged.

Anticariogenic property
Both metal modified ionomers have anticariogenic capability due to leaching of fluoride.
However, less fluoride is released from Cermet cement than restorative GIC, since the glass
particle is metal coated. On the other hand the admixed cement releases more fluoride than
restorative GIC. Here the metal filler particles are not bonded to the cement matrix and thus
there are pathways for fluid exchange. This increases leaching of fluoride.

Esthetics
These materials are gray in color because of metallic phases within them; therefore, they are
unsuitable for use in anterior teeth.

RESIN-MODIFIED GLASS IONOMER

These are relatively new materials having various names like compomer, resin-ionomers, RMGI
(resin-modified glass ionomer), light cured GIC, dual cure GIC, tricure GIC, reinforced GIC,
hybrid ionomers, etc. These materials were developed to overcome some of the drawbacks
of conventional GIC like
1. Moisture sensitivity
2. Low initial strength
3. Fixed working times.

CLASSIFICATION
Depending on which is the predominant component. These mate­rials may be classified as
(McClean et al).
 Dental Cements  CHAPTER 8  117

A B C
FIGURES 8.23A TO C  Resin-modified glass ionomer cements. (A) A light cured base/liner. (B) GC’s Fuji II LC is a radiopaque
light cured restorative cement. (C) Resin-modified luting cement.

1. Resin-modified glass ionomer cement (RMGI), e.g. Fuji II LC (Figs. 8.23A to C), Vitremer,
Photac Fil, etc.
2. Compomers or polyacid-modified composites (PMC), e.g. Dyract Variglass VLC (this category
will be discussed subsequently under the heading compomers).

Uses
1. Restoration of Class I, III or V cavities.
2. Bases and liners.
3. As adhesives for orthodontic brackets.
4. Cementation of crowns and FDPs.
5. Repair of damaged amalgam cores or cusps.
6. Retrograde root filling.
Note  Uses vary according to brand.

SUPPLIED AS
They are supplied as
 Chemical cure (acid-base setting reaction of the glass ionomer portion).
 Dual cure (combines acid-base setting reaction of the GIC portion and light curing of
the resin portion).
 Tricure (combines acid-base setting reaction, chemical and light cured polymerization
of the resin portion).
All of them are usually supplied as powder and liquid. The light cured type is supplied in dark
shaded bottles (for light protection).

COMPOSITION
Since these are combination materials, they contain components of both resin and glass
ionomer. However, their proportions vary.
Powder Liquid
Ion leachable glasses (silica, alumina) Polyacrylic acid
Photoinitiators or chemical initiators or both Water
Polymerizable resin Methacrylate monomer
Hydroxyethyl methacrylate monomers
118  PART 2  Direct Restorative Materials
SETTING REACTION
Setting includes both polymerization and acid-base reaction. The initial setting occurs by
polymerization of the methacrylate groups giving it a high early strength. Polymerization
may be light cured or chemical cured depending on the type of cement. Subsequently the
acid-base reaction sets it thereby completing the setting reaction and giving the cement its
final strength.

MANIPULATION
RMGI is mixed and applied after conditioning the tooth with polyacrylic acid (10–25%). The
powder and liquid is mixed according to the manufacturer’s instruction. Light cured RMGI is
cured by exposure to blue light (which is used for curing composite).

PROPERTIES
Strength
The compressive strength is slightly lower (105 MPa) when compared to conventional GIC. The
diametral tensile strength is however greater (20 MPa). They have a greater fracture toughness
because of the greater resilience of the resin component.

Hardness
The hardness (40 KHN) is comparable to that of conventional GIC.

Adhesion
The bonding mechanism to tooth structure is similar to that of conventional GIC.
Micromechanical retention also plays a role in the bonding process. These materials bond
better to composite resins than conventional GIC. This may be because of the presence of
residual unreacted monomers within the RMGI.

Microleakage
These materials have a greater amount of microleakage when compared to GIC. This may
be partly due to the polymerization shrinkage and partly due to the reduced wetting of the
tooth by the cement.

Anticariogenicity
These materials have a significant anticariogenic effect because of the fluoride release. Some
tests indicate fluoride release may be equivalent to that of conventional GIC.

Pulpal response
The pulpal response to the cement is mild (similar to conventional GIC).

Esthetics
They are more translucent and therefore more esthetic than conventional GIC. This is due to
the closeness of the refractive indices of the powder and the monomer in the liquid.

CALCIUM HYDROXIDE CEMENT

Calcium hydroxide is a relatively weak cement commonly employed as direct or indirect pulp
capping agents. Due to their alkaline nature they also serve as a protective barrier against
irritants from certain restorations.
 Dental Cements  CHAPTER 8  119
A light cured calcium hydroxide base material and a calcium hydroxide root canal sealing
paste is also available.

APPLICATIONS
1. For direct and indirect pulp capping.
2. As low strength bases beneath
restora­tions for pulp protection.
3. Apexification procedure in young
permanent teeth where root
formation is incomplete.

AVAILABLE AS
FIGURE 8.24  Dycal is a well-known brand of calcium
 Two paste system containing base hydroxide pulp capping agent.
and catalyst pastes in soft tubes
(Fig. 8.24)
 Light cured system
 Single paste in syringe form
(Pulpdent, Fig. 8.25)
 Powder form (mixed with distilled
water)
 Some representative commercial
products
 Regular set—Dycal (Dentsply),
Calcidor (Dorident), Recal (PSP),
Hydrox (Bosworth) FIGURE 8.25  Calcium hydroxide root canal pastes. The
syringe form (top) allows the material to be conveniently
 Light cured—Septocal LC (Septodont) applied into the narrow root canal.
and Calcimol LC (VOCO).

COMPOSITION

Base paste
Ingredient Weight (%) Liquid
l-methyl trimethylene disalicylate 40 Reacts with Ca(OH)2 and ZnO
Calcium sulphate
Titanium dioxide Inert fillers, pigments
Calcium tungstate or barium sulphate Provides radiopacity

Catalyst paste
Ingredient Weight (%) Liquid
Calcium hydroxide 50 Principal reactive ingredient
Zinc oxide 10
Zinc stearate 0.5 Accelerator
Titanium oxide Provides radiopacity, filler
Ethylene toluene sulfonamide 39.5 Oily compound, acts as carrier
120  PART 2  Direct Restorative Materials
SETTING REACTION
Calcium hydroxide reacts with the l-methyl trimethylene disalicylate ester to form a chelate
viz. amorphous calcium disalicylate. Zinc oxide also takes part in the reaction.
Ca (OH)2 + l-methyl trimethylene disalicylate → calcium disalicylate

PROPERTIES
Calcium hydroxide cements have poor mechanical properties. However, they are better than
zinc oxide eugenol.

Mechanical properties
Compressive strength (10-27 MPa after 24 hours). It has a low compressive strength. The strength
continues to increase with time.
Tensile strength (1.0 MPa) is low.
Modulus of elasticity (0.37 GPa/m2). The low elastic modulus limits their use to areas not critical
to the support of the restoration.

Thermal properties
If used in sufficiently thick layers they provide some thermal insu­lation. However, a thickness
greater than 0.5 mm is not recom­mended. Thermal protection should be provided with a
separate base.

Solubility and disintegration

The solubility in water is high (0.4–7.8%). Some solubility of the calcium hydroxide cement
is necessary to achieve its therapeutic properties. Solubility is higher when exposed to
phosphoric acid and ether. So care should be taken during acid etching and during application
of varnish in the presence of this cement.

Biological properties
Effect on pulp: The cement is alkaline in nature. The high pH is due to the presence of free
Ca(OH)2 in the set cement. The pH ranges from 9.2 to 11.7.
Formation of secondary dentin: The high alkalinity and its consequent antibacterial and protein
lysing effect helps in the formation of reparative dentin.

Adhesion
The material is sensitive to moisture and does not adhere in the presence of blood, water or
saliva. The adhesive bond is weak.

MANIPULATION
Equal lengths of the two pastes are dispensed on a paper and mixed to a uniform color. The
material is carried and applied using a calcium hydroxide carrier or applicator (a ball-ended
instrument). It is applied to deep areas of the cavity or directly over mildly exposed pulp
(contraindicated if there is active bleeding).

SETTING TIME
Ranges from 2.5 to 5.5 minutes.
 Dental Cements  CHAPTER 8  121
Factors affecting setting time  The reaction is greatly accelerated by moisture and accelerators.
It therefore sets faster in the mouth.

LIGHT ACTIVATED CALCIUM HYDROXIDE CEMENT

Light activated calcium hydroxide cements
are available. It consists of calcium hydroxide
and barium sulphate dispersed in a urethane
dimethacrylate resin. It also contains HEMA
and polymerization activators. Some contain
fluoride.
Light activated cements have a long working
time and is less brittle than the conventional
two paste system. They are radiopaque. They
are supplied in syringe form (Fig. 8.26) and is
expressed directly on to the tooth through a
replaceable nozzle. Examples are Septocal LC FIGURE 8.26  Light-cured calcium hydroxide.
(Septodont) and Calcimol LC (VOCO).

CALCIUM HYDROXIDE ROOT CANAL SEALING PASTES

Root canal sealers containing calcium hydroxide are available (Fig. 8.25). These are similar to
the ones used for pulp capping but contain increased amount of retarders in order to extend
the working time while they are being manipulated in the warm environment of the root
canal. They are also radiopaque.
Commercial names  Sealapex (Kerr), Pulpdent, etc.
Their advantages are
1. Effective antibacterial properties without irritation.
2. They stimulate hard tissue repair in the apical foramen.

RESIN CEMENTS
Resin cements based on methyl methacrylate have been available since 1952 for cementation
of inlays, crowns and other appliances. Development of resin cements came naturally with the
development of composites resins. They are essentially low viscosity flowable composites. These
cements are known for their high esthetics and high bond strengths. They were widely used
for the cementation of orthodontic brackets
and resin-bonded restorations (Figs 8.27 and
28). The development of esthetic all-ceramic
restorations led to a renewed interest in an
esthetic bonding system which complemented
the esthetics of the restoration. The color of the
underlying cement can influence the esthetics
in translucent restorations. The resin cement
also improves the esthetics at the margins of
the restoration. According to some studies
resin cements reduce fractures of all-ceramic
restorations. Thus, they are popular for the
cementation of all-porcelain restorations. FIGURE 8.27  Bonding of orthodontic brackets.
122  PART 2  Direct Restorative Materials
APPLICATIONS
1. For bonding of orthodontic brackets to
acid-etched enamel (Fig. 8.27).
2. Cementation of porcelain veneers and
inlays.
3. Cementation of all-porcelain crowns and
FDPs (Fig. 8.29B).
4. Cementation of etched cast restorations
(Fig. 8.28). FIGURE 8.28  An etched resin-bonded cast
restoration (Maryland bridge).
CLASSIFICATION
Based on curing system
 Chemical cure
 Light cure
 Dual cure
Chemically activated resins can be used for all types of restorations.
Light activated resins cannot be used in all situations because of problems of light penetration.
Thus their use is limited to thin ceramic restorations which allows some passage of light,
composite restorations like inlays, ceramic or plastic orthodontic brackets, etc.
Dual cure resins are used when the material being bonded allows some degree of light
penetration, e.g. ceramic crown, brackets, inlays, etc. The resin around the margins are cured
using light to initiate setting. The portions where light cannot penetrate cure subsequently
by chemical reaction.

SUPPLIED AS
They are supplied in syringes
1. Chemical cured
–– Two paste system containing base and accelerator
–– Single paste system with activator in the bonding liquid
2. Light cured: Single paste system.
Most systems also include a bonding agent and etchant.
Representative Commercial Names  Panavia F, Infinity, ResiLute (Pulpdent), Transbond XT
(3M), Maxcem Elite (Kerr), Variolink Esthetic (Ivoclar) (Fig. 8.29A), etc.

A B
FIGURES 8.29A AND B  (A) Representative resin luting cement (dual cured). (B) Resin cement is directly injected into
the crown through the static mixing tip.
 Dental Cements  CHAPTER 8  123
COMPOSITION
The resin cements have a composition similar to that of modern composites (refer chapter on
composites). The filler content has to be lowered and diluent monomers are added to adjust
the viscosity. Some contain fluoride (e.g. Panavia F).
To promote adhesion to enamel and dentin, organophosphates (MDP), HEMA and 4 META
are used as bonding agent (refer chapter on resin-based composites for details).

POLYMERIZATION
1. Chemically by peroxide-amine system
2. Or by light activation
3. Or by both chemical and light activation (dual cure).
Polymerization mechanisms are similar to those of resin-based composites.

PROPERTIES
Compressive strength : 180 MPa (26000 Psi)
Tensile strength : 30 MPa (4000 Psi)
Film thickness : 10–25 µm
Biological properties : Irritating to the pulp. Pulp protection with calcium hydroxide
or GIC liner is necessary for areas close to the pulp.
Solubility : Insoluble in oral fluids.
Polymerization shrinkage : Is high
Adhesion properties : They do not adhere to tooth structure, which may lead to
microleakage if used without etching and bonding.
Bond strength to enamel : 7.4 MPa (1070 Psi). Bond strength to enamel is usually strong.
Failure most often occurs at the metal-resin interphase.

MANIPULATION AND TECHNICAL CONSIDERATIONS

Like composites, resin cements are technique sensitive. Improper procedure can lead to poor
bond strength and failure. The following processes are involved.
1. Etching the restoration
2. Etching the tooth surface
3. Bonding and curing
4. Removal of excess cement

ETCHING THE RESTORATION

Etching metal  The metal surface can be etched or roughened by blasting with 30–50 µm
alumina to improve retention. Etching is usually more effective. The process is carried out in a
electrolytic bath containing an acid like sulfuric acid—also known as electrochemical etching. The
non-bonding surface is protected with wax. Silica coating can also be used to improve bonding.
Etching porcelain  Ceramic is a highly inert material and is immune to attack by most acids.
However, it can be etched by using hydrofluoric acid (refer chapter on ceramics). The esthetic
surfaces are protected with a coating of wax.
124  PART 2  Direct Restorative Materials
Orthodontic brackets  In the case of orthodontic brackets, a fine mesh on the bonding
side of the bracket helps to improve its retention. The cement flows into the mesh and
locks to provide good mechanical retention. Coating with organosilane also improves
bond strength.

ETCHING THE TOOTH SURFACE

The tooth surface is etched with phosphoric acid (similar to procedure described in restorative
resins). This is followed by an application of bonding agent.

BONDING AND CURING

Chemically activated systems

Two paste systems  The two components are combined by mixing on a paper pad. Mixing
time is 20–30 seconds.
Single paste system with activator in bonding agent  In some systems, the activator is present
in the bonding agent. The bonding agent is painted on to the etched tooth surface as well
as on to the restoration. Setting occurs when the cement on the restoration contacts the
bonding agent on the tooth.

Dual cure system

 The two components are mixed and light cured.
 Time of exposure should never be less than 40 seconds.
 Light curing gives high initial strength.
 Light curing polymerizes the exposed cement at the margins of the restoration which is
affected by air inhibition.

REMOVAL OF EXCESS CEMENT

Excess cement removal is critical. Removal of excess cement can sometimes be very difficult
because of the high strength of the material. Therefore, removal of the excess cement should
be attempted soon after seating before the material has fully hardened. Some manufacturers
recommend a partial light cure to facilitate removal followed by completion of curing.

COMPOMER (POLYACID-MODIFIED COMPOSITE RESINS)

Shortly after the introduction of RM GICs, ‘compomers’ were introduced to the market. They
were marketed as a new class of dental materials that would provide the combined benefits
of composites (the ‘comp’ in their name) and glass ionomers (‘omer’). These materials had the
fluoride release features of GIC with the durability of composite. Based on their structure and
properties, these materials belong to the class of dental composites. Often they have been
erroneously referred to as ‘hybrid glass ionomers’, ‘light-cured GICs’ or ‘resin-modified glass
ionomers’. The proposed nomenclature for these materials is polyacid-modified composite
resins, a nomenclature that is widely used in the literature.

APPLICATIONS
1. Restorative materials in pedodontics.
2. Restorative material in nonstress bearing areas.
3. Class V lesions.
 Dental Cements  CHAPTER 8  125
4. Bases.
5. Luting (permacem) (Fig. 8.33).
Their applicability as orthodontic adhesives, amalgam bonding systems and veterinary
restorative materials has also been reported.

SUPPLIED AS
These materials are sensitive to moisture. They are usually supplied as
 Light cured single paste in moisture proof packets (Dyract, Compoglass) (Fig. 8.30)
 Powder/liquid (Principle) (Fig. 8.32)
 Two paste static mixing system (PermaCem) (Fig. 8.31).
Commercial names Restorative —Dyract (Dentsply), Compoglass (Ivoclar).
Luting —Permacem, Principle (Dentsply), etc.

COMPOSITION
These materials have two main constituents: dimethacrylate monomer(s) with two carboxylic
groups present in their structure and a filler that is similar to the ion-leachable glass present
in GICs. The ratio of carboxylic groups to backbone carbon atoms is approximately 1:8. There
is no water in the composition of these materials and the ion-leachable glass is partially
silanized to ensure some bonding with the matrix.
Single component system - Silicate glass, sodium fluoride, and polyacid
modified monomer, photoinitiator.
Double component system Powder - Glass fillers, accelerators, initiator, TiO2
Liquid - Acrylic monomers, photoinitiator, water,
carboxylic acid dimethacrylate.

SETTING REACTION
The initial set is via a free radical polymerization reaction activated by light. Subsequently
water from saliva is absorbed by the cement and an acid-base reaction sets in between the
carboxylic groups and areas of filler not contaminated by the silane coupling agents. It is this
reaction which releases fluoride.

FIGURE 8.30 Single component compomer restorative FIGURE 8.31  Two paste static mixing compomer luting
cement (Dyract, Dentsply). cement (PermaCem by DMG).
126  PART 2  Direct Restorative Materials

FIGURE 8.32  Powder/liquid type luting FIGURE 8.33 Luting procedure of 2 all ceramic
cement (Principle by Dentsply). anterior crowns. Excess cement is removed.

BONDING AND CURING

Bonding and curing mechanisms are similar to the resin luting cements.
 Light cured
 Chemically cured
 Dual cured
Etching and bonding are similar to the resin luting cements. Some current materials are self-
etching and bonding (e.g. Permacem by DMG, Fig. 8.31). No additional etching and bonding
are required in these materials.

MANIPULATION
For the single component system the tooth is etched and bonding agent applied. The material
is injected into the cavity and cured by light.
For the powder/liquid system the powder and liquid is dispensed and mixed according to
the manufacturer’s instruction for 30 seconds.
For the static mixing system, the material comes out mixed when it is extruded through the
spirals in the mixing tips.

PROPERTIES
Considering the low volume fraction filler and the incomplete silanization of the filler, it could
be postulated that they are inferior to composites. Both in vitro and in vivo investigations
have confirmed this expectation. Lower flexural strength, modulus of elasticity, compressive
strength, flexural strength fracture toughness and hardness, along with significantly higher
wear rates compared to clinically proven hybrid composites, have been reported for these
materials. Their clinical performance received mixed reviews during in vivo clinical trials.

Fluoride release
Though these materials release fluoride they have significantly lower levels of fluoride release
than GICs. Although low, the level of fluoride release has been reported to last at least 300 days.

Adhesion
Unlike glass ionomer they do not have the ability to bond to hard tooth tissues. Like composites
acid etching and use of bond agents are necessary.
 Dental Cements  CHAPTER 8  127
Biocompatibility
With the exception of concerns about the release of HEMA from these materials, no other
biocompatibility issues have been associated with their usage.

ADVANTAGES AND DISADVANTAGES

The prime advantage of these materials are their fluoride release anticariogenic potential.
The disadvantage is their lack of adhesion. Thus bonding agents are required which increase
in the number of steps and time required for placement.
Constant reformulations of these types of materials may eventually make them comparable or
even superior to existing composites, but as long as they do not set via an acid-base reaction
and do not bond to hard-tooth tissues, they cannot and should not be classified with GICs.
 9
Chapter

Dental Amalgam

Chapter Outline
• History of Dental Amalgam –– Microstructure of Set Single- –– Cavity Design
–– Indications composition Amalgam –– Selection of Materials
–– Contraindications –– Advantages/ Disadvantages –– Dispensers
–– Classification of Amalgam of Spherical High-Copper –– Tablets
–– Manufacture Amalgam –– Preproportioned Capsules
–– Composition • Properties of Set Amalgam –– Mercury: Alloy Ratio
–– Comparison of Lathe Cut and • Safety of Dental Amalgams (Proportioning)
Spherical Alloys • Microleakage –– Eames Technique
• Low Copper Alloys • Dimensional Change –– Trituration
–– Composition • Effect of Moisture Contamination –– Mulling
–– Available As (Delayed Expansion) –– Condensation
–– Setting Reaction • Strength –– Shaping and Finishing
–– Microstructure • Tensile Strength • Mercury Toxicity
–– Advantages/Disadvantages • Creep • Amalgam Disposal
of Admixed Amalgam • Retention of Amalgam –– Amalgam Separators
• Single-composition Alloys • Tarnish and Corrosion • Advantages/Disadvantages
–– Composition • Technical Considerations • The Amalgam Controversy
–– Setting Reaction –– Manipulation of Amalgam

An amalgam is defined as a special type of alloy in which mer­cury is one of the components.
Mercury is able to react with certain alloys to form a plastic mass, which is conveniently packed
into a prepared cavity in a tooth. This plastic mass hardens and is stronger than any dental
cement or anterior filling material. Dental amalgam is the most widely used filling material for
posterior teeth.
The alloys before combining with mercury are known as den­tal amalgam alloys. Strictly
speaking, however, this is a misnomer as they are not dental amalgam alloys but alloys from
which dental amalgam is prepared.
In dentistry, amalgam has been successfully used for more than a century as a restoration
material for tooth decay. Over the years its quality has greatly improved, thanks to a lower
amount of mercury and the addition of new components which can reduce its corrosion in
the oral cavity.
 Dental Amalgam  Chapter 9  129

History of Dental Amalgam 

There are indications that dental amalgam was used in the first part of the T’ang Dynasty in China
(618-907 CE). Prior to amalgam, dentists restored teeth using filling material such as stone chips,
resin, cork, turpentine, gum, lead and gold leaf, among other metals. The renowned physician
Ambroise Paré (1510–1590) used lead or cork to fill teeth.
In 1603, a German named Tobias Dorn Kreilius described a process for creating an amalgam filling
by dissolving copper sulfide with strong acids, adding mercury, bringing to a boil and then pouring
onto the teeth. In France, D’Arcet’s Mineral Cement was popular, but it had to be boiled into a liquid
before being poured on patient’s teeth. Louis Regnart added mercury to the mixture, lowering
the temperature required significantly, and for this became known as the ‘Father of Amalgam’.
Amalgam was placed by Taveau of Paris as early as 1826, although he had developed it in 1816. Early GV Black
amalgam had drawbacks including marginal breakdown. Some mixtures caused expansion resulting in fractured teeth.
In the 1830s, a fusible alloy of lead, bismuth and tin, known as “Darcet’s metal” was used to fill teeth. This material was
heated and then poured into the tooth in the molten state, after which it quickly hardened.
Amalgam was introduced into the USA by the Crawcour brothers (from France) in 1833. However, at that point the use
of dental amalgam was declared to be malpractice, and the American Society of Dental Surgeons (ASDS), the only US
dental association at the time, forced all of its members to sign a pledge to abstain from using the mercury fillings. This
was the beginning of what are known as the first dental amalgam war. The war ended in 1856 with the rescission of
the old association. The American Dental Association was founded in its place in 1859, which has since then strongly
defended dental amalgam from allegations of being too risky from the health standpoint.
Early amalgam was made by mixing mercury with the filings of silver coins. The early amalgams expanded on setting. In
1895, GV Black developed a balanced formula (67% silver, 27% tin, 5% copper, 1% zinc) for modern amalgam alloy. Black’s
formula overcame the expansion problems of the existing amalgam formulations.

INDICATIONS
1. As a permanent filling material for
–– Class I and class II cavities (Fig. 9.1)
–– Class V cavities where esthetics is not required (Fig. 9.1)
2. In combination with retentive pins to restore a crown.
3. For making dies.
4. In retrograde root canal fillings.
5. As a core material in abutment teeth.

Contraindications
1. Amalgam should not be placed
in patients with impaired kidney
function.
2. I n d i v i d u a l s w i t h a l l e r g i c
hypersensitivity to mercury or
components of the alloy
3. New amalgam fillings should
not be placed in contact with
nonamalgam restoration like
gold and metal devices, such as Figure 9.1 Amalgam restorations—Class I, class II and
orthodontic braces. class V.
130  Part 2  Direct Restorative Materials

Box 9.1    ISO standards covering dental amalgam and related products and equipment

ISO 24234:2015 Dentistry—Mercury and alloys for dental amalgam

ISO 7488:1991 Dental amalgamators
ISO 8282:1994 Dental equipment—Mercury and alloy mixers and dispensers
ISO 13897:2003 Dentistry -- Amalgam capsules

CLASSIFICATION OF AMALGAM ALLOYS

Based on Copper Content
 Low copper alloys  Contain less than 6% copper (conventional alloys)
 High copper alloys  Contain between 13–30% copper

The high copper alloys are further classified as

 Admixed or dispersion or blended alloys.
 Single composition or unicompositional alloys

Based on Zinc Content

 Zinc-containing alloys  Contain more than 0.01% zinc
 Zinc-free alloys  Contain less than 0.01% zinc

Based on Shape of the Alloy Particle

 Lathe-cut alloys (irregular shape)
 Spherical alloys
 Spheroidal alloys

Based on Number of Alloyed Metals

 Binary alloys, e.g. silver-tin
 Ternary alloys, e.g. silver-tin-copper
 Quaternary alloys, e.g. silver-tin-copper-indium

Based on Size of Alloy POWDER PARTICLE

 Microcut
 Macrocut

MANUFACTURE OF ALLOY POWDER

The various components of the amalgam alloy are combined together by melting to form
ingots. The ingots have to be heat-treated in an oven for a set period of time. This process
is called annealing. Annealing improves the homogeneity and grain structure of the alloy.

Lathe-Cut Alloy Powder

An annealed ingot of silver-tin alloy is placed in a lathe and fed into a cutting tool. The
resulting chips obtained are often needlelike and some manufacturers reduce the chip size
by ball-milling (Fig. 9.2A).
 Dental Amalgam  Chapter 9  131

A B C
Figures 9.2A to C  Photomicrograph of the various alloy powders. (A) Lathe cut. (B) Spherical. (C) Admixed.

Aging, acid treatment and annealing of particles

A freshly cut alloy reacts too rapidly with mercury. If the alloy filings are stored at room
temperature for a few months, the reactivity gradually decreases. Such alloys are said to
have been aged. The filings can be aged faster by boiling in water for 30 minutes. Aging also
improves the shelf life of the product.
Some manufacturers treat the filings with acid to improve reactivity.
The stresses induced during the cutting and grinding process must be relieved by an annealing
process (100 °C for several hours). Failure to anneal results in a slow release of stress over time
(during storage) which can adversely affect the properties of the amalgam.

Spherical Alloy Powder

The spherical alloy (Fig. 9.2B) is prepared by an atomization process. The liquid alloy is
sprayed under high pressure of an inert gas through a fine crack into a large chamber.
If the droplets solidify before hitting a surface, the spherical shape is preserved. Like the
lathe-cut powders, spherical powders are aged. A comparison of two types of powders is
detailed in Table 9.1.

SUPPLIED AS
 Bulk powder and mercury in separate containers (Figs. 9.3A and B).
 Alloy and mercury in disposable capsules (Figs. 9.4, 9.7 and 9.9).
 Preweighed alloy as tablet form in tubes (Fig. 9.5) and mercury in sachets.

A B
Figures 9.3A and B  (A) dpi alloy powder. (B) Various brands of commercially available mercury (Courtesy: Vijay Dental,
Chennai).
132  Part 2  Direct Restorative Materials

Figure 9.4 Alloy/mercury in
preproportioned capsule form. Figure 9.5  Alloy in tablet form.

COMPOSITION
Low copper High copper
Admixed Unicomposition
Lathe-cut or spherical Lathe-cut 2/3 Spherical 1/3 Spherical
Silver 63–70% 40–70% 40–65% 40–60%
Tin 26–29% 26–30% 0–30% 22–30%
Copper 2–5% 2–30% 20–40% 13–30%
Zinc 0–2% 0–2% 0 0–40%

FUNCTION OF CONSTITUENTS

Silver
 Major element in the reaction.
 Whitens the alloy.
 Decreases the creep.
 Increases the strength.
 Increases the expansion on setting.
 Increases tarnish resistance in the resulting amalgam.

Tin
 Tin controls the reaction between silver and mercury. Without tin the reaction would be
too fast and the setting expansion would be unacceptable.
 Reduces strength and hardness.
 Reduces the resistance to tarnish and corrosion, hence the tin content should be
controlled.

Copper
 Increases hardness and strength.
 Increases setting expansion.

Zinc
 In small amounts, it does not influence the setting reaction or properties of amalgam.
Zinc acts as a scavenger or deoxidizer during manufacture, thus prevents the oxidation of
 Dental Amalgam  Chapter 9  133
important elements like silver, copper or tin. Oxidation of these elements would seriously
affect the properties of the alloy and amalgam. Alloys without zinc are more brittle, and
amalgam formed by them are less plastic.
 Zinc causes delayed expansion if the amalgam mix is conta­minated with moisture during
manipulation.

Mercury
In some brands, a small amount of mercury (up to 3%) is added to the alloy. They are known
as pre-amalgamated alloys. Pre-amalgamation produces a more rapid reaction.

Platinum
Hardens the alloy and increases resistance to corrosion.

Palladium
Hardens and whitens the alloy.

Indium
Indium when added to the mercury reduces mercury vapor and improves wetting. Indium
can also added to the powder. Though it reduces early strength it increases the final strength.
It reduces creep.

COMPARISON of lathe cut and spherical alloys

A comparison of the two types of powders is presented in Table 9.1.
Table 9.1  Comparison of lathe cut and spherical alloys
Spherical alloys Lathe-cut alloys
Particles are spherical Particles are irregular
Manufactured by atomization of molten alloy Manufactured by milling an annealed ingot of alloy
More plastic (a contoured matrix is essential to Less plastic and resists condensation pressure
establish proximal contour)
Requires less mercury hence has improved properties More mercury required hence has inferior properties

LOW COPPER ALLOYS

Historically amalgam alloys were low copper alloys. The composition recommended by GV.
Black in the late 18th century remained virtually unchanged until the late 1960s when the
high copper amalgams were introduced.

Composition
Constituents Percent
Silver 63–70%
Tin 26–29%
Copper 2–5%
Zinc 0–2%
134  Part 2  Direct Restorative Materials
Available As
 Lathe-cut alloys, which are further available as coarse or fine grain (fine grain type is
preferred, because of the ease of carving).
 Spherical alloys.
 Blend of lathe-cut and spherical particles.

Setting Reaction
When alloy powder and mercury are triturated, the silver and tin in the outer portion of the
particles dissolve into the mercury. Simultaneously, the mercury diffuses into the alloy particles
and starts reacting with the silver and tin within forming crystals of silver-mercury (Ag2Hg3)
and tin-mercury compounds (Sn8Hg).
Silver-tin compound (unreacted alloy powder) is known as the gamma (γ) phase. The silver-
mercury compound is known as gamma 1 (γ1) phase and the tin-mercury as the gamma 2 (γ2)
phase (Table 9.2).
A simplified reaction is outlined below
Ag3Sn + Hg → Ag2Hg3 + Sn8Hg + (unreacted) Ag3Sn
(β+γ) (γ1) (γ2) (β+γ)
The alloy particles do not react completely with mercury. About 27% of the original Ag3Sn
remains as unreacted particles, which as previously mentioned is known as the gamma (γ) phase.

The properties of the hardened amalgam depends on the proportion of the reaction phases. If more unconsumed Ag3Sn
(γ phase) is present, the stronger the amalgam. The γ2 phase is the weakest component and is least stable to corrosion.

Microstructure
Set amalgam consists of unreacted particles (γ) surrounded by a matrix of the reaction products
(γ1 and γ2) (Fig. 9.6).

Table 9.2  Amalgam reaction phases and symbols

Phases Symbol Chemically
Gamma γ Ag3Sn
Beta β AgSn
Gamma 1 γ1 Ag2Hg3
Gamma 2 γ2 Sn8Hg
Eta η Cu6Sn5
Epsilon ε Cu3S

Figure 9.6  Schematic representation of setting reaction and microstructure of low copper amalgam.
 Dental Amalgam  Chapter 9  135
Note  The properties of the hardened amalgam depends upon the proportion of each of the
reaction phases. If more unconsumed Ag3Sn (γ phase) is present, the stronger the amalgam.
The γ2 phase is the weakest component and is least stable to corrosion process. Also present are
Cu3Sn phase (ε or epsilon) formed from the small amounts of copper present in the composition.

HIGH COPPER ALLOYS

High copper alloys contain between 13 to 30% wt. copper. The majority of amalgam
restorations placed currently are high copper. They are preferred because of their improved
mechanical properties, resis­tance to corrosion and better marginal integrity.

Types
1. Admixed alloy.
2. Single-composition alloy.

ADMIXED ALLOY POWDER

The admixed alloy (Figs. 9.2C and 9.7) was introduced in 1963 and were originally made by
mixing 1 part silver-copper eutectic alloy (high copper spherical particles) with 2 parts silver-
tin alloy (low-copper lathe-cut particles).
(An eutectic alloy is one in which the components
exhibit com­plete liquid solubility but limited solid
solubility. The silver-copper phase exhibits a eutectic
structure at the composition of silver 71.9% and copper
28.1%).
Amalgam made from admixed powders is stronger than
amal­gam made from lathe-cut low-copper powder,
because of three reasons
1. A change in the nature of the filler particles. The
silver-copper particles are present in greater
amounts, in addition to the silver-tin particles. Figure 9.7  Admixed alloy (Dentsply).
2. A greater residual filler content thereby changing
the filler to matrix ratio.
3. A reduction in the weaker γ2 phase.
Synonyms  Dispersed phase alloy.

TYPES
Admixed alloys are of two types
1. Regular or conventional admixed alloy—contains irregular and spherical alloy particles
having different compositions (low copper and high copper).
2. Unicomposition admixed alloys—contains irregular and spherical particles of uniform
composition.

Composition
Admixed alloy powders usually contain between 30 to 55 weight per­cent spherical high-
copper alloy powder. The total copper content ranges from 9 to 20 weight percent. A sample
composition is presented below.
136  Part 2  Direct Restorative Materials

Constituents Percent
Silver 69%
Tin 17%
Copper 13%
Zinc 1%

Setting Reaction
When the components are mixed the mercury begins to dissolve the outer portion of the
particles. Silver from the silver-copper eutectic alloy particles, and both silver and tin from
the silver-tin alloy particles enter the mercury. The tin dissolved in the mercury reacts with
the copper of the silver-copper particles and forms the Cu6Sn5 (η or Eta). The η crystals form
around the unreacted silver-copper particle. At the same time γ1 phase is also formed. As
in the low copper alloys γ1 surrounds everything forming the matrix. γ2 is also formed at
the same time but is later replaced by η. Thus in admixed alloy the undesirable γ2 phase is
greatly reduced.
The reaction may be simplified as follows

Ag3Sn + Ag-Cu + Hg → Ag2Hg3 + Cu6Sn5 + Ag3Sn unreacted + Ag-Cu unreacted

(β+γ) (eutectic) (γ1) (η) (β+γ) (eutectic)

Note  In this reaction, γ2 has been eliminated and is replaced by η phase. To accomplish
this, it is necessary to have a net copper content of at least 12 percent in the alloy powder.

Microstructure of Set high copper admixed Amalgam

The Cu6Sn5 is present as a ‘halo’ surrounding the Ag-Cu particles.
The final set material consists of
Core particles of
 Unreacted Ag3Sn, (γ phase) and
 Unreacted Ag-Cu surrounded by a halo of Cu6Sn5 (η).
Embedded in a matrix made up of
 γ1 (Ag2Hg3).
Schematic representation of the setting reaction and microstructure is shown in
Figs. 9.8A to C.

A B C
Figures 9.8A to C  Schematic representation of setting reaction and microstructure of admixed amalgam.
 Dental Amalgam  Chapter 9  137
SINGLE COMPOSITION ALLOYS
High copper amalgam was developed by a Canadian metallurgist, Dr. William Youdelis in 1963.
Single composition alloys are high copper amalgam alloys. Unlike admixed alloy powders,
each particle of the alloy powder has the same com­position. Therefore they are called single
composition or ‘unicompositional alloys’ (Fig. 9.9). The spherical alloy particles are 5 to 40 µm
in size.
Synonyms  Single composition, unicompositional, non-gamma 2.

Composition
Constituents Percent
Silver 40–60%
Tin 22–30%
Copper 13–30%
Zinc 0–4%
Indium or palladium Small amounts

Figure 9.9  Single composition

Setting Reaction high copper alloy (Ivoclar).

Though each particle has the same composition, the silver, tin and copper present exist in
various phases within the particle. Thus each particle contains Ag3Sn (γ), AgSn (β) and Cu3Sn
(ε ). When triturated, silver and tin from the particle dissolve in mercury forming the γ1 (Ag2-
Hg3) crystal matrix that binds together the partially dissolved alloy particles. At this stage very
little copper dissolves. Later, a layer of η (Cu6Sn5) crystals are formed at the surface of alloy
particles. Some η (Cu6Sn5) crystals also form in the matrix.
The overall simplified reaction is

Ag-Sn-Cu + Hg → Cu6Sn5 + Ag2Hg3 + Ag-Sn-Cu

(γ + β + ε) (η) (γ1) (unreacted)
Note  The undesirable γ2 does not usually form in most single composition alloys. The η
(Cu6Sn5) crystals are much larger and rod-shaped than those in the admixed amalgam.

Microstructure of set single-composition amalgam

Final set material (Fig. 9.10) consists of
Particles of
 Unreacted Ag3Sn (γ phase) and surrounded
by a mesh of rod shaped η (Cu6Sn5).
Embedded in a matrix made up of
 γ1 (Ag2Hg3)

Advantages/disadvantages of Spherical
high-copper amalgam
Advantages
1. Faster set. Figure 9.10  Schematic representation of setting
2. Lower residual mercury. reaction and microstructure of admixed amalgam.
138  Part 2  Direct Restorative Materials
3. Lower creep during condensation.
4. Faster finishing.
5. Higher early strength.
6. Low condensation pressure.

Disadvantages
1. Less working time.
2. Condensation pressure not sufficient to displace matrix during condensation (while
restoring proximal cavities). Contouring of matrix band required.

PROPERTIES OF SET AMALGAM

Microleakage
Penetration of fluids and debris around the margins may cause secondary caries. Dental
amalgam has an exceptionally fine record of clinical performance because of its tendency to
minimize marginal leakage (see tarnish and corrosion).
Self sealing  The small amount of leakage under amalgam resto­rations is unique. If the
restoration is properly inserted, leakage decreases as the restoration ages in the mouth. This
may be due to the formation of corrosion products in the tooth-restoration interface. Over
a period of time they seal the interface and reduce leakage. Thus amalgam is a self sealing
restoration. Both low and high copper amalgams are capable of sealing against microleakage
but the accumulation of corrosion products is slower with the high-copper alloys. Initial
leakage can be reduced through the application of varnish on the cavity walls. Use of dentin
bonding agents (bonded amalgam technique) also show promise.

Dimensional Change
The earliest amalgams exhibited expansion while setting. This was because of the
greater mercury/alloy ratio used. Amalgams may expand or contract, depending on its
manipulation. Ideally, dimensional change should be small. Excessive contrac­tion can
lead to microleakage, sensitivity and secondary caries. Excessive expansion can produce
pressure on the pulp and postoperative sensitivity. Protrusion of the restoration can also
occur.
ISO Sp. 24234:2015 requires that amalgam should not expand more than 0.15% or contract
less than –0.1% at 37 °C, during hardening. Mechanically, triturated modern amalgams, both
low and high copper, prepared from low mercury/alloy ratios show a slight contraction.

Theory of dimensional change

Contraction  When the alloy and mercury are mixed contraction results initially as the
particles dissolve and the γ1 grows. The final volume of γ1 is less than the initial volumes of
silver and mercury that go into making the γ1. Therefore, contraction will continue as long as
growth of γ1 continue.
Expansion  The γ1 crystals as they grow, impinge against one another, and produce an
outward pressure tending to oppose contraction. If there is sufficient mercury present to
provide a plastic matrix, an expansion will occur when γ1 crystals impinge on each other.
After a rigid γ1 matrix has formed, growth of γ1 crystals cannot force the matrix to expand.
Instead γ1 crystals will grow into interstices containing mercury, consuming mercury,
 Dental Amalgam  Chapter 9  139
and pro­ducing continued reaction. Therefore, reducing mercury in the mix will favor
contraction.
Thus, factors favoring contraction are
 Low mercury/alloy ratio
 Higher condensation pressure (squeezes out mercury)
 Smaller particles (consumes more mercury because of increased surface area)
 More trituration (accelerates setting)
Modern amalgams show a net contraction, whereas older amalgams always showed
expansion. Two reasons for this diffe­rence are
 Older amalgams contained larger alloy particles and were mixed at higher mercury/
alloy ratios.
 Hand trituration was used before. Modern amalgams are mixed with high speed
amalgamators (equivalent to increase in trituration time).

Effect of Moisture Contamination (Delayed Expansion)

If a zinc-containing-low-copper or high-copper
amalgam is contaminated by moisture during trituration
or condensation, a large expansion can take place.
It usually starts after 3-5 days and may continue for
months, reaching values greater than 400 µm (4%). This
is known as delayed expansion or secondary expansion
(Fig. 9.11). The expansion is caused by the releases of
hydrogen gas from the reaction of zinc with water.
H2O + Zn → ZnO + H2 (gas)
This hydrogen gas does not combine with the amalgam,
but collects within the restoration, creating extreme
internal pressure and expansion of the mass. This causes
protrusion of the resto­ration out of the cavity, increased
creep, increased microleakage, pitted surfaces and Figure 9.11  Delayed expansion of
corrosion. Dental pain, recurrence of caries, and fracture amalgam.
of the restoration are seen as a result of these poorly
inserted restorations.
Note
Moisture contamination after the cavity has been filled does not cause delayed expansion.
Nonzinc alloys do not show this type of expan­sion when contaminated with water. However,
moisture conta­mination of the mix of any alloy results in inferior physical properties.

Indications for zinc free alloys

Amalgam without zinc tends to be less plastic and less workable. These alloys are used only
for cases where it is difficult to control moisture, e.g. patients having excessive salivation,
retrograde root canal filling, subgingival lesions, etc.

Strength
Well designed amalgam restorations have sufficient compressive strength to withstand normal
intraoral masticatory forces.
140  Part 2  Direct Restorative Materials

Compressive strength Hour 7 Days

Low copper (lathe cut) 45 MPa 302 MPa
Low copper (spherical) 141 MPa 366 MPa
Admixed 137 MPa 431 MPa
Single composition 262 MPa 510 MPa

Tensile Strength
Amalgam cannot withstand high tensile or bending stresses and can fracture easily in
improperly designed restorations (Fig. 9.12). Therefore, the cavity should be designed so that
the restoration will receive minimal tension or shear forces in service.
Low Copper Admixed Single composition
60 MPa 48 MPa 64 MPa

Factors affecting strength

Effect of rate of hardening  Amalgams do not gain strength as rapidly as might be desired.
After 20 minutes, compressive strength may be only 6% of the one week strength. ISO
specifications stipulates a minimum of 100 MPa at one hour and 350 MPa after 24 hours. Since
the initial strength of amalgam is low, patients should be cautioned not to bite too hard for
a least 8 hours after placement, the time at which at least 70% of its strength is gained. The
one hour compressive strength of high-copper single-composition amalgams is exceptionally
high (262 MPa), so the chances of accidental fracture is less.
Even after six months, some amalgams may still be increa­sing in strength, suggesting that
the reactions between the matrix phases and the alloy particles may continue indefinitely.
Clinical significance The rate of hardening should be considered during the placement of
amalgam. In class II restorations where a supporting matrix has been placed, removal of the
matrix should be done at the appropriate time. Early removal can result in fracture. Excessive
pressure on the restoration by the patient prematurely to test the occlusion can also result
in fracture.

Effect of trituration  Either undertrituration or overtrituration will decrease the strength for
both low-copper, and high-copper amalgams.

Figure 9.12  A fractured amalgam restoration. Amalgam Figure 9.13  Amalgam with high
is technique sensitive. If improperly placed it can result creep rate displaying marginal
in many problems including fracture, leakage, sensitivity, breakdown.
periodontal problems, etc.
 Dental Amalgam  Chapter 9  141
Effect of mercury content  Sufficient mercury should be mixed with the alloy to wet each
particle of the alloy. Insufficient mercury produces a dry, granular mix (Fig. 9.18) which can
result in a rough and pitted restoration which is prone to corrosion.
Excess mercury in the mix can produce a marked reduction in strength because of the higher
γ2 content (which is the weakest phase—see setting reaction).

Effect of condensation  Higher condensation pressure results in higher compressive strength

(only for lathe-cut alloys).
Reason  A good condensation technique will minimize porosity and remove excess mercury
from lathe-cut amalgams. If heavy pressures are used in spherical amalgams, the condenser
will punch through. However, spherical amalgams condensed with lighter pressures produce
adequate strength.

Effect of porosity  Voids and porosities reduce strength.

Porosity is caused by
1. Decreased plasticity of the mix (caused by too low Hg/ alloy ratio, under trituration and
over trituration).
2. Inadequate condensation pressure.
3. Irregularly shaped particles of alloy powder.
4. Insertion of too large increments.
Increased condensation pressure improves adaptation and decreases voids. Fortunately, voids
are not a problem with spherical alloys.

Effect of cavity design

 The cavity should be designed to reduce tensile stresses.
 Amalgam has strength in bulk, therefore, the cavity should have adequate depth and
width.

Creep
It is defined as a time dependent plastic deformation.
Creep of dental amalgam is a slow progressive Box 9.2    Creep test
permanent deformation of set amalgam, which occurs Creep is tested by subjecting a 7 day
under constant stress (static creep) or intermittent old cylindri­cal specimen to a load of 36
stress (dynamic creep). MPa (at 37 °C) for a specified time usually
between 1 and 4 hours.
Significance of creep
Creep is related to marginal breakdown of low-copper amalgams. The higher the creep, the
greater is the degree of marginal deterioration (Fig. 9.13).
According to ISO 24234:2015 creep should be below 2% See Box 9.2.

Creep values
In general lathe-cut low-copper alloys show the highest creep values, often exceeding ADA
limits. The lowest creep values are shown by the high copper amalgams.
Amalgam Type Creep
Low-copper lathe cut amalgam 6%
Low-copper spherical 1.5%
High-copper admixed amalgam 0.5%
High-copper unicompositional amalgam 0.05 to 0.09%
142  Part 2  Direct Restorative Materials
Factors affecting creep
Microstructure  The γ1 (Ag-Hg) phase has a big effect on low-copper amalgam creep rates.
Increased creep rate is shown by larger γ1 volume fractions. Decreased creep rate is shown
by larger γ1 grain sizes. The γ2 phase is associated with higher creep rates.
Single composition high-copper amalgams have very low creep rates, due to absence of γ2
phase and due to the presence of η (Cu6Sn5) rods, which acts as barrier to deformation of the
γ1 phase. Increased zinc content reduces creep.
Effect of manipulative variables  For increased strength and low creep values
 Mercury/alloy ratio should be minimum.
 Condensation pressure should be maximum for lathe-cut or admixed alloys.
 Careful attention should be paid to timing of trituration and condensation. Either under
or over-trituration or delayed condensation tend to increase the creep rate.

Retention of Amalgam
Amalgam does not adhere to tooth structure. Retention of the amalgam filling is obtained
through mechanical locking. This is achieved by proper cavity design (see cavity design in
technical considerations). Additional retention if needed can be obtained by placing pins
within the cavity. Amalgam can also be bonded using special bonding agents.

Tarnish and Corrosion

Amalgam restorations often tarnish and corrode in the mouth. Black silver sulfide can form on
the surface of an amalgam restoration in some patients. Both high and low-copper amalgams
show corrosion. However corrosion in high-copper amalgams is limited because η phase is
less susceptible.

Factors related to excess tarnish and corrosion

 High residual mercury.
 Surface texture—small scratches and exposed voids.
 Contact of dissimilar metals, e.g. gold, and amalgam.
 Patients on a high sulphur diet.
 Moisture contamination during condensation.
 Type of alloy—low copper amalgam is more susceptible to corrosion (due to higher γ2
content) than high copper. Also η (Cu6Sn5) phase of high copper is less susceptible to
corrosion.
 A high copper amalgam is cathodic in respect to a low-copper amalgam. Therefore, mixed
high copper and low copper restorations should be avoided.

Corrosion of amalgam can be reduced by

 Smoothing and polishing the restoration.
 Correct Hg/alloy ratio and proper manipulation.
 Avoid dissimilar metals including mixing of high and low copper amalgams.

Biological considerations
Two types of potential biological effects can occur.
1. Adverse systemic effects of the mercury component.
2. Contact reaction of the mucosa with amalgam or amalgam corrosion products. (Oral
lichenoid reaction).
 Dental Amalgam  Chapter 9  143
Mercury  Mercury is toxic to the human body and
to the environment. Fortunately risk to the patient
of mercury exposure from dental restorations is very
low even with multiple restorations (Boxes 9.3 and
9.5). However, mercury vapors pose a greater risk
to the dental personnel as they as they are more
easily inhaled and absorbed through the lungs.
Mercury vapors may be produced during trituration
and condensation of amalgam and removal of old
restorations. Further information is under the section
mercury toxicity at the end of the chapter.
Contact reactions  Reactions occurring from Figure 9.14  Lichenoid reaction on mucosa
adjacent to amalgam restoration.
proximity or contact with amalgam are rare. The
symptoms are normally classified as delayed hypersensitivity reactions (type IV), and they
were called oral lichenoid reactions (OLRs) by Finne et al. These are lesions that clinically
and histologically resemble lichen planus (Fig. 9.14), but have an identifiable etiology.
These reactions are presumably due to allergic or toxic reactions to compounds released or
generated from the restoration.
It is recommended that patch tests should be performed in patients with OLR if the lesions
are in close contact with amalgam fillings. Replacement of such restorations is recommended
if there is a positive patch test reaction to mercury or components of amalgam and if there
are no signs of concomitant generalized lichen planus.

Technical considerations
Manipulation of Amalgam
The clinical success of amalgam restorations is highly dependent on the correct cavity design
and selection and manipulation of the alloy. If a restoration is defective, it is usually the fault
of the operator and not the material.

CAVITY DESIGN
Providing retention  Since amalgam does not adhere to tooth structure, proper design of the
cavity is very important. The amalgam cavity is designed to provide maximum mechanical
locking of the amalgam (Fig. 9.15). This is achieved by creating a cavity with walls that diverge
towards the floor of the cavity (or converge towards the mouth of the cavity). This results in a
cavity mouth that is narrower, effectively locking the amalgam within the cavity. Additional
retention if needed can be obtained by placing pins within the cavity.

Box 9.3    Current position on safety of dental amalgams

Although dental amalgam is the single largest source of mercury exposure for many individuals, current evidence does
not indicate that dental amalgam is causing illness in the general population. However, there is a small percentage of
the population which is hypersensitive to mercury and can suffer health effects from even a low exposure.
A total ban on amalgam is not considered justified. Neither is the removal of sound amalgam fillings in patients who
have no indication of adverse health effects attributable to mercury exposure.
As recently as May 2005, the ADA endorsed amalgam as being safe for pregnant women.
As a general principle, it is advisable to reduce human exposure to heavy metals in the environment, even if there is no
clinical evidence of adverse health effects, provided the reduction can be achieved by other materials at reasonable cost
and without introducing other adverse effects.
144  Part 2  Direct Restorative Materials

Figure 9.15  The cavity walls are designed to

lock the amalgam restoration. This is achieved
by creating walls that taper, effectively making
the mouth of the cavity narrower than the base.

Four wall support  For effective condensation, the cavity should have four walls and a floor.
If one or more of the walls of the cavity is absent, a stainless steel matrix (Figs. 9.21 and
9.22) can compensate for the missing walls. Failure to have a four wall support can result
in inadequate condensation which can weaken the amalgam. Additional retention can be
obtained with amalgam pins or screws.
Preventing tensile fracture  Since amalgam has poor tensile strength, the cavity should have
sufficient depth and width in order to provide sufficient bulk to the amalgam, especially those
in high stress areas.
Cavosurface angle  The junction of the cavity with the external surface should be as close
to a right angles as possible. Beveling is not indicated for amalgam as it can cause fracture of
the amalgam at the margins.

SELECTION OF MATERIALS

Alloy
The alloy is selected based on clinical need.
 For restorations subjected to occlusal forces, an amalgam with high resistance to marginal
fracture is desirable.
 If strength is needed quickly the best choice is spherical or high copper alloys, but they
require a fast operator.
 A nonzinc alloy is selected in cases where it is difficult to control moisture.
 Indium containing alloys  Indium performs the same functions as zinc and in addition,
it decreases the γ2 phase.

Mercury
There is only one requisite for dental mercury and that is its purity. Common contaminating
elements such as arsenic, can lead to pulpal damage. A lack of purity may also adversely affect
physical properties. High purity mercury is labelled as ‘triple distilled’.
 Freezing point –38.87 °C
 Boiling point 356.9 °C
ADA Sp. No. 6 for dental mercury requires that the mercury should possess no surface
contamination and less than 0.02% nonvolatile residue.
 Dental Amalgam  Chapter 9  145
Dispensers
Because proportioning is important, manufacturers
have develo­ped some simple dispensers for alloy and
mercury (Fig. 9.16). Dispensing by volume is unreliable
because it is affected by particle size and the degree of
packing (trapped air and voids) in the dispenser.

Tablets
Figure 9.16  Mercury/alloy dispenser.
This is the most accurate method of dispensing.
Manufacturers compress alloy powder into tablets of controlled weight which is used with
measured amounts of mercury.

PreProportioned Capsules
Preproportioned capsules containing alloy powder and mercury in compartments separated
by a membrane are available (Figs. 9.17A and B). They usually contain 400, 600, 800 or in
rare cases 1200 mg of alloy powder with corresponding proportion of mercury. Before use,
the membrane is ruptured by compressing the capsule, and the cap­sule is then placed in a
mechanical amalgamator.

Advantages
1. Consistent proportioning.
2. Low mercury/alloy ratio.
3. Physical handling not required thus reducing health hazard.

Disadvantages
Mercury and alloy may leak. The dentist is forced to use one alloy/mercury ratio for all situations
when using disposable capsules. Also, the disposable capsules are expensive.

MERCURY: ALLOY RATIO (PROPORTIONING)

Prior to mechanical triturators, when amalgam was triturated manually excess mercury had
to be used in order to achieve smooth and plastic amalgam mixes.
This excess mercury was removed from the amalgam by
1. Using a squeeze cloth to squeeze out the excess mercury.
2. Increasing dryness technique  During condensation of each increment, a mercury rich
soft layer comes to the surface. This is removed by condensing excess amalgam and
carving off the excess.

A B
Figures 9.17A and B  (A) Preproportioned capsules. (B) Diagram of the capsule showing separating membrane.
146  Part 2  Direct Restorative Materials
Eames’ technique
The better method of reducing mercury content is to reduce the original mercury/alloy ratio.
In 1959 Dr. Wilmer Eames proposed 1:1 ratio of mercury: alloy. This is came to be known as the
minimal mer­cury or Eames’ technique (mercury/alloy 1:1). (Prior to this manufacturers usually
recommended higher mercury/alloy ratios of 6.5:5,7:5 and even 8:5 to ensure adequate
amalgamation.) However, it is still necessary to squeeze mercury out of the mix using the
increa­sing dryness technique. Hence, with this technique, 50% or less mercury will be in the
final restoration, with obvious advantages.
Mercury alloy ratios ranges from 43 to 54%. In preproportioned capsule the mercury/alloy
ratio is determined by the manufacturer and is usually less than 50%.
Low mercury/alloy ratios are not easy to triturate manually. In order to benefit from a low
mercury/alloy ratio a high speed mechanical triturator (amalgamator) is absolutely essential.

TRITURATION
The objective of trituration is to wet all the surfaces of the alloy particles with mercury. For
proper wetting, the alloy surface should be clean. Rubbing of the particles mechanically
removes the oxide film coating on alloy particles.

Trituration is achieved either by

 Manually by hand
 Mechanical mixing

Manual mixing
A glass mortar and pestle is used (Fig. 9.18). The
mortar has its inner surface roughened to increase the
friction between amalgam and glass surface. A rough
surface can be maintained by occasional grinding
with carborundum paste. A pestle is a glass rod with
a round end.

The three factors to obtain a well mixed amalgam mass

are
1. The number of rotations,
Figure 9.18  Glass mortar and pestle.
2. The speed of rotation and
3. The magnitude of pressure placed on the pestle. Typically a 25 to 45 second period is
sufficient.

Mechanical trituration
Mechanical amalgamators are more commonly used to triturate amalgam alloy and mercury
(Fig. 9.19).
 The disposable capsule serves as a mortar. Some capsules have a cylindrical metal or
plastic piece in the capsule which serves as the pestle. The capsule is inserted between the
arms on top of the machines. When switched on, the arms holding the capsule oscillate
at high speed thus triturating the amalgam. Most amalgamators have hoods that cover
the arms holding the capsule in order to confine mercury spray and prevent accidents.
 Reusable capsules are available with friction fit or screw-type lids. This type uses alloy in
tablet form and capsulated mercury. At one time not more than two pellets alloy should
be mixed in a capsule.
 Dental Amalgam  Chapter 9  147

A B
Figures 9.19A and B  (A) Mechanical amalgamator for preproportioned capsules. (B) Close-up of the mechanical arm
that grips and vibrates the capsules (right).

With either type, the lid should fit the capsule tightly, other­wise, the mercury can spray out
from the capsule, and the inhala­tion of fine mist of mercury droplets is a health hazard.
Amalgamators have automatic timer and speed control device. The speed ranges from
3200 to 4400 cycles per minute. High copper alloys require higher mixing speeds.
Mixing time  The mixing time can vary depending on the speed, oscillating pattern, and
cap­sule designs. Spherical alloys usually require less amalgamation time than do lathe-cut
alloys. A large mix requires slightly longer mixing time than a smaller one. Manufacturer’s
recommendations should be followed when determining mixing speed and time.

Advantages of mechanical trituration

1. Shorter mixing time.
2. More standardized procedure.
3. Requires less mercury when compared to hand mixing technique.

Under-triturated mix
 It is rough and grainy and may crumble (Fig. 9.20 A).
 It gives a rough surface after carving and tarnish and corro­sion can occur.
 Strength is less.
 Mix hardens too rapidly and excess mercury will remain.

Normal mix
 It has a shiny surface and a smooth and soft consistency (Fig. 9.20 B).
 It may be warm (not hot) when removed from the capsule.
 It has the best compressive and tensile strength.
 The carved surface retains its lustre after polishing, hence increased resistance to tarnish
and corrosion.

Over-triturated mix
 The mix is soupy, difficult to remove from capsule and too plastic to manipulate (Fig. 9.20 C).
 Working time is decreased.
 Results in higher contraction of the amalgam.
 Strength increases for lathe-cut alloys, whereas it is reduced in high copper alloys.
 Creep is increased.
148  Part 2  Direct Restorative Materials

A B C
Figures 9.20A to C  Three possible mixes. (A) An under-triturated mix. (B) Correct mix. (C) An over-triturated mix.

MULLING
Mulling is actually a continuation of trituration. It is done to improve the homogeneity of the
mass and get a single consistent mix. It can be accomplished in two ways
 The mix is enveloped in a dry piece of rubber dam and vigo­rously rubbed between the first
finger and thumb, or the thumb of one hand and palm of another hand for 2–5 seconds.
 After trituration the pestle is removed and the mix is triturated in the pestle-free capsule
for 2–3 seconds.
Mulling is not required for mechanical triturated amalgams.

CONDENSATION
The amalgam is placed in the cavity after trituration, and packed (condensed) using suitable
instruments.

Aims
1. To compact the mass to increase the density of the restoration.
2. To reduce voids.
3. To remove excess mercury.
4. To adapt the amalgam to the preparation walls and margins.
Proper condensation increases the strength and decreases the creep of the amalgam.
Condensation must always be done within the four walls and floor. If one or more walls of the
cavity are missing, a steel matrix (Figs. 9.21 and 9.22) may be used to compensate for it. Failure

A B
Figure 9.22  Tofflemire matrix. Wooden pegs help
Figures 9.21A and B  Matrix retainers and bands. seal the embrasure area and contain the amalgam.
 Dental Amalgam  Chapter 9  149
to use a matrix can result in a poorly condensed and
weak restoration. Amalgam can also escape into the
interdental space (amalgam overhang—Fig. 9.23)
resulting in inflammation, bleeding and pain.

Condensers
Condensers are instruments with serrated tips of
different shapes and sizes (Figs. 9.24A and B). The
shapes are oval, crescent, trapezoidal, triangular,
circular or square. The condenser type is selected Figure 9.23  Amalgam overhang resulting
from failure to use matrix effectively.
as per the area and shape of the cavity. Smaller the
condenser, greater is the pressure exerted on the
amalgam. Condensation can be done manually
or mechanically. For spherical amalgams, a large
condenser tip should be selected to reduce punching
through and improve condensation.
A

Manual condensation
The mixed amalgam is held in an amalgam well (Fig.
9.25). The mixed material is packed in increments. B
Each increment is carried to the prepared cavity by Figures 9.24Aand B  Amalgam condensers.
means of a small forceps or an amalgam carrier (Fig. (A) Circular serrated. (B) Rectangular
9.26). serrated.

Once inserted, it should be condensed immediately

with suffi­c ient pressure (approximately 3 to 4
pounds). Condensation is started at the center, and
the condenser point is stepped sequentially towards
the cavity walls.
The smaller the condenser the greater the force.
Serrated condensers are preferable. The shape of
the condenser should conform to the area under
Figure 9.25  Amalgam well.
condensation. A large circular condenser may be
ineffective for cavity corners. For corners a smaller
point or a triangular or rectangular condenser is
more effective.
As the mix is condensed some mercury rich material
rises to the surface. Some of this can be removed,
to reduce the final mercury content and improve
the mechanical properties. The remainder will assist
bonding with the next increment.
Modern amalgams are fast setting and so working
time is short. Therefore, condensation should be as
rapid as possible. A fresh mix of amalgam should be
ready if condensation takes more than 3 or 4 minutes.
Long delays between mixing and condensation,
results in weaker amalgam.
Spherical alloys have little ‘body’ and thus offer
only mild resistance to the con­densation. When
condensing these alloys, a larger condenser is Figure 9.26  Two commonly used amalgam
recommended. carriers.
150  Part 2  Direct Restorative Materials
The cavity is overfilled (Fig. 9.27) so that the
excess mercury rich layer can be subsequently
trimmed away during the carving process.

Mechanical condensation
Mechanical condensers (Figs. 9.28A and B)
provide vibration or impact type of force to
pack the amalgam mix. Less effort is needed
than for hand condensation.

SHAPING AND FINISHING

Precarve Burnishing
Some operators perform a precarve burnishing.
This condenses and smooths the surface Figure 9.27  Amalgam condensation.
amalgam and reduces the voids and
irregularities caused by the serrated condenser.
It also removes some of the overfilled mercury
rich surface layer from the surface.

Carving
The restoration is carved to reproduce the
tooth anatomy. Carving also removes the
weaker mercury rich surface layer. The carving
A
should not be started until the amalgam is
hard enough to offer resistance to the carving
instrument. A scraping or ringing sound should
be heard when it is carved. If the carving is
started too soon, the amalgam may be so
plastic that it may pull away from the margins. B
Sharp carvers are used with strokes proceeding Figures 9.28A and B  A mechanical pneumatic
from tooth surface to amalgam surface. Various condenser (A) with handpieces (B).
carving instruments are shown in Fig. 9.29.

Burnishing
After the carving, the restoration is smoothened, by burnishing the surface and margins of
the restoration. Burnishing is the plastic deformation of a surface casued by sliding contact

Frahm Cleoid Discoid Ward 2 Hollenback

A B C D E
Figures 9.29A to E  Various amalgam carving instruments.
 Dental Amalgam  Chapter 9  151
Ball Ovate T-Ball Acorn

A B C D
Figures 9.30A to D  Various types of amalgam burnishers.

with another object. Fast setting alloys gain sufficient strength by this time to resist rubbing
pressure. Burnishing slow setting alloys can damage the margins of the restoration.
Burnishing is done with various types of burnishers (Figs. 9.30A to D) using light stroke
proceeding from the amalgam surface to the tooth surface. Final smoothing can be done by
rubbing the surface with a moist cotton pellet.

Polishing
Polishing minimizes corrosion and prevents adherence
of plaque. The polishing should be delayed for at least
24 hours after condensation, or preferably longer. Wet
polishing is advised, so a wet abrasive powder in a
paste form is used. Dry polishing powders can raise
the temperature above 60°C. If the temperature rises
above 60°C, mercury is released which may cause
corrosion and fracture at the margins. High copper
unicompositional alloys with high early strength may
be polished at the same sitting after the materials has
hardened sufficiently. However, polishing should be
carried out delicately using soft abrasives and gentle
pressure. A completed amalgam restoration is shown Figure 9.31  A completed amalgam
restoration.
in Fig. 9.31.

AMALGAM BONDING
Amalgam restorations do not reinforce the teeth. Teeth with MOD cavities are susceptible
to cuspal fractures. Bonding of the amalgam with a suitable adhesive (4-META) has been
shown to improve fracture resistance of the tooth (twice as much as nonbonded restorations).
Amalgam bonding also reduces marginal leakage and postoperative sensitive. The bonding
mechanism is similar to that of resin bonding agents. The bonding agent penetrates the
dentinal tubules and forms a hybrid zone. The bond with the amalgam is micromechanical
through the formation of resin tags when amalgam is condensed into the uncured bonding
agent. However, amalgam to amalgam bond is not so effective and therefore repair with
bonding agents is not recommended. A variety of amalgam bonding agents are available
commercially (Fig. 9.32).
152  Part 2  Direct Restorative Materials
MERCURY TOXICITY
Mercury is toxic to living creatures. Free mercury should not
be sprayed or exposed to the atmosphere. This hazard can
arise during trituration, condensation and finishing of the
restora­tion, and also during the removal of old restorations at
high speed. Mercury vapors can be inhaled. Skin contact with
mercury should be avoided as it can be absorbed.
Any excess mercury should not be allowed to get into the
sink, as it reacts with some of the alloys used in plumbing. It
also reacts with gold ornaments.
Mercury has a cumulative toxic effect. Dentists and dental
assistants, are at high risk. Though it can be absorbed by the
skin or by ingestion, the primary risk is from inhalation.
Figure 9.32  Amalgam bond.
Precautions
In placing and removing amalgam fillings, dentists should use techniques and equipment
to minimize the exposure of the patient and the dentist to mercury vapor and to prevent
amalgam waste from being flushed into municipal sewage systems
1. The clinic should be well ventilated.
2. Use preproportioned capsules possible to control mercury alloy ratio .
3. The alloy mercury capsules, should have a tightly fitting cap to avoid leakage.
4. Whenever possible use of protective barriers such as rubber dam isolation.
5. High volume evacuation should be used when condensing and carving amalgam.
6. While removing old fillings, a water spray, mouth mask and high volume suction should
be used.
7. The use of ultrasonic amalgam condenser is not recommen­ded as a spray of small mercury
droplets is observed surrounding condenser point during conden­sation.
8. All excess mercury and amalgam waste should be stored in well-sealed containers under
fixer solutions.
9. Amalgam scrap and materials contaminated with mercury or amalgam should not be
subjected to heat sterilization.
10. Proper disposal systems should be followed, to avoid environme­ntal pollution. Amalgam
separators should be used to capture the amalgam from the spittoon and the suction
devices and to prevent amalgam waste from being flushed into public sewage systems
11. Amalgam scrap should be disposed or recycled through the appropriate agencies.
12. Extracted teeth containing silver restorations should not be disposed in the infectious
waste and incinerated. Rather they should treated as hazardous amalgam scrap and
disposed accordingly.
13. Spilled mercury is cleaned as soon as
possible. Avoid carpeted floors in the
operatory as it is extremely difficult to clean
it from carpets. Vacuum cleaners are not
used because they disperse the mercury
further through the exhaust. Mercury
suppressant powders are helpful but these
are tempo­rary measures. A mercury spill
kit (Fig. 9.33) is commercially available for
management of mercury spills. Figure 9.33  Mercury spill kit.
 Dental Amalgam  Chapter 9  153
14. Skin contacted with mercury should be washed with soap and water.
15. Annually, a program for handling toxic materials is moni­tored for actual exposure
levels.

Amalgam Disposal
Residual amalgam and empty amalgam capsules must be disposed of separately in special
containers. These containers contain fixing salts or other chemical substances to bind mercury
vapours. These containers must be disposed of according to legal requirements, returning
them to the respective manufacturer. Local/regional instructions for waste disposal must be
observed.

Amalgam separators (ISO 11143:2008)

Dentists should use dental amalgam separators to catch and hold the
excess amalgam waste coming from office spittoons. The amalgam
separators separate the heavier metal particles from the liquid.
Removal of old fillings and placement of new amalgam restorations
are sources of amalgam contamination. Without dental amalgam
separators, the excess amalgam waste will be released to the sewers
via drains in the dental offices.
Many companies market amalgam separators (Fig. 9.34). The unit acts
as a collection tank allowing settling and decantation, thus separating
liquids from solids. The maintenance is done on a periodic basis to
decant off the liquid in your canister that will build up faster than the
sediment. When full the heavy metal sediment unit is emptied into Figure 9.34  Amalgam
a separate container. The collected sludge is either shipped directly separator.
to a recycler or collected by an appropriate hauler who will ship it to
a recycler.

Extracted teeth containing amalgam fillings

Extracted teeth (not containing amalgam) are considered potentially infectious material
and should be disposed into medical waste containers subject to the containerization and
labelling provisions of the Occupational Safety and Health Administration (OSHA) blood-borne
Pathogen Standard. However, extracted teeth containing amalgam should not be placed in a
medical waste container that uses an incinerator for final disposal. Incinerating teeth releases
mercury directly into the atmosphere. Many metal recycling companies will accept extracted
teeth with amalgam. A recycler may be contacted and ask about their policies and any specific
handling instructions they may have.

How does amalgam waste affect the environment?

If improperly managed by dental offices, dental amalgam waste can be released into
the environment. If an amalgam separator is not used, the excess amalgam waste will
be released to the sewers via drains in the dental offices (Box 9.4). Not all public sewage
management facilities are equipped to manage hazardous waste like amalgam. At the
treatment plant, the amalgam waste settles out as a component of sewage sludge that is then
disposed through various means.
1. In landfills thereby contaminating the surrounding land and water sources.
2. Through incineration, thereby contaminating the air.
3. As sludge when used as fertilizer contaminates agricultural land and water bodies and
enters the food source.
154  Part 2  Direct Restorative Materials

Box 9.4    Amalgam waste management in India

The surveys carried out by the Central Board and various other agencies indicated that health care establishments and
private clinics in India did not give due attention to their waste management. It did not form an integral part of their
health care program. The negligence on the part of the health care establishments was reflected in various articles in the
newspapers and a public interest litigation in the Supreme Court. Realizing the gravity of the issue, the Central Board took
up the matter with the Ministry of Environment and Forests. This led to the notification of ‘Biomedical waste (Handling
and management) Rules’, 1998. Now that there is legal binding on the health care establishments, the state government
is slowly streamlining the process of waste segregation, collection, treatment and disposal. However in spite of the
legislation, in reality, little is being done to effect proper monitoring, implementation and penalty for noncompliance.
Huge amounts of hazardous amalgam scrap is being released into the environment through drains and public garbage
disposal. It is imperative that national dental association and their local branches (IDA) find adequate solutions for safe
disposal. The dangers of environmental pollution affect all including the dental service providers and families.

ADVANTAGES AND DISADVANTAGES OF AMALGAM RESTORATIONS

Advantages
1. Reasonably easy to insert.
2. Not overly technique sensitive.
3. Maintains anatomic form well.
4. Has adequate resistance to fracture.
5. Self-sealing; minimal-to-no shrinkage and resists leakage.
6. Durable and long lasting.
7. Wears well and causes minimal wear of natural teeth.
8. More economic than other alternative posterior restorative materials like cast gold alloys
and composite.

Disadvantages
1. The color does not match tooth structure.
2. They are more brittle and can fracture if incorrectly placed.
3. Requires removal of some healthy tooth structure for cavity designing.
4. They are subject to corrosion and may darken as it corrodes.
5. Corrosion products may stain teeth over time
6. Galvanic action. Contact with other metals may cause occasional, minute electrical flow.
7. They eventually show marginal breakdown.
8. Temporary sensitivity to hot and cold because it is a metal.
9. They do not bond to tooth structure.
10. Environmental mercury concerns.

Box 9.5    The amalgam controversy

Amalgam has been the subject of much public concern from America to India because of the presence of mercury.
Studies have often been taken out of context resulting in considerable alarm among the general public. Some of these
controversies have been created by dentists themselves. It is of the uppermost importance that people be correctly
informed on the position taken by the international scientific community and the leading health care agencies with
respect to the potential risk of amalgam. The following reports have justified the continued use of amalgam.
 Dental Amalgam  Chapter 9  155

In the US, the Assistant Secretary for Health established in 1991, a research committee with the aim of carefully reviewing
nearly 500 scientific publications on amalgam. The study, which appeared in 1995, failed to show any harmfulness for
the amalgam fillings.
Following the advice of the General Surgeon and the Center for Disease Control and Prevention of the Food and Drug
Administration, the US Public Health Service recently published an article in a magazine with a very high circulation. The
purpose was to clarify the issue and reassure the American people, who had been alarmed by the many news reports
on the amalgam risk.
In Switzerland, Chairmen from the four Dental Departments at Universities of Berne, Basel, Geneva and Zurich replied
to the alleged charges of amalgam-induced damages which appeared on newspapers and nonscientific journals with
a review article. Amalgam was judged as a safe and effective material for posterior tooth filling, with the only exception
of allergic patients.
At two meetings of the Federation Dentaire Internationale held in 1994 in Vancouver and Budapest, amalgam was
acquitted on the charge of toxicity and was judged as a valid, cheap and still irreplaceable material.
In 1995, a joint statement from the World Health Organization (through two of its agencies, the Oral Health Program
and the Office for Global and Integrated Environmental Health, and from the FDA, amalgam fillings were considered
to be safe and inexpensive, although their color was different from that of natural teeth. For environmental reasons,
the document also reported, there could be in the future some limitation to the use of amalgam. Unfortunately, such
restrictions were misinterpreted by the mass media, causing unjustified fears in the public opinion and a rising demand
for substitution of the restorations.
Ever since the first environmentalist protests against the use of amalgam, a research center was created in Germany by
the University Departments of Münster and Erlangen. After reviewing several scientific papers and following hundreds of
patients, including 200 pregnant women, the center concluded that: (i) no harmful effects from amalgam had been found
in both the general population and the newborns; (ii) high plasma levels of mercury had been found as a consequence
of elevated fish consumption.
After careful studies, the Swedish Medical Research Council concluded that all restoration materials currently in use,
including amalgam and composite resins, are safe and effective. Nevertheless the Swedish government, through the
Department of Environment, recently issued a series of rules to limit the use of amalgam for filling purposes. The main
argument was based on an ecological ground, as it was estimated that between 40 and 60 tons of amalgam are carried
in the mouth of Swedish people. It was feared that, as a consequence of crematory habits, mercury would be massively
released in the environment. In Sweden alone, nearly 300 kilograms of mercury are estimated to be dispersed in the
atmosphere, and between 200 and 400 kilograms in the water mains, every year.
There is no question about the fact that the international dental community has been strongly reducing the use of
amalgam for filling carious teeth; the main reason, however, has been an esthetic demand from patients rather than a
toxicological need. Not unexpectedly, most colleagues from all over the world have kept using amalgam in their own or
their offspring’s mouth, whenever needed.
As reported in the literature, a certain number of patophobic or easily influenced patients still prefer to have restorations
with materials other than amalgam, even after receiving all possible information. Their demands should be satisfied as
long as this decision may have a placebo effect; however, these patients should be discouraged from having their still
perfect amalgam restorations substituted by other materials. In fact removal of these restorations pose a bigger risk of
releasing mercury into the environment.
As a useful reminder to the student, the best filling is the one that has never been applied; the most effective therapy is
prevention.
10
Chapter

Direct Filling Gold

Chapter Outline
• Applications –– Mat Foil –– Hand Mallet
• Contraindications –– Alloyed Electrolytic –– Condensers
• Composition and Purity Precipitates –– Finishing
• Gold Foil • Powdered Gold • Mechanical Condensers
–– Manufacture –– Synonym • Properties of Compacted Gold
–– Supplied As –– Manufacture –– Strength
–– Preformed Foils –– Available As –– Hardness
–– Platinized Foil • Manipulation of Direct Filling –– Density
–– Cohesive and Noncohesive Gold –– Effect of Voids
Gold –– Desorbing or Degassing –– Tarnish and Corrosion
• Electrolytic Precipitate –– Electric Annealing –– Biocompatibility
–– Available As –– Flame Desorption –– Disadvantages
–– Mat Gold –– Compaction –– Advantages

Prior to the discovery of amalgam, pure gold was very

popular as a filling material. The use of gold foil in
modern dentistry starts around 1400 in renaissance
Italy. Its use is described in a medical text written in 1425
by Giovanni Arcolani (Johannas D’Arcola) a professor
of the University of Bologna. Robert Woofendale is
credited to have introduced it to the USA in 1766 on
his arrival from England. However, its use became
widespread in the USA only towards the beginning of
the 19th century (Fig. 10.1).
It is the most noble of metals and rarely tarnishes in
the oral cavity. Gold in its pure form is very soft (25
BHN). Its malle­ability and lack of a surface oxide layer Figure 10.1  An example of gold foil
marketed in the early 1900s.
permit increments to be welded together. This unique
characteristic of gold to be welded at room temperature (cold-welded), allows gold to be used
as a direct filling material.
Although the dental profession sometimes refers to all direct filling golds (DFGs) as ‘Gold Foils’
the present products may be divided into three categories. All are of 99.99% or higher purity,
except two (Platinized foil and Electraloy RV).
Currently, direct filling gold is not as widely used as it once was. However, it will continue to be
described because it is still used and is an excellent restorative material when placed properly.
 Direct Filling Gold  Chapter 10  157
APPLICATIONS
1. Pits and small class I restorations (Fig. 10.2).
2. For repair of casting margins.
3. For class II, class V and class VI restorations
(Fig. 10.3).
4. Repair of cement vent holes and perfor­
ations in gold crowns (Figs. 10.4A to C).

Contraindications
Figrue 10.2  Class I gold restoration. Gold
1. Teeth with very large pulp chambers. restorations are esthetic, corrosion resistant and
2. Periodontally compromised teeth. long lasting if placed properly. (Courtesy: Sechena).

3. Handicapped patients who are unable

to sit for the long dental appointments
required for the procedures.
4. Root canal filled teeth because these teeth
are brittle.

Types
Many categories of direct filling gold are
available and is based on its physical form and
manufacturing process.
1. Foil (fibrous gold)
–– Sheet
-- Cohesive Figure 10.3  Class V gold restoration on a
premolar. (Courtesy: Sechena).
-- Noncohesive
–– Ropes
–– Cylinders
–– Laminates
–– Platinized
2. Electrolytic precipitate (crystalline gold)
–– Mat

A B C
Figures 10.4A to C  Above illustrations demonstrate how a perforation in a cast gold crown can be repaired with DFG.
(Courtesy: Sechena).
158  Part 2  Direct Restorative Materials

A B A
Figures 10.5A and B  (A) Gold foil booklet from the early twentieth century. (B) Gold foil.

–– Mat foil
–– Gold-calcium alloy B
3. Granulated gold (encapsulated powder) Figures 10.6A and B 
Gold foil cylinders (Morgan
Hastings).
Composition and purity
Most modern gold restorations are made of gold of high purity (99.99 % or higher) excepting
for the platinized and alloyed gold.

GOLD FOIL
Gold foil is the oldest of all products described. It was manufactured for dental applications
as early as 1812 by Marcus Bull (USA). It is manufactured by beating gold into sheets.

Manufacture
Gold is malleable. A cast ingot of 15 mm thickness is beaten to a submicroscopic thickness
of 15 or 25 µm. The product is called gold foil (Figs. 10.5A and B). The crystals of the original
cast metal are deformed and elongated so that they have a fibrous structure, hence it is also
known as fibrous gold.

Supplied As
1. Flat square sheets (of varying thickness) in booklet form, 12 sheets (each 10 cm × 10 cm)
per booklet.
–– No. 4 wt. 4 grains (0.259 gram) 0.51 µm thick.
–– No. 3 wt. 3 grains (0.194 gram) 0.38 µm thick.
The number denotes the weight of the gold. Other sheets also available are Nos. 20, 40,
60 and 90. No. 3 foil is used to manufacture electrolytic and powder gold.
2. Preformed cylinders (Figs. 10.6A and B) and ropes.These are made by cutting the No. 4
gold foil sheets into strips of varying widths (3.2, 4.8, etc.) and then rolling and compressing
them into pellets or cylinders. They may be ‘carbonized’.
3. A number of sheets of foil may be placed one top of each other to form laminated gold
foil. One type of laminated foil is the platinized foil, which is a sheet of pure platinum foil
sandwiched between two sheets of pure gold foil.
 Direct Filling Gold  Chapter 10  159
Carbonized or corrugated gold
Rolling into a pellet or cylinder form is convenient for carrying and compacting into cavities.
Many dentists cut and roll their own gold. Preformed gold foil in the form of ropes and
cylinders may be available in ‘carbonized’ or ‘corru­gated’ form (made from No. 4 foil that has
been ‘carbonized’ or ‘corru­gated’). This form of gold foil is of historical interest because it was
an outcome of the great Chicago fire in 1871. Corrugated foil is obtained by placing the gold
foil in between sheets of paper and igniting it in a closed container. On igniting, the paper
gets char­red, but the gold foil is left unharmed except that it becomes ‘corrugated’. This is
because of the shriveling of the paper while oxidizing in the airtight safe. After the carbon is
removed it is found that the gold exhibits superior welding property.

Platinized foil
This is a laminated foil in which pure platinum foil is sandwiched between two sheets of No. 4
gold foil. The sheets are beaten and joined together. Platinum is added to gold foil to increase
the hardness of the restoration. This product is available only in No. 4 sheet form.

Cohesive and noncohesive gold

In practice only the sheet foil is furnished in both conditions, though all forms of direct filling
gold could be supplied in cohesive and noncohesive form.

Noncohesive  The earliest gold foils were ‘noncohesive’ in nature. The manufacturer subjects
the foil to a volatile agent such as ammonia, which is absorbed on the surface of the gold.
Ammonia-treated foil is called noncohesive foil. This adsorption of ammonia gas onto the
surface of the gold prevents the gold foil from adhering if it folds back on itself, or contacts
other pieces of foil. This is also useful when pellets or cylinders are packed together in
containers. It prevents premature cohesion of pellets in their container. It also protects the
surface of the gold from contamination which can’t be removed. This treatment enables the
user of the foil to handle it with a little more ease.
Noncohesive gold can also have adsorbed agents like iron salt or an acidic gas (sulfur or phos­
phorous containing groups) on its surface. The volatile film is readily removed by heating (see
annealing), thereby restoring the cohesive character of the foil. Noncohesive gold is rarely
used currently, but may be used to build-up the bulk of a direct gold restoration.
Disadvantage of noncohesive gold Because the gold wouldn’t stick to itself one could not build
contour above the cavosurface. Fillings were pretty much flat from cavosurface to cavosurface.
Cohesive  Cohesive gold is also called ‘sticky gold’. It was introduced in 1854 by Dr. Robert
Arthur when he published his paper on sticky gold (cohesive gold), “A New Method of Using
Gold Foil”.
For cold-welding, gold should have a clean surface free from impurities. Gold attracts gases,
e.g. oxygen to its surface and any absorbed gas film prevents cohesion of individual increments
of gold during their compaction. The manufacturer, therefore, supp­lies the gold essentially
free of surface contaminants. This type of gold is known as cohesive gold foil.
Representative commercial products  Jensen Gold Foil

ELECTROLYTIC PRECIPITATE
Crystalline gold powder is formed by electrolytic precipitation. The powder has a dendritic
crystalline structure. The powder is formed into shapes or strips by sintering (heat fusion) at
high temperatures but below their melting point. The particles coalesce or join together at
this temperature.
160  Part 2  Direct Restorative Materials
Available As
Mat, mat foil and alloyed.

Mat Gold
Mat gold is electrolytically precipitated gold sandwiched between sheets of foil and then
formed into strips. The strips can be cut by the dentist into the desired size. Mat gold is used
to build-up the bulk of the restoration, as it can be more easily compacted and adapted to the
cavity. However, mat gold has lots of voids and results in a pitted exter­nal surface. Therefore,
foil gold is used to cover the mat gold and form the surface of the restoration.

Mat Foil
It is a sandwich of electrolytic precipitated gold powder between sheets of No. 3 gold foil. The
sandwich is sintered and cut into strips of differing widths. The dentist can then cut these to
the desired lengths. Sandwiching mat between foil sheets was done to try to eliminate the
need to veneer the restoration with a layer of foil. This type is no longer marketed.

Alloyed Electrolytic Precipitates

A form of electrolytic gold is an alloy of gold and calcium (0.1% by wt.) called ‘Electraloy
RV’. For greater ease of handling, the alloy is sandwiched between two layers of gold foil.
Calcium produces stronger restorations by dispersion strengthen­ing, which locks in cold work
strengthening. Thus, alloying with calcium changes the crystalline structure and makes it
harder and stronger.

POWDERED GOLD

Synonym  Granular gold

Since the 19th century, chemically precipitated gold powders have been available in
agglomerated form with a liquid such as alcohol or dilute carbolic acid, which held the
agglome­rate together. The agglomerates usually disintegrated when compaction was
attempted, so the gold powder was mixed with a wax binder and enclosed in a No. 3 gold
foil. This form was first marketed commercially in the 1960s as ‘Goldent’ (Morgan Hastings
Co.) (Figs. 10.6A and B). In the 1980s another brand ‘EZ Gold’ (Ivoclar North America) was
introduced.

Manufacture
A fine powder is formed by chemical precipitation or by atomizing the metal. The particle sizes
vary (average 15 µm). The pellets are mixed with soft wax (0.01% organic wax, which is burnt
off prior to use) and then wrapped with gold foil (No. 3), rather than sintering the mass, like
for mat gold.

Available As
The powdered gold pellets have a cylindrical or irregular shape and a diameter of 1 to 2 mm.
The ratio of gold foil to powder varies from 1 to 3 for the smallest pellets to approximately
1 to 9 for the largest.
 Direct Filling Gold  Chapter 10  161
The foil acts as an effective container and matrix for the powdered metal, while it is condensed.
Some operators believe that the use of powdered gold pellets increases cohesion during
compaction and reduces the time required for placing the restora­tion. This is because each
pellet contains 10 times more metal by volume than comparable sized pellet of gold foil.

MANIPULATION OF DIRECT FILLING GOLD

There are three processes involved
 Desorbing
 Compaction
 Finishing

DESORBING OR DEGASSING
Synonym  Degassing, annealing
The direct filling golds are received by the dentist in a cohesive condition, except for the
noncohesive golds. However, during storage and packaging, they absorb gases from the
atmosphere. Adsorbed gases prevent gold from fusing. Hence, it is necessary for the dentist
to heat the foil or pellet immediately before it is carried into the prepared cavity. This heating
process which removes surface gases (oxygen, nitrogen, ammonia, moisture or sulfur dioxide)
and ensures a clean surface is called desorbing or degassing (rather than annealing). Storage
in air tight containers is advised and the operator should wear chamois finger tips to protect
the gold from contamination. A totally dry cavity is essential throughout the compaction
process in order to allow complete cohesion.
Direct filling golds may be heated by one of two methods
 In bulk on a tray by gas-flame or electricity (Figs. 10.7A and B).
 Piece by piece, in a well-adjusted alco