ISTANBUL TECHNICAL UNIVERSITY GRADUATE SCHOOL OF SCIENCE

ENGINEERING AND TECHNOLOGY

PRODUCTION AND CHARACTERIZATION OF MODIFIED PET FOAM

M.Sc. THESIS

Hatice Bilge ÇEBİŞLİ

Department of Polymer Science and Technology

Polymer Science and Technology Programme

MAY, 2012
ISTANBUL TECHNICAL UNIVERSITY GRADUATE SCHOOL OF SCIENCE
ENGINEERING AND TECHNOLOGY

PRODUCTION AND CHARACTERIZATION OF MODIFIED PET FOAM

M.Sc. THESIS

Hatice Bilge ÇEBİŞLİ

(515091035)

Department of Polymer Science and Technology

Polymer Science and Technology Programme

Thesis Advisor: Prof. Dr. Nurseli UYANIK (ITU)

Co-Advisor: Assoc. Prof. Dr. Tuncer YALÇINYUVA (IU)

MAY, 2012
 İSTANBUL TEKNİK ÜNİVERSİTESİ FEN BİLİMLERİ ENSTİTÜSÜ

MODİFİYE EDİLMİŞ PET KÖPÜK ÜRETİMİ VE KARAKTERİZASYONU

YÜKSEK LİSANS TEZİ

Hatice Bilge ÇEBİŞLİ

(515091035)

Polimer Bilim ve Teknolojisi Bölümü

Polimer Bilim ve Teknolojisi Programı

Tez Danışmanı: Prof. Dr. Nurseli UYANIK (ITU)

Eş-Danışman: Doç. Dr. Tuncer YALÇINYUVA (IU)

MAYIS 2012
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 To my family,

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viii
FOREWORD

This M.Sc. study has been done in Polymer Science and Technology Graduate
Program of Institute of Science and Technology at Istanbul Technical University.
First and foremost I would like to express my indebtedness to my advisors Prof. Dr.
Nurseli UYANIK and Assoc. Prof. Dr. Tuncer YALÇINYUVA who have supported
and encouraged me from the beginning of this study and shared their deep
knowledge’s and experiences.
I would like to acknowledge to AKSOY Inc. for kindly providing our raw material,
PET. I would like to thank to ZWICK Avrasya Company to enable me testing
products in their laboratories with dear Heybül GÜMRÜK ‘s help.
I am also thankful to my colleagues in Department of Chemistry and Polymer
Science and Technology from Istanbul Technical University for sharing their ideas,
support, and knowledge with me. I would like to thank to Gülçin TORUNOĞLU
TURAN, Merve MOCAN ÇETİNTAŞ from our laboratory group, and to Dr.
Hidayet Özgür ŞANLI for their contributions during my study.
I would like to thank to Ayça BAL from Istanbul University for TGA and DTA
characterizations and for her interpretations for thermal analysis data, to Tolga
GÜMÜŞOĞLU for his help in contact angle measurements, to Assis. Prof. Dr. Ali
DURMUŞ and Koray YURDAKUL sharing with us their compression technique
experiences, to Zehra ÖZBAŞ for her kind support in laboratory. In addition, a
special thank to Prof. Dr. Ahmet KAŞGÖZ for enabling me to make my studies in
his laboratory at tough times.
I would like to thank to Dr. M.S.Saffet BAYSAL from ASES AVIATION S&S Inc.
supporting me to finish my thesis study.
Last, but not least, I am so grateful to my family, without them I could not be able to
finish this thesis. I would like to express my deep gratitude; to my parents, Ülkü and
Cemil Sait ÇEBİŞLİ who raised me with their love and who never get tired to
support me for every subject in my life, even in this thesis, as material and as
spiritual; and to my brother Osman Erdem ÇEBİŞLİ for his tender care, support for
me.

December 2011 Hatice Bilge ÇEBİŞLİ

Polymer Science and Technology

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TABLE OF CONTENTS

Page

FOREWORD ............................................................................................................. ix
TABLE OF CONTENTS......................................................................................... xii
ABBREVIATIONS ................................................................................................. xiii
LIST OF TABLES ................................................................................................... xv
LIST OF FIGURES ............................................................................................. xviiii
SUMMARY ........................................................................................................... xixx
ÖZET...................................................................................................................... xxiii
1. INTRODUCTION .................................................................................................. 1
2. THEORETICAL PART ........................................................................................ 5
2.1 Thermoplastic Polymers ..................................................................................... 5
2.1.1 Poly(butylene terephthalate) ....................................................................... 6
2.1.2 Poly(ethylene terephthalate) ....................................................................... 7
2.2 Polymer Foams ................................................................................................. 11
2.2.1 Types of polymer foams ........................................................................... 12
2.2.1.1 Thermoplastic and thermoset polymer foams .................................... 12
2.2.1.2 Open- and closed-cell polymer foams................................................ 14
2.2.1.3 Flexible, Semirigid and Rigid Polymer Foams .................................. 18
2.3 Production of Polymer Foams .......................................................................... 19
2.3.1 Blowing agents .......................................................................................... 20
2.3.1.1 Physical blowing agents ..................................................................... 21
2.3.1.2 Chemical blowing agents ................................................................... 22
2.3.1.3 Determining the amount of gas generated ......................................... 28
2.3.1.4 Control of cell size and cell stability .................................................. 29
2.3.2 Production methods of polymer foams ..................................................... 30
2.3.2.1 Extrusion of thermoplastic foam sheet ............................................... 31
2.3.2.2 Compression molding method ........................................................... 32
2.3.2.3 Reaction injection molding of foams ................................................. 35
2.3.2.4 Injection molding method .................................................................. 37
2.3.2.5 Rapid rotational foam molding .......................................................... 39
2.4 Properties of Polymer Foams ........................................................................... 40
2.4.1 Foam geometry ......................................................................................... 40
2.4.2 Foam density ............................................................................................. 42
2.4.3 Foam structure........................................................................................... 42
2.4.4 Cell size distribution ................................................................................. 42
2.4.5 Foam anisotropy ........................................................................................ 43
2.4.6 Melt rheology suitable for foaming .......................................................... 43
2.5 Characterization Methods of Polymer Foams .................................................. 45
2.6 Application Areas of Polymer Foams .............................................................. 49
2.7 Literature Review of PET Foams ..................................................................... 51
2.8 Polycaprolactone–Poly(dimethylsiloxane) Block Copolymers ....................... 54

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3. EXPERIMENTAL PART ................................................................................... 57
3.1 Chemicals Used ................................................................................................ 57
3.1.1 Poly(ethylene terephthalate) (PET) ........................................................... 57
3.1.2 5-Phenyl-1H-tetrazole (5-PT) ................................................................... 57
3.1.3 Polycaprolactone–poly(dimethylsiloxane), (PCL-PDMS-PCL) ............... 57
3.1.4 Paraffin liquid (medium) ........................................................................... 58
3.2 Equipments Used .............................................................................................. 58
3.2.1 Vacuum Oven ............................................................................................ 58
3.2.2 Melt flow index device (MFI) ................................................................... 59
3.2.3 Hydraulic hot press.................................................................................... 59
3.2.4 Hydraulic cold press .................................................................................. 60
3.2.5 Mechanical test device .............................................................................. 61
3.2.6 Contact angle measurement instrument .................................................... 61
3.2.7 Calliper ...................................................................................................... 62
3.2.8 Thermogravimetric (TGA) and differential thermal (DTA) analysis
instrument ........................................................................................................... 63
3.3 Experimental Procedure ................................................................................... 64
3.3.1 Preparation of the mixture ......................................................................... 64
3.3.2 Production of cellular structure ................................................................. 64
3.3.2.1 Heating process in hydraulic hot press ............................................... 65
3.3.2.2 Cooling process in hydraulic cold press ............................................. 65
3.4 Tests and Analysis ............................................................................................ 65
3.4.1 Melt flow index ......................................................................................... 65
3.4.2 Mechanical test .......................................................................................... 66
3.4.3 Contact angle analysis ............................................................................... 66
3.4.4 Bulk density analysis................................................................................. 67
3.4.5 Cell density analysis .................................................................................. 67
3.4.6 Thermogravimetric (TGA) and differential thermal (DTA) analysis ....... 68
4. RESULTS AND DISCUSSION........................................................................... 71
4.1 The Optimization of Processing Conditions..................................................... 72
4.2 Density Analysis Results .................................................................................. 73
4.2.1 Bulk density analysis results ..................................................................... 73
4.2.2 Cell density analysis results ...................................................................... 75
4.3 Contact Angle Analysis Results ....................................................................... 80
4.4 Three-Point Bending Mode Flexural Test Results ........................................... 82
5. CONCLUSION ..................................................................................................... 85
REFERENCES ......................................................................................................... 89
APPENDICES .......................................................................................................... 99
CURRICULUM VITAE ........................................................................................ 109

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ABBREVIATIONS

ABS : Acrylonitrile-Butadiene-Styrene Copolymer

ASTM : American Society for Testing and Materials
BMC : Bulk Molding Compound
C.A. : Contact Angle
CBA : Chemical Blowing Agent
DSC : Differential Scanning Calorimeter
DMA : Dynamic Mechanical Analysis
DTA : Differential Thermal Analysis
EVA : Poly(ethylene vinyl acetate)
HCFCs : Hydro Chlorofluoro Carbons
HDPE : High Density Polyethylene
IS : Isoprene–Styrene Copolymer
L.A. : Left Angle
LDPE : Low Density Polyethylene
LLDPE : Linear Low-Density Polyethylene
MCFs : Microcellular Foams
MFI : Melt Flow Index
Min : Minute
PBA : Physical Blowing Agent
PC : Polycarbonate
PCL : Polycaprolactone
PCL-PDMS-PCL : Polycaprolactone and Poly(dimethyl siloxane) Block Copolymer
PDMS : Poly(dimethyl siloxane)
PE : Polyethylene
PET : Poly(ethylene terephthalate)
PFA : Physical Foaming Agent
PPG : Poly(propylene glycol)
PS : Polystyrene
5-PT : 5-Phenyl-1H-tetrazole
PU : Polyurethane
PVA : Poly(vinyl alcohol)
R.A. : Right Angle
SAN : Styrene-Acrylonitrile Copolymer
SEM : Scanning Electron Microscopy
SMC : Sheet Molding Compound
TGA : Termogravimetric Analysis
Tg : Glass Transition Temperature
Tm : Melting Temperature

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xiv
LIST OF TABLES

Page

Table 2.1 : Thermoplastics commonly used for closed-cell foams............................. 5

Table 2.2 : Properties of engineering polyester, PET ................................................. 8
Table 2.3 : Maximum gas pressure at decomposition and remaining pressure in
room temperature for various chemical blowing agents ......................... 27
Table 2.4 : Properties of chemical blowing agents ................................................... 27
Table 2.5 : Useful microstructural parameters to describe foams............................. 45
Table 2.6 : Summary of the most popular mechanical testing methods used for
foams. ...................................................................................................... 47
Table 2.7 : Characterization methods and standards of rigid cellular plastics .......... 47
Table 2.8 : Typical markets for low-density Foams ................................................. 51
Table 2.9 : Typical markets for high-density foams ................................................. 51
Table 4.1 : The average cell diameter and the bulk density analysis results of PET
foam samples that are changing with processing time ............................ 74
Table 4.2 : The cell density and cell size dispersity ratio analysis of PET foam
samples .................................................................................................... 75
Table 4.3 : The average cell size and density analysis results of cellular PET
samples changing with process variables in terms of temperature and
5-PT % content ........................................................................................ 76
Table 4.4 : The average cell size and density analysis results of cellular PET
samples changing with process variable in terms of PCL-PDMS-PCL
% content. ................................................................................................ 78
Table 4.5 : The average cell size and density analysis of PET foam samples
without PCL-PDMS-PCL additive.......................................................... 79
Table 4.6 : Contact angle measurement results of PET foam samples with the
average of +/- 0.19 standard deviation .................................................... 81
Table 4.7 : Three-point bending mechanical test results of PET foam samples with
the average of +/- 0.09 standard deviation .............................................. 83
Table A.1: Processing conditions for common exothermic blowing agents ........... 101
Table A.2: Properties of PET .................................................................................. 102

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LIST OF FIGURES

Page

Figure 2.1 : Polymerization reaction mechanism of PET ........................................... 8

Figure 2.2 : SEM photograph of (a) PU open-cell foam of density 28 kg m-3,
(b) Closed-cell LDPE foam of density 24 kg m-3 ................................. 15
Figure 2.3 : (a)Modelling the growth of an isolated spherical bubble in a PE melt.
(b)The predicted growth in the radii of the bubble and melt with time.16
Figure 2.4 : Developing foam in a structure with two large to every small bubble,
at the dimensionless times indicated ..................................................... 17
Figure 2.5 : Abnormally large cells, with >20 faces, formed by cell face collapse in
EVA foam of density 150 kg m-3, with a background of normal cells. 30
Figure 2.6 : Schematic of the extrusion foam process .............................................. 32
Figure 2.7 : Schematic of the compression molding foam process .......................... 33
Figure 2.8 : Schematic of the reaction injection molding foam process ................... 36
Figure 2.9 : Schematic of the injection molding machine ........................................ 37
Figure 2.10 : Schematic of the injection molding foam processes ........................... 38
Figure 2.11 : Single-charge rotational foam molding processing steps .................... 40
Figure 2.12 : Change in the structure of a foam containing a regular array of
bubbles as the volume fraction of gas increases ................................. 41
Figure 2.13 : Impact of temperature and pressure on the blowing agent .................. 45
Figure 2.14 : Typical compression stress–strain curve of a low-density elasto-
plastic foam, with compressive modulus of elasticity E*,
compressive strength σy*, and strain at densification εd*................... 48
Figure 3.1 : Vacuum oven instrument and vacuum desiccator. ................................ 58
Figure 3.2 : “Melt flow index” MFI device. ............................................................. 59
Figure 3.3 : Temperature control panel and pressure gauge of hydraulic hot press
instrument ............................................................................................. 60
Figure 3.4 : Hydraulic hot press ................................................................................ 60
Figure 3.5 : Three-point bending mode flexure test instrument ............................... 61
Figure 3.6 : Contact angle measurement instrument................................................. 62
Figure 3.7 : Linseis STA PT 1750 model TGA/DTA combined instrument ............ 63
Figure 3.8 : Charging of the mold within PET mixture into hot press instrument ... 64
Figure 3.9 : The three point bending flexural test layout, loading ............................ 66
Figure 3.10 : Contact angle, hydrophobic and hydrophilic surfaces ........................ 67
Figure 3.11 : Thermal analysis (TGA and DTA) graphs of PET and 5-PT .............. 69
Figure 3.12 : Decomposition behaviour of 5-PT with increasing temperature......... 70
Figure 4.1 : Time versus bulk density graph of PET foam samples ......................... 74
Figure 4.2 : Temperature versus cell density graph of PET foam samples .............. 77
Figure 4.3 : CBA percentage versus bulk density graph of PET foam samples with
0.075 % PCL-PDMS-PCL .................................................................... 77
Figure 4.4 : PCL-PDMS-PCL weight percentage versus cell density graph of PET
foam samples ......................................................................................... 78

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Figure 4.5 : Pressure versus cell density graph of PET foam samples ..................... 79
Figure 4.6 : CBA % versus cell density graph of PET foam samples ...................... 80
Figure 4.7 : Bulk density versus elastic modulus graph of PET foam samples with
0.075 % PCL-PDMS-PCL ..................................................................... 84
Figure 4.8 : PCL-PDMS-PCL % versus elastic modulus graph of PET foam
samples ................................................................................................... 84
Figure A.3 : Bubble Analysis Photos of PET Foam Samples ................................. 102
Figure A.4 : Cell Density Analysis Graphs of PET Foam Samples........................ 105
Figure A.5 : Water Contact Angle Measurement Photos of PET Foam Samples... 108

xviii
PRODUCTION AND CHARACTERIZATION OF MODIFIED PET FOAM

SUMMARY

Polymeric structural foams have been widely used in automotive, wind turbine,
aerospace, construction, marine, electronic and packaging industries. Foam plastics
are one of the fastest growing sectors of the plastics industry. As the consumption of
plastic materials increased, the concept of generating cells or bubbles in plastics
industry became an attractive option to reduce the cost of plastic material as long as
the mechanical properties of products were not sacrificed.
Foaming of thermoplastics is an advanced technology used in extrusion,
compounding, injection molding, blow molding, rotational molding, thermoforming,
and compression molding. There are two general types of foaming agents: a physical
foaming agent is metered directly under pressure into the polymer melt, is nearly
always the primary source for low density foams; a chemical foaming agent is a pure
chemical that reacts to produce blowing gas through heat-induced decomposition, is
usually the primary source for higher density foams.
Nearly all thermoplastics can be foamed, but commercially important foams are
mainly based on commodity plastics such that polyolefin (polyethylene,
polypropylene), polyurethane, polystyrene, poly(vinyl chloride), poly(ethylene
terephthalate), polycarbonate, and poly(methyl methacrylate) appeared as
thermoplastic matrices. Among all important commercial thermoplastics, semi-
crystalline poly(ethylene terephthalate) (PET) was chosen for foaming polymer
recently due to its superior characteristics, i.e. good resistance to high temperatures
and high compressive strength. The semicrystalline materials exhibit ten to one
thousand times higher cell nucleation densities compared with the amorphous
materials, resulting from heterogeneous nucleation contributions.
The aim of this study is to produce poly(etylene terephthalate) rigid foams in closed-
cell structure with a chemical blowing agent (CBA), by compression molding
method. A commercial ABA type triblock copolymer of polycaprolactone and
poly(dimethyl siloxane) which is α,ω-dihydroxy polycaprolactone–
poly(dimethylsiloxane) (PCL-PDMS-PCL) with Mn = 6500 +/-600; Mw PDMS = 3000
and Mw PCL endblocks = 2000 g/mol was used as additive.
The foaming of thermoplastic polymer was carried out with compression molding
process, which provides a convenient method for quick evaluation of material
formulations instead of labor and material intensive extrusion processing. The
process parameters, which are processing temperature, processing time and
processing pressure, can be optimized in this compression method.
Poly(ethylene terephthalate) is one of the high-temperature foaming polymers among
other thermoplastic polymers, and foamed with an exothermic type of chemical
blowing agent that is 5-phenyl-1H-tetrazole (5-PT). For most molding and extrusion
applications, the general rule of thumb is to select a chemical blowing agent that has
xix
a decomposition, or gas release, temperature closely matching with the processing
temperature to be used for the polymer. Due to the fact that, 5-PT was chosen as a
chemical blowing agent which decomposes into gas form at elevated temperatures
(above 250 oC), and the decomposition temperature of 5-PT closely matching with
the melting range of PET (around 250 oC) for foaming process.
Polymer foams were prepared by using hydraulic hot press with the processing
temperature and pressure in the ranges of 255 - 275 oC and 10 - 100 bar, respectively.
The process foaming time were taken from 6 to 22 minutes. The amount of 5-PT
addition as chemical blowing agent was changed between 0.05 % and 0.25 % (wt)
during the preparation of PET foam mixtures. After the foaming process in hydraulic
hot press was carried out, the foamed products were cooled in hydraulic cold press
with contant cooling time as 5 minutes under 50 bar pressure. Although the content
of the chemical blowing agent was kept constant as 0.10 % and 0.20 % in PET foam
samples, 0.10 % CBA content gave the best results. The optimum conditions were
achieved after several experiments, and then the PET foam samples to be analysed
were prepared by compression molding technique in hydraulic hot and cold presses.
The optimum conditions were presented as at 260 °C the processing temperature,
under 15 bar the processing pressure, 0.10 % (wt) CBA and 0.075 % (wt) PDMS
contents with 10 minutes the processing time in hydraulic hot press, and 5 min
cooling time under 50 bar pressure in hydraulic cold press.
The PCL-PDMS-PCL copolymer as surface modifying additive in polymer were
mixed at low levels (0.050 % – 0.300 % by weight) with PET, the resulting systems
displayed silicone-like, hydrophobic surface properties, as determined by critical
surface tension measurements or water contact angles. The effect of PCL-PDMS-
PCL content, the base polymer type and the morphology on the resulting surfaces are
discussed. PCL-PDMS-PCL addition to the foamed PET samples gave increased
toughness and better surface properties than those of the foamed PET samples
without PCL-PDMS-PCL additive under the same conditions. The brittleness of the
PET foams was also decreased although PCL-PDMS-PCL was added at very low
weight percentages during the preparation of the PET foam mixture.
The prepared 27 samples were investigated structural, morphological, mechanical
and processing points of view. The produced PET foams were analysed with contact
angle measurement, density calculation, cell size analysis and three-point bending
mode flexural test. A cellular foamed plastics were characterized by a cell size of one
milimeter or less in diameter and a cell density of at least a thousand cells per cubic
centimeter. These thermoplastic foams are produced by supersaturating a polymer
with a gas and then using a thermodynamic instability to generate thousands of
microvoids instantaneously. Elastic modulus, and contact angle measurements of the
foamed PET samples were measured for different cell structures. The results showed
that the mechanical properties are significantly affected by the foaming parameters;
the PCL-PDMS-PCL additive and the chemical blowing agent contents of the
thermoplastic polymer matrix. The prepared closed-cell PET foams were
characterized morphologically, physically and mechanically in terms of contact angle
measurement (ASTM D5946, ASTM D5725), density calculation (ASTM D1622-
08), and 3-point bending mode flexural test (ASTM D790-10).
This study also focuses on the feasibility study of improving mechanical properties
of high density poly(ethylene terephtlate) (PET) foams having closed-cell structure.

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The bulk density values are changing between 0.945 g/cm3 and 1.190 g/cm3. These
results shows that high density foams were formed.
The experimental results show that the elastic modulus of PET foam increased as
PCL-PDMS-PCL additive increased. Besides, as the bulk density increased the
elasticity of the foam was also increased, as the cell density increased the elasticity of
the foam was decreased. In general, crystallized products are more brittle than
amorphous products. PDMS addition to the foamed PET samples gave increased
toughness and better surface properties than those of the foamed PET samples
without PDMS additive under the same conditions. The weight reduction of PET was
achieved without sacrificing much of the mechanical properties by introducing
cellular structure in thermoplastic materials. It was observed that the elastic modulus
increased nonlinearly as the relative foam density and PDMS additive content
increased.
When the foaming time was more than 6 minutes, the tensile strength and elongation
at break values of cellular PET started to decrease. This was because the longer the
gas was allowed to diffuse into the cells, the larger the cell size was. Therefore, the
larger cell size (larger to some extent) decreased the tensile strength and elongation
at break. The foaming time had a relatively strong influence on cell nucleation and
cell growth for the amorphous and semicrystalline polyester meaning there was an
effect on the mechanical properties. Similar strong cell-size dependence on foaming
time was reported for styrenic resins. The foaming time in our experiment did have
effects on the mechanical properties, too.
The solubility of nitrogen in polymers increases linearly with pressure up to about 25
MPa. Therefore, increasing foaming pressure actually increased the foaming gas
concentration inside of PET, and the net result was a cell-size decrease and a cell
density increase. When the the cell density was larger, the elongation at break (% εb)
became larger. This explains why the elongation at break increased with increasing
foaming pressure under our foaming pressure scope. When the foaming pressure was
smaller than 10 MPa, the PET sample showed no detectable cell structure. This
means that the foaming pressure should exceed 10 MPa if one hopes to obtain
microcellular PET foam.
The effect of foaming temperature on the mechanical properties occurred in the
temperature range between 250 and 275 °C. When the foaming temperature was
lower than 250 °C, there was no detectable cell structure. One of the reasons was
that the foaming reagent 5-PT could not decompose completely at lower temperature;
hence, there was probably not enough gas necessary to form microcellular PET.
Another reason was that at lower foaming temperatures, the PET matrix stiffness
may have been sufficiently large enough to prevent nucleated cells from growing to
detectable size, even though the allotted foaming time should have allowed all of the
available gas to diffuse into the cells.
The effects of polycaprolactone block poly(dimethyl siloxane) (PCL-PDMS-PCL)
additive content on rigid PET foams were investigated mainly. There is an
increasement in contact angle measurement results with certain amount of PDMS
percentage increasement because of the migration of PDMS molecules to air-
polymer surface in PET foam samples. According to the calculated results, for the
samples which do not include PCL-PDMS-PCL, showed decrease in elongation at
break. It was observed that when the PCL-PDMS-PCL additive content was

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increased, the elastic modulus of PET foams increased, and the elastic modulus was
also increased as the relative foam density was increased.
Each sample description refers to a specific composition involving the components
used in the preparation of the samples. This description code explanation is presented
in results and discussion section.

xxii
MODİFİYE EDİLMİŞ PET KÖPÜK ÜRETİMİ VE KARAKTERİZASYONU

ÖZET

Polimer yapılı köpükler otomotiv, rüzgar türbini, uçak, uzay, inşaat, denizcilik,
elektronik ve ambalaj sektörlerinde kullanılmaktadır. Termoplastik ve termoset
olmak üzere iki ana gruba ayrılan polimerik köpükler plastik endüstrisi baz
alındığında en hızlı büyüme gösteren sektörlerin başında gelmektedir. Son
zamanlarda plastik malzemelerin tüketimindeki artış da bunu kanıtlamaktadır.
Dolayısıyla, plastik üretiminde “hücre” ya da “habbecik” oluşturma konsepti,
(mekanik özelliklerinden ödün verilmeden) hafif ürün eldesinin yanısıra maliyet
düşürmede etkin bir seçenek olmuştur.
Termoplastik köpük üretimi ileri bir teknoloji bilgisi gerektiren ekstrüzyon,
enjeksiyonla kalıplama, üflemeli kalıplama, döner kalıplama, ısıl şekillendirme
(termoforming) ve basınçla kalıplama (pres) yöntemleriyle gerçekleştirilmektedir.
Köpürtücü ajanların iki genel tipi vardır. Fiziksel bir köpürtücü ajanlar, basınç
altında doğrudan polimer eriyiğine beslenir, ve düşük yoğunluklu köpüklerin
üretiminde neredeyse her zaman birincil kaynak olarak geçmektedir. Kimyasal
köpürtücü ajanlar ise köpük ürünü eldesi için gerekli olan gazı üretmek amacıyla
yüksek ısı ile indüklenme sonucu bozunma reaksiyonu veren saf kimyasallardır.
Termoplastiklerin neredeyse tamamından termoplastik köpük ürün elde edilebilir;
ancak ticari değeri olan köpükler, köpük malzemelerde termoplastik matrisler olarak
beliren poliolefin (polietilen, polipropilen), poliüretan, polistiren, poli(vinil klorür),
polikarbonat, poly(etilen tereftalat), poli(metil metakrilat) gibi yaygın olarak
kullanılan plastiklere dayanır. Belirtilen önemli ticari termoplastik malzemeler
arasından, üstün özellikli yarı-kristal termoplastik malzeme poly(etilen tereftalat)
(PET), bu çalışmada köpük üretimi için seçilmiştir. Dolayısıyla, PET köpük eldesi bu
çalışmanın ana konusu olarak belirlenmiştir, çünkü PET yüksek sıcaklık, basınç ve
darbe dayanımı gibi üstün özelliklere sahiptir. Yarı-kristal malzemeler amorf
termoplastiklere göre heterojen hücre yoğunluğuna katkı sağladıkları için, on ile bin
kat arasında değişen hücre oluşumunu tetiklerler, dolayısıyla daha fazla hücre
yoğunluğu elde edilir.
Bu çalışmanın amacı, kimyasal köpürtücü ajan kullanılarak presle kalıplama yöntemi
ile kapalı-hücre morfolojisine sahip, yapısal olarak sert poly(etilen tereftalat) köpük
üretmektir. Polikaprolakton (PCL) ve poli(dimetil siloksan) (PDMS) ‘in üç bloklu
ABA tipi ticari bir kopolimeri olan α,ω-dihidroksi polykaprolakton–poly(dimetil
siloksan) (PCL-PDMS-PCL) Mn = 6500 (+/-600); Mw PDMS = 3000 ve Mw PCL uç
blokları = 2000 gr/mol, katkı maddesi olarak kullanılmıştır.

Bu çalışmada termoplastik polimer köpük üretimi presle kalıplama prosesi ile

gerçekleştirilmiştir. Bu proses, oldukça zahmetli ekstrüzyon prosesine kıyasla
malzeme formülasyonlarının çok daha hızlı geliştirilmesine olanak sağlar. Presle

xxiii
kalıplama metodunda optimize edilebilen proses parametreleri ise proses sıcaklığı,
proses süresi ve proses basıncıdır.
Termoplastik polimerler arsında oldukça yüksek sıcaklıklarda köpük elde edilebilen
bir polimer olan poly(etilen tereftalat), ekzotermik tipteki kimyasal şişirici maddesi
5-fenil-1H-tetrazol (5-PT) ile şişirilerek köpük eldesi sağlanmıştır. Birçok kalıplama
ve ekstrüzyon uygulamalarında, geçerli olan genel kural kimyasal şişirici ajanının
bozunma sıcaklığı ya da diğer bir deyişle gaz salınımının gerçekleşmesi için gereken
sıcaklığın, polimer işleme koşulları için gerekli olan sıcaklık değerinde seçilmesidir.
Bu genel kural baz alınarak, bu çalışmada PET’in işleme sıcaklığı (∼250oC) ile
uyumlu olan ve dolayısıyla yüksek sıcaklıklarda (~250 oC), parçalanıp gaz formuna
geçebilen ekzotermik bir kimyasal şişirici ajan olan 5-fenil-1H-tetrazol (5-PT)
kullanılmıştır.
Polimer köpükler hidrolik sıcak pres makinesi kullanılarak 255 - 275 oC aralığındaki
işleme sıcaklığı, 6 – 22 dakika aralığında değişen proses süresi ve 10 - 100 bar
aralığındaki proses basıncı ile üretilmiştir. Köpük üretiminde kimyasal şişirici madde
olarak kullanılan 5-PT miktarı kütlece % 0,05 ve % 0,25 aralığında değişmiştir.
Hidrolik sıcak pres makinesinde yüksek sıcaklıklarda elde edilen eriyik karışımı, 50
bar basınç altında 5 dakika boyunca hidrolik soğuk pres makinesinde soğutulmuş ve
sert formdaki PET köpük eldesi sağlanmıştır. Şişirici kimyasal madde miktarı kütlece
% 0,10 – % 0,25 aralığında değişmesine rağmen en iyi sonucu kütlece % 0,10
kimyasal şişirici madde içeriği vermiştir. Kütlece % 0,10 kimyasal şişirici ajan ve
kütlece % 0,075 PCL-PDMS-PCL katkısı içeriği ile oluşturulan karışım sıcak pres
makinesinde 260 °C proses sıcaklığı, 15 bar basınç uygulaması, 10 dakika proses
süresi ile ısıtma işlemi yapıldıktan sonra, soğuk pres makinesinde 15 bar basınç
altında 5 dakika süreyle soğutma işlemi yapılarak PET köpük üretimi için optimum
koşullar belirlenmiştir.
Polikaprolakton blok poli(dimetil siloksan), (PCL-PDMS-PCL) kopolimeri yüzey
modifikasyon katkısı olarak kullanılmış ve PET ile düşük oranlarda ( kütlece %
0,050 – % 0,300 aralığında) karıştırılmıştır. Eklenen PCL-PDMS-PCL miktarının
etkileri, elde edilen köpük ürününün morfolojik yüzey özellikleri ve baz alınan
polimer tipi tartışılmıştır. Sonuçta, kritik yüzey gerilimi ölçümleri veya su ile temas
açısı ölçümlerinden yararlanılarak, ürünlerin silikon benzeri bir hidrofobik yüzey
özelliği gösterdiği belirlenmiştir. PCL-PDMS-PCL katkısı maddesi eklenerek elde
edilen PET köpük örnekleri, aynı koşullar altında PCL-PDMS-PCL katkı maddesi
olmadan elde edilen PET köpük örneklerine göre artan bir tokluk ve daha iyi yüzey
özelliği sağlamıştır. PET köpük karışımı hazırlanması sırasında çok düşük
miktarlarda PCL-PDMS-PCL katkısı kullanılmasına rağmen elde edilen PET
köpüklerde kırılganlık da azalmıştır.
Deneyler sonucunda hazırlanan 27 örnek farklı proses parametreleri denenerek,
yapısal, yüzeysel ve mekanik özellikleri açısından incelenmiştir. Farklı hücre
özellikleriyle elde edilen tüm PET köpük örnekleri temas açısı ölçümü, yoğunluk
hesaplaması, hücre boyutlarının analizi ve üç-nokta eğme mekanik testi ile analiz
edilmiştir. Termoplastik köpük örnekleri, hücresel olarak 1mm veya daha düşük çap
uzunluğunda, ve santimetreküp başına en az bin tane hücreden oluşan hücre
yoğunluğuyla karakterize edilmiştir. Bu termoplastik köpükler, bir gazla bir
polimerin süper-doygunlaştırılmasını takiben, aynı anda milyonlarca mikro-boşluk
yaratılması sırasında oluşan termodinamik bir kararsızlık etkisiyle üretilmiştir. Farklı
hücre yapıları için elastik modülü ve temas açısı ölçümleri yapılmıştır. Sonuçlar,

xxiv
değişken proses parametrelerinin; PET matrisindeki PCL-PDMS-PCL katkısı ve
kimyasal şişirici madde içeriği, elde edilen ürünlerdeki mekanik özellikleri önemli
ölçüde etkilediğini göstermiştir. Hazırlanan kapalı hücre yapısındaki PET köpük
örnekleri için morfolojik, fiziksel ve kimyasal olarak; ASTM D5946 ve ASTM
D5725 standartlarına uygun olarak yapılan temas açısı ölçümleri, ASTM D1622-08
standartına uygun olarak yapılan yoğunluk hesaplamaları ve ASTM D790-10
standartına uygun olarak yapılan 3-nokta eğme testleri ile karakterize edilmiştir.
Bu çalışma ile kapalı hücre yapısına sahip yüksek yoğunluklu poli(etilen teraftalat)
(PET) köpüklerinin mekanik özelliklerinin iyileştirilmesine odaklanılmıştır.
Çalışmalar sonucunda yoğunluk değerlerinin 0,945 g/cm3 ve 1,190 g/cm3 aralığında
değiştiği gözlemlenmiştir. Bu sonuçlar yüksek yoğunluklu köpük eldesinin
gerçekleştiğini göstermektedir.
Deneysel sonuçlar, PET köpük elastik modülünün PCL-PDMS-PCL katkısı arttıkça
arttığını göstermektedir. Ayrıca, köpük yoğunluğu arttıkça köpük elastisitesi de
artarken, habbecik yoğunluğu arttıkça köpük elastisitesi azalmıştır. Kristal yapıdaki
ürünler, amorf yapıdaki ürünlere göre daha çok kırılganlık gösterir. PCL-PDMS-PCL
katkısı içeren PET köpük örnekleri, aynı koşullar altında PCL-PDMS-PCL katkısı
olmadan elde edilen PET köpük örneklerine göre artan bir tokluk ve daha iyi yüzey
özellikleri sergilemiştir. Termoplastik malzemelerden hücresel yapılı köpük üretimi
eldesi, sarf edilen PET ağırlığındaki azalma avantajı ile mekanik özelliklerden ödün
verilmeden sağlanmıştır. Bağıl köpük yoğunluğu ve PCL-PDMS-PCL katkı içeriği
arttıkça, örneklerde doğrusal olmayan bir elastik modül artışı gözlenmiştir.
5-PT kimyasal şişirici ajanının bozunarak gaz formuna dönüşmesi ve PET
granüllerinin tamamıyla erimesiyle oluşan eriyik karışımı sisteminda bir dengeye
ulaşıldıktan sonra, üründe homojen baloncuk dağılımı gözlenebilmesi için, PET
köpük üretimi 6 dakikadan daha uzun sürelerde gerçekleştirilmiştir. Süre ilerledikçe,
oluşan hücresel yapıdaki PET köpüğün çekme mukavemeti ve uzamada kopma
mekanik özellikleri azalmaya başlamıştır. Bunun nedeni, gazın süre ilerledikçe hücre
içine difüzlenmesindeki artış ile hücre boyutunun büyümesidir. Bu yüzden, büyük bir
çap değerine ulaşan hücreler (belli bir dereceye kadar büyüme), çekme dayanımı ve
uzamada kopma değerini düşürmüştür. Amorf ve yarı kristal yapıdaki polyester
köpük eldesinde, habbecik oluşum süreci ve proses süresinin mekanik özellikler
üzerine etkisi olduğu ispatlanmıştır. Benzer özellik stirenli reçineler için de hücre-
boyutunun, köpük oluşumu için gerekli olan proses süresi ile bağıntılı olduğu rapor
edilmiştir. Bizim deneyimizde de habbecik oluşum süresi ürünlerin mekanik
özelliklerini etkilemiştir.
Polimerlerdeki azot çözünürlüğü yaklaşık 25 MPa basınca kadar doğrusal olarak
artmaktadır. Bu nedenle, köpük oluşumunda basıncın artırılması aslında PET içinde
çözünen köpürtücü gaz konsantrasyonu artırmıştır, ve bu durumun net sonucu ise
hücre boyutunda küçülme ve hücre yoğunluğunda artış şeklinde olmuştur. Hücre
yoğunluğu ne kadar fazlaysa, uzamada kopma (% εb) değeri de o kadar büyüktür. Bu
durum, mekanik testlerimizin deneysel sonuçları kapsamındaki uzamada kopma
değerlerinin, basınç yükselmesiyle neden arttığını açıklamaktadır. Köpük oluşum
basıncı 10 MPa ‘dan daha düşük iken, PET örneği saptanabilir bir hücre yapısı
göstermemiştir. Bu durum, PET köpük elde edilmek isteniyorsa 10 MPa basıncın
aşılması gerektiği anlamına gelmektedir.
Köpük oluşum sıcaklığının ürünlerdeki mekanik özelliklere etkisi, 250 ve 275 °C
sıcaklık aralığındaki çalışmalarda sonuç vermiştir. Köpük oluşum sıcaklığı 250
xxv
°C’den daha düşük iken, oluşmuş herhangi bir hücre yapısı saptanamamıştır. Bu
durumun nedenlerinden biri, 5-PT kimyasal şişirici ajanının düşük sıcaklıklarda
tamamiyle bozunmuş olmamasından dolayı hücresel yapı formundaki PET köpük
eldesi için gerekli olan gaz miktarının bu ortamda muhtemelen yeterli miktarda
bulunmamasından kaynaklanmış olmasıdır. Diğer bir nedeni ise, düşük sıcaklıklarda
gerçekleşen köpük üretiminde, mevcut olan bütün gazın hücrelerin içine doğru
difüzlenebilmesi için gerekli olan habbecik oluşum süreci sağlanmış olsa bile, hücre
oluşumu sürecinde saptanabilir bir hücre boyutuna ulaşılmasını engelleyen PET
matrisinin sertlik değerinin yeterince büyük olmasından dolayı kaynaklanmaktadır.
Elde edilen sert PET köpüğün özellikleri üzerine, polikaprolakton blok poli(dimetil
siloksan) (PCL-PDMS-PCL) katkısının etkisi çalışmalar sırasında önemli ölçüde
araştırılmıştır. Belirli miktarlarda PCL-PDMS-PCL yüzdesi artışı ile orantılı olarak,
PET köpük örneklerinde bulunan PCL-PDMS-PCL moleküllerinin hava-polimer
yüzeyine göç etmesinden dolayı, temas açısı ölçüm sonuçlarında artış
gözlemlenmiştir. Deneysel sonuçlara göre, PCL-PDMS-PCL katkısı içermeyen
örneklerin uzamada kopma değerlerinde azalma olmuştur. PET köpük örneklerinde
PCL-PDMS-PCL katkısının yüzdesi arttıkça, elastik modül artmıştır. Bağıl köpük
yoğunluğundaki artış ile de elastik modülün arttığı gözlemlenmiştir.
Her örnek tanımlaması, örneklerin hazırlanılmasında kullanılan bileşenleri içerecek
şekilde yapılmıştır. Bu kod sistemi sonuçlar ve yorumlar kısmında figürlenerek
açıklanmıştır.

xxvi
1. INTRODUCTION

Polymeric structural foams came into being in the 1910s and have been widely used
in automotive, aerospace, construction, electronic and packaging industries since that
time. Foam plastics are one of the fastest growing sectors of the plastics industry. At
the beginning of the 21st century, about 23 billion pounds of foamed products were
consumed each year around the world [1], and this number is expected to increase
significantly in the future as more applications are discovered. Foam processing in
general has gained a significant technical and scientific sophistication [2], [3].
However, notwithstanding the capability to develop new classes of cellular materials
by foaming, the literature is still limited.

Over the last decades, foaming of polymers has evolved into a well-developed
technology for equipping materials with a set of desired properties. The achieved
scientific understanding, the technological progress as well as the broad range of
realized commercial applications have further driven the significant growth of this
particular field. Besides the continuous enhancement of foam formulations and the
ever-increasing improvement of processing technologies, the evolution of new fields
of research related to foams and their successful technological transfer into industrial
applications are steadily proceeding.

Nearly all thermoplastics can be foamed, but commercially important foams are
mainly based on commodity plastics. Foamed thermoplastic matrices are polyolefin,
polyurethane, polystyrene, poly(vinyl chloride), poly(methyl methacrylate),
poly(ethylene terephthalate), generally.

There are several categories of polymeric foams; however, only structural polymeric
foams (i.e., high density foams with closed-cell structure) are of concern in the
thesis.

The recent European ban of the use of azo based foaming agent “azodicarbonamide”
in gaskets and other products that come in contact with food [38] result in the fact

1
that the preference of environmentally friendly blowing agent “5-phenyl tetrazole”
usage in this study.

Recently a number of leading materials suppliers have tried to place clarified

polypropylene, polystyrene, and even new grades of nearly transparent high-density
polyethylene as potential substitutes for poly(ethylene terephthalate). So far, market
acceptance of these appears to be very limited. PET remains a favorite among brand
owners, who value its appearance, ease of processing and performance in packaging
lines, and its positive environmental image [4]. Foaming of polyesters in particular
can be identified as a topic of potential interest, both from a scientific as well as from
a commercial point of view.

Poly(ethylene terephthalate) (PET) is a low-cost engineering polymer with good

mechanical and thermal characteristics and exhibits high elastic moduli, high glass-
transition temperature (Tg), and good crystallinity and solvent resistance, appearing
one of the most versatile plastics in the world [5].

The availability of foams based on PET could be very interesting, mainly for the
temperature range allowed by the high melting temperature (Tm) of the bulk polymer
and its crystallinity. Such foams can be used in applications such as packaging,
thermal insulating panels, transportation, construction, and cores for sandwich
structures.

Although the market finds excellent utilities for PET, the low shear and elongational
viscosities and low melt strength of conventional PET prevents from being easily
foamed by typical technologies such as gas extrusion foaming, and complex
procedures have to be used [6]. In many cases PET has to be modified chemically or
physically to have homogeneous cell distribution in polymer matrix. In chemical
modifications, different treatments have been developed to improve the PET
macromolecular characteristics, in particular, to extend the polymer chain lengths
[7]. In physical type modification, PET is processed with additives to achieve
specific physical properties such as flexural, tensile, and barrier properties.

Microcellular semicrystalline polymers such as poly(ethy1ene terephthalate) show

great promise for engineering applications because of their unique properties,
particularly at higher densities. Recent studies reveal some high-density
microcellular polymers have longer fatigue lives and/or equal strengths to the neat

2
polymer. Relatively few microcellular-processing studies of semicrystalline
polymers have been presented. In general, semicrystalline polymers are relatively
difficult to microcellular process compared to amorphous polymers. The
semicrystalline materials exhibit ten to one thousand times higher cell nucleation
densities compared with the amorphous materials, resulting from heterogeneous
nucleation contributions [8].

Considering everything, PET was chosen recently among thermoplastic polymers

due to its superior characteristics, i.e. good resistance to high temperatures and high
compressive strength.

Furthermore, to produce polymeric cellular structures the blowing agents are needed.
Chemical blowing agents (CBAs) are made of a class of solid or liquid compounds
that decompose to form gases under processing conditions [9]. Most CBAs are solids
and decompose within a given temperature range. For most molding and extrusion
applications, the general rule of thumb is to select a CBA that has a decomposition,
or gas release, temperature closely matching the processing temperature to be used
for the polymer [10]. PET melts at higher temperatures around 250 °C, and 5-PT
decomposes at around 250 °C, too. Due to the fact that, 5-phenyl tetrazole (5-PT)
was chosen as the suitable chemical blowing agent to foam poly(etylene
terephthalate) PET in this study.

In this study, closed-cell structured poly(ethylene terephthalate) rigid foams were

produced with the help of a chemical blowing agent (5-PT) by compression method.
A commercial α,ω-dihydroxy polycaprolactone–poly(dimethylsiloxane) (PCL-
PDMS-PCL) additive were used at very low weight percentages to improve surface
properties of the PET foam samples, and to decrease the property of brittleness of the
PET foams. The PET foams produced with and without PCL-PDMS-PCL triblock
copolymer additive were analysed with structural, morphological and mechanical
testing methods. Besides, bubble formation characteristics were reviewed in a
thermoplastic polymer matrix.

3
4
2. THEORETICAL PART

2.1 Thermoplastic Polymers

Plastics are an important group of raw materials for a wide array of manufacturing
operations. Applications range from small food containers to large chemical storage
tanks, from domestic water piping systems to industrial piping systems that handle
highly corrosive chemicals, from toys to boat hulls, from plastic wrap to incubators,
and a multitude of other products. When properly designed and applied, plastic
provides light weight, sturdy/economic/resistant, and corrosion products. Plastics are
polymers. The term plastic is defined as “capable of being easily molded,” such as
putty or wet clay. The term plastics was originally adopted to describe the early
polymeric materials because they could be easily molded. Unfortunately, many
current polymers are quite brittle, and once they are formed they cannot be molded
[11].

Polymers can be subdivided into three main categories; thermoplastics consist of

individual long chain molecules, and in principle any product can be reprocessed by
chopping it up and feeding it back into the appropriate machine; thermosets contain
an infinite three dimensional network which is only created when the product is in its
final form, and cannot be broken down by reheating whilst rubbers contain looser
three dimensional networks, where the chains are free to change their shapes.

Table 2.1 : Thermoplastics commonly used for closed-cell foams.

Polymer name Abbreviation Type
Polyethylene PE Semi-crystalline
Ethylene-vinyl acetate
EVA Semi-crystalline
copolymer
Polypropylene PP Semi-crystalline
Polystyrene PS Glass
Polyvinylchloride PVC Glass + 10% crystalline
Polyphenyleneoxide
PPO Glass
blend with PS

5
The foam behaviour depends on the properties of the polymer from which it is made.
Nearly all thermoplastics can be foamed, but commercially important foams are
mainly based on commodity plastics – PE, PP, PS, and PVC (Table 2.1). This partly
reflects their low cost, and partly the availability of grades with highly elastic melts
[12].

In terms of microstructure thermoplastics can be divided into amorphous and semi-

crystalline solids. The amorphous ones are glassy up to a temperature called the glass
transition temperature Tg, whereupon they change into a rubbery liquid, the viscosity
of which falls as the temperature is raised further. Semi-crystalline thermoplastics
can be regarded as two phase materials, with an amorphous phase, and a crystalline
phase with a melting temperature Tm. The chemical structures and transition
temperatures of several thermoplastics can be considered to control the mechanical
properties. The melting values are not as precise as the melting points of pure metals;
the crystalline phase of polymers melts over a temperature range that ends at Tm, and
the exact values of Tg, and Tm, depend on the molecular weight. For semi-crystalline
polymers the percentage crystallinity is another important parameter due to
possibility of fabricating highly anisotropic forms of semi-crystalline polymers [13].

The thermoplastic polyester resin such as poly(butylene terephthalate) and

poly(ethy1ene terephthalate) are the examples of semi-crystalline polymers. The
melting point of PBT resins is about 30 °K lower than that of PET resins, resulting in
lower melt temperatures during moulding as well as slightly lower allowable design
temperatures for moulded parts. PET and PBT are mentioned on the ‘green list’ of
the European Regulation EEC 259/93, Annex II [14].

The class of thermoplastic polyesters has two major subclasses – polybutylene

terephthalate and polyethylene terephthalate - and two minor subclasses - PET
copolymer such as Eastman's PETG, and polyethylene naphthanate or PEN.

2.1.1 Poly(butylene terephthalate)

Polybutylene terephthalate (PBT) is a thermoplastic engineering polymer that is used

as an insulator in the electrical and electronics industries, produced by
the polymerization of butanediol and terephthalic acid. It is a thermoplastic (semi-
crystalline) polymer, and a type of polyester. PBT is resistant to solvents, shrinks
very little during forming, is mechanically strong, heat-resistant up to 150 °C (or 200

6
°C with glass-fibre reinforcement) and can be treated with flame retardants to make it
noncombustible.

PBT is closely related to other thermoplastic polyesters. PBT is similar in structure

to polyethylene terephthalate (PET), the difference being in the number of methylene
(CH2) groups present in the repeating units of the polymer molecules. Compared to
PET (polyethylene terephthalate), PBT has slightly lower strength and rigidity,
slightly better impact resistance, and a slightly lower glass transition temperature.
The mechanical properties of the two materials are also similar. However, PBT has a
lower melting point (223 °C [433 °F]) than PET (255 °C [491 °F]), so it can be
processed at lower temperatures. This property, combined with its excellent flow
when molten and its rapid crystallization upon cooling, makes PBT highly suitable
for injection-molding into solid parts. Either unmodified or reinforced with glass
fibres or mineral fillers, it is used in numerous applications, especially electrical and
small machine parts, owing to its excellent electrical resistance, surface finish, and
toughness.

2.1.2 Poly(ethylene terephthalate)

Polyesters are produced commercially by melt polymerization, ester interchanges,

and interfacial polymerization. Commercial poly(ethylene terephthalate) is produced
traditionally by two successive ester interchange reactions. In the first step, dimethyl
terephthalate is heated with ethylene glycol at temperatures near 200 °C. This yields
an oligomeric dihydroxyethyl terephthalate (x = 1 to 4) and methanol, which is
removed. In the second step, the temperature is increased, leading to polymer
formation, while ethylene glycol is distilled off (Figure 2.1) [15].

Commercially important polyesters are based on polymers with the p-phenylene

group in the polymer chain. In contrast to the low melting, linear aliphatic polyesters,
the stiffening action of this group coupled with the high degree of symmetry results
in a high melting point and other important engineering properties. For example, all
commercial polyester fibers are based on terephthalic acid as the primary building
block. Different products are obtained by varying the difunctional alcohols used in
polycondensation reaction with this acid. However, the major engineering polyesters
are poly(ethylene terephthalate) and poly(butylene terephthalate).

7
 O O HO
CH 2 150 - 200°C
x + 2x
C C catalyst
H2C
H3C O O CH 3 OH

2x H3 C OH +

O O

HO H2 C H2 C O C C O CH2 CH 2 O H

O O

HO H 2C H 2C O C C O CH 2 CH2 O H

x
260 - 300°C
catalyst

O O

C C O CH 2 CH2 O

nx

H2 H2
+ nx HO C C OH

Figure 2.1 : Polymerization reaction mechanism of PET.

PET is characterized by high strength, rigidity, and toughness; low creep at elevated
temperatures; excellent dimensional stability; low coefficient of friction; good
chemical, grease, oil, and solvent resistance; minimal moisture absorption; and
excellent electrical properties (Table 2.2).

PET has many advantages, which include:

• Lightweight: reduces transport fuel consumption and the cost of distributing

products.

• Performance: provides insulation and protection from contamination and

impact.

8
 • Economy: usually less expensive than alternative materials resulting in
savings to the consumer.

• Energy Savings: PET manufacture requires less energy than alternatives

resulting in lower "greenhouse" emissions. As insulation, PET foams enable
enormous energy savings in commercial installations such as cool stores.

Table 2.2 : Properties of engineering polyester, PET.

Property Property
Flexural strength 96.5–124.1
Specific gravity 1.34–1.39
(MPa)
Melting temperature Flexural modulus 2413–3102
265
(°C) (MPa)
Impact strength (Izod) 0.25–0.65
Tensile strength (MPa) 58.6–72.4
(ft-lb/in)
Tensile modulus Water absorption 0.1–0.2
2758–4136
(MPa) (24 hr)

Microcellular semicrystalline polymers such as poly(ethy1ene terephthalate) show

great promise for engineering applications because of their unique properties,
particularly at higher densities. Recent studies reveal some high density microcellular
polymers have longer fatigue lives and/or equal strengths to the neat polymer.
Relatively few microcellular processing studies of semicrystalline polymers have
been presented. In general, semicrystalline polymers are relatively difficult to
microcellular process compared to amorphous polymers. The semicrystalline
materials exhibit ten to one thousand times higher cell nucleation densities compared
with the amorphous materials, resulting from heterogeneous nucleation
contributions. The amorphous materials show a strong dependence on cell density,
while the semicrystalline materials show a weaker dependence. Moreover, classical
nucleation theory is not adequate to quantitatively predict the effects of saturation
pressure on cell nucleation for either the amorphous or the semicrystalline polyesters.
Both the semicrystalline and amorphous materials exhibit constant nucleation cell
densities with increasing foaming time. Foaming temperatures near the glass
transition are found to influence the cell density of the amorphous polyesters,
indicating some degree of thermally activated nucleation. Furthermore, classical
nucleation theory is not adequate to predict the cell density dependence on foaming
temperature. Similar to the amorphous polyesters above the glass transition

9
temperature, nucleation in the semicrystalline materials is found to be independent of
the foaming temperature [8].

Melt strength of poly(ethylene terephthalate)

Melt strength, a property of the polymer melt which indicates its ability to withstand
drawing without breaking. Melt strength is improved by the presence of high
molecular weight tail or long chain branches [117]. It is well-known that a melt
viscosity is a primary material property in the formation of stable bubbles.

High melt strength polypropylene is an example for foaming. It was first presented
by Himont [17], in which, by chain extension, semicrystalline polypropylene
demonstrates a wider processing window and a much better foaming structure over
the nonextended conventional PP. As a result, more polypropylene research and
development has been initiated. It is anticipated to have more grades of better
structured PP in the market for foaming. Recently, a polyethylene terephethalate
(PET) resin supplier reported solid state polymerization technology enhancement to
allow improved polymer strength PET for foaming [18]. In brief, resin structure
development opens interesting possibilities to further enhance foamed plastic
strength/weight performance.

In this study, the complexity is the non-uniform distribution of pressure and

temperature throughout the product that may cause a non-uniform cell structure. The
polymer could not be cooled sufficiently to prevent bubble collapse before it
crystallized. Among engineering plastics poly(ethylene terephthalate) is relatively
difficult to process microcellularly compared to general thermal plastics because of
its low melting viscosity.

In chemical modifications, different treatments have been developed to improve the

PET macromolecular characteristics, in particular, to extend the polymer chain
lengths. In fact, the molecular weight increase, through chain extension or branching,
is responsible for the increases in both viscosity and melt strength; these, in turn,
facilitate the production of expanded structures [19].

The evolution of shear and extensional behavior as a function of molecular weight

(Mw), degree of branching, and molecular weight distribution (MWD) studies
showed that an increase in the degree of branching and Mw and the broadening of the
MWD induce an increase in Newtonian viscosity, relaxation time, flow activation

10
energy and transient extensional viscosity, while the shear thinning onset and the
Hencky strain at the fiber break decreased. The semicrystalline polymers had
considerably higher cell densities than the amorphous polymers, which was
attributed to the significant heterogeneous nucleation contributions in the amorphous
crystalline interfacial regions. The amorphous foam experienced diffusional
controlled cell growth, whereas the semicrystalline foams experienced viscoelastic
controlled cell growth, and the longer the gas was allowed to diffuse into the cells,
the larger the cell size was.

Chain branching in some polymers is known to improve certain properties and is

practiced commercially (e.g., polyethylene and polycarbonate). In PET, many types
of branch structures have been synthesized and the effect of branch structure on
properties studied. Some of the branch structures possible in PET are star, comb, H-,
random, hyper, POM POM branched. Most of the recent studies of branched PET
have focused on new synthetic methodologies and on rheological properties.

2.2 Polymer Foams

Foams can be defined as a gaseous void surrounded by a much denser continuum

matrix, which is usually in a liquid or solid phase. It exists widely in nature, in
cellulositic wood, marine organisms, and other phenomena, and it can be made using
synthetic processes (i.e., foamed plastics). The presence of gas voids can be outside,
encapsulation, or inside, irreversible volume expansion. In most cases, a gas phase
possesses dramatically different properties and structures (or states) than the
surrounding solid phase, as opposed to different property and similar structure (or
state) blends, to make a lighter heterogeneous composite structure [20].

Foamed plastics can be classified in different ways, for instance, by nature as flexible
and rigid, by dimension as sheet and board, by weight as low density and high
density, by structure as open cell and closed cell, and by cell size as foam and
microcellular [2].

The cellular plastics encompass a range of materials with widely varying properties
and fields of application. Virtually any polymer, thermoplastic or thermoset, can be
made into a cellular or foamed form with the resulting products having densities

11
ranging from 60 pounds per cubic foot (pcf) (0.96 g/cm3) all the way down to 0.1 pcf
(0.0016 g/cm3).

2.2.1 Types of polymer foams

The cellular plastics can have either of two structural configurations: (a) the closed-
cell type, in which each individual cell, more or less spherical in shape, is completely
enclosed by a wall of plastic, or (b) the open-cell type, in which the individual cells
are intercommunicating. The foams can be rigid, semirigid, or flexible. In general,
the properties of the respective plastics are present in the foamed products, except, of
course, those that are changed by conversion to the cellular structure.

Currently achievable apparent foam densities range from 2 kg/m3 to 960 kg/m3

[22]. Based on these values, plastic foams can be classified into one of three classes:

1. Low Density Foams: foams having an apparent density value between 2 kg/m3
(0.002 g/cm3) and 50 kg/m3 (0.050 g/cm3).

2. Medium Density Foams: foams having an apparent density value between 50

kg/m3 (0.050 g/cm3) and 350 kg/m3 (0,350 g/cm3).

3. High Density Foams: foams having an apparent density value between 350 kg/m3
(0,350 g/cm3) and 960 kg/m3 (0.960 g/cm3).

In terms of cell size and cell density, plastic foams can be classified into one of three
categories [23]:

1. Conventional foams: foam structures with an average cell size greater than 300 µm
and a cell density less than 106 cells/cm3.

2. Fine celled foams: foam structures with an average cell size between 10 and 300
µm and a cell density between 106 and 109 cells/cm3.

3. Microcellular foams: foam structures with an average cell size less than 10 µm
and a cell density greater than 109 cells/cm3.

2.2.1.1 Thermoplastic and thermoset polymer foams

The thermoplastics that can be produced as structural foams already run a wide
gamut - ABS, acetals, acrylics, styrenes, polyethylenes, nylon, PVC, PC, modified
polyphenylene oxide, PP, polysulfone, thermoplastic polyesters, and various glass-

12
reinforced nylons, polyethylenes, polypropylenes, and other thermoplastics. Among
the thermosets, urethane structural foams are most in use.

Bubble formation theory

In polyurethane foam production, the correct foaming process requires that these two
reactions take place at the same rate.

Isocyanate + Polyol Polymer (First Reaction)

Isocyanate + Water CO2 for Foaming (Second Reaction)

If the polymerization (the first reaction) is faster, the polymer formed will have final
strength before foaming and the result will be a high density foam (low degree of
foaming). If the second reaction is much faster, the evolved gas will blow the foam.
Due to the low ‘green’ strength and viscosity of the polymerizing mixture, the gas
will leave the mixture, and the foam will collapse to a high density foam, as in the
first case. In the balanced process, the polymerization should proceed fast enough to
give high viscosity and melt strength of the mixture, which will trap fast evolving gas
and finish the polymerization at the end of foam growth [24 - 29].

The initial polyol and isocyanate mixture is a low molecular weight, low viscosity
fluid, which is reflected in the low strength of the bubble wall formed during
foaming. The wall of such a bubble breaks easily and gas escapes. Therefore, it is
necessary to increase the strength and elastic properties of the bubble wall (gel
strength), which is achieved by increasing the molecular weight of the polymer. The
mechanism of the bubble formation is a science ‘per se’, and it is essential to
understand the basics of the process. This process is similar to bubble generation
during boiling of a liquid. Gas which is formed in the chemical reaction, or by
evaporation of the added low boiling foaming agent, is partially soluble in the
polymer mass. When the limit of solubility is reached, i.e., when enough gas is
generated to exceed the solubility limit (saturation), the excess separates in the form
of bubble. First stage of bubble formation is called nucleation. The number of
bubbles will depend on the number of nuclei (seeds) present in the system.
Nucleation can be homogeneous (in the absence of foreign particles, nucleants) or
heterogeneous (in the presence of nucleants). The bubble nucleus is usually a small
amount of air caught in the crevasses or in the roughness on the surface of the solid
or liquid particle, in case of heterogeneous nucleation. The beginning of foam

13
formation is characterized by formation of large number of nuclei. Their creation
causes refraction of light on the walls of nuclei, which is manifested as whitening of
the mass without significant volume increase. The next stage is bubble growth from
the nucleus due to the incoming evolved gas, and the volume increase of the foaming
mixture. This stage is observed as the foam rise. Stability of a growing bubble
depends on the surface tension. If the surface tension is too large and there is no
nucleation, a small number of large bubbles will grow, and the shape should be
elongated in the direction of rise. Such foams are usually not desirable since they
show anisotropy in their mechanical properties. Regulation of bubble growth is
achieved by the addition of surfactants (usually silicone copolymers). The surfactant
has multiple role, to lower surface tension and facilitate division of cells into smaller,
and since it is a separate phase, to act as a nucleant. Increasing the amount of
surfactant gives finer cells with thinner walls until the limit is reached above which it
causes foam collapse, more regularly shaped bubbles [29], [30].

2.2.1.2 Open- and closed-cell polymer foams

During foaming, two types of foam cells are observed: open- and closed- cell.
Closed-cell structure may entrap hydrogen, carbon dioxide and volatile liquids. The
entrapped fluid (e.g. air) plays a major role in increasing in compressive strength and
energy absorption capability for closed- cell foams [31]. On the other hand, open-cell
foamed plastics have a higher absorptive capacity for water and moisture, a higher
permeability to gas and vapor, less insulation capabilities for heat or electricity and a
better ability to absorb and damp sound.

Foams may have open or closed cells. Open cells are obtained by crushing the foam
after gelation, but the amount of open cells is regulated by the selection of catalysts.
Foams used in the furniture industry contain open cells while those used for thermal
insulation (rigid foams) are required to have closed cells, since they contain a gas of
low thermal conductivity. Polyester urethane flexible foams have better strength and
oxidative stability but lower hydrolytic stability than polyether urethane foams. They
also show higher hysteresis in the stress–strain cycling test. Polyester urethane foams
are more resistant to chemicals, particularly those used for chemical cleaning, but are
also more expensive than PPG based foams [32].

14
Figure 2.2 compares typical microstructures of open- and closed-cell polymer foams,
respectively, as seen in a scanning electron microscope (SEM). The good depth of
focus allows complete cells to be seen in the interior of open-cell polyurethane (PU)
foams. Air can pass freely between the cells of such foams.

Although in Figure 2.2(a) all the cell faces are open, only a small fraction of cell
faces need to be open to create continuous air passages. In a typical closed-cell
foamed thermoplastic, each cell is surrounded by connected faces.

Cut
edge

Edge

Vertex

(a)

Cut
face

Cut
edge

Face
Vertex

Edge

(b)

Figure 2.2 : SEM photograph of (a) PU open-cell foam of density 28 kg m-3,

(b) Closed-cell LDPE foam of density 24 kg m-3 [12].

Partial cells, with cut faces and edges, are visible on the cut surfaces (Fig. 2.2(b)),
while complete cells exist in the interior of the sample. The cell faces can sometimes
be split or otherwise damaged [12].

15
Closed-cell foam development

Compared with the five stages of PU foaming, the only two stages in thermoplastics
are the growth of isolated spherical bubbles and the formation of polyhedral closed
cells.

Isolated bubble growth in a melt, the first stage of bubble growth occurs in a polymer
melt under pressure, containing dissolved gas. A variety of gases have been used.
CFCs have ideal physical properties of low diffusivity, low thermal conductivity, and
low boiling point, but have been phased out as they deplete the ozone layer in the
stratosphere. Hydrocarbon gases, hydro chlorofluoro carbons (HCFCs), carbon
dioxide, and nitrogen are all used.

Figure 2.3 : (a)Modelling the growth of an isolated spherical bubble in a PE melt.

(b)The predicted growth in the radii of the bubble and melt with time
[3].

A pressure reduction, or the generation of more gas, causes bubbles to nucleate.

Figure 2.3 (a) shows an isolated spherical bubble in a polymer melt, the first stage of
the foaming process.

Shafi et al. [35] assumed that there are spherically symmetric flows:

(a) radial heat flow;

(b) radial gas diffusion from the melt to the bubble;

(c) extensional polymer melt flow, in directions tangential to the sphere, and
compressive melt flow in the radial direction.

16
It is assumed that no further bubble nucleation occurs during bubble growth. The
pressure balance of the bubble depends not only on its curvature and surface tension,
but also on the biaxial tensile stresses in the melt. In Figure 2.3(a), the outer radius of
the melt sphere indicates the approximate amount of melt per growing bubble. The
viscosity of the polymer melt is a function of its temperature and the amount of
dissolved blowing agent. The coupled equations were solved by finite difference
methods. Figure 2.3(b) shows the predicted increase in the cell radius with time in a
PS melt. Since the model does not consider the interaction between touching
bubbles, it is unlikely to be correct at long times.

Multiple bubble growth in a melt, melt extensional flow in cell faces draws melt
from the vertices. Everitt et al. [36] modelled the interaction of a sheet of large and
small bubbles in a 2-dimensional (2D) polymer melt. The bubble array had
hexagonal symmetry, so it was possible to consider a small representative unit cell
(RUC), containing parts of a small and a large bubble plus a mirror symmetry plane.

Figure 2.4 : Developing foam in a structure with two large to every small bubble, at
the dimensionless times indicated (the grey scale indicates orientation)
[36].

There are separate time scales for polymer viscoelasticity, bubble growth, and for gas
diffusion in the melt. Figure 2.4 shows how, with increasing bubble expansion, the
melt is elongated between two neighbouring large bubbles. The dimensionless time
in the simulation is time divided by the fluid relaxation time. A full 3D consideration
of such flow will eventually lead to better models of foam development.

17
2.2.1.3 Flexible, semirigid and rigid polymer foams

Polyols, one of the major ingredient of a PU foam, are active hydrogen-containing

compounds, primarily variations of polyesters and polyethers. As a rule of thumb,
high molecular weight, low fuctionality polyols produce molecules with a low
amount of cross-linking and, consequently, a flexible foam. Conversely, low
molecular weight polyols of high functionality produce a structure with a high degree
of cross-linking, a rigid foam. Also, it is possible to vary the formulation to produce
any degree of flexibility or rigidity between the two extremes [37].

Flexible foams differ from the aforementioned rigid foams in that they can be
elastically deformed and return to their original contours when the force is removed.
They are usually in the 1 to 6 pcf density range. The two major production
techniques in the flexible foam area are the slabstock and the molded foam
processes.

When foams are made either by free foaming or in a mold, a skin is formed on the
foam surface called Integral Skin Foams, in which the foam comes out of the mold
with a continuous skin that can replace the separate vinyl or ABS surface (e.g., RIM
process). This fact is utilized to prepare foamed products with a controlled thickness
of the skin. The formulation for integral foams generally does not contain water but it
has physical blowing agents. The objects are made in closed molds. Density of the
skin can be regulated by the mold temperature, amount of the mixture poured in the
mold (larger amount exerts higher pressure) and mold release agents (usually
silicones). As a rule lower temperature favor thicker skin. Higher pressure and
release agents, which act as antifoaming agents in contact with the skin, also favor
thicker skin [32].

Rigid foam compositions differ from those of flexible foams as they use short triols
or higher functionality polyols, typically with Mn = 400. They are made with crude
MDI, and main part of foaming is done with physical blowing agents. Due to the
high concentration of crosslinks the foams are rigid. Rigid foams are used primarily
for heat insulation in refrigeration and construction, and partly in automobile
industry [38].

A variety of rigidity grades of flexible foams are manufactured, with grades having
rigidity between soft and rigid foams being called semirigid. Semi-rigid foams are

18
used for automobile seats and components for interior and exterior safety. These
foams are characterized by low resilience, in that they recover very slowly from
compression, and by high-energy-absorbing characteristics. Semirigid foams also are
cold-curing in nature and usually involve special polymeric isocynates [37].

2.3 Production of Polymer Foams

The cellular plastics can be produced in the form of slabs, blocks, boards, sheets,
molded shapes, and sprayed coatings. Some can also be “foamed-in-place” in an
open cavity. The type of process used (casting, extrusion, injection molding) will
affect the properties of the endproduct.

As originally conceived, most foamed plastics were completely cellular in structure;

today, it is possible to arrange the cells so that a product may have an essantially
solid skin surface and a cellular core.

The ways in which the cellular structure is produced in plastics vary widely. The
following are the basic ones among them:

1. Air is whipped into a suspension or solution of the plastic, which is then

hardened by heat or catalytic action or both.

2. A gas is dissolved in the mix and expands when pressure is reduced.

3. A component of the mix is volatilized by heat.

4. Water produced in an exothermic chemical reaction is volatilized within

the mass by the heat of reaction.

5. Carbon dioxide gas is produced within the mass by chemical reaction.

6. A gas, such as nitrogen, is liberated within the mass by thermal

decomposition of a chemical blowing agent.

7. Tiny beads of resin or even glass (e.g. micro-balloons) are incorporated in

a plastic mix.

Moreover, many different processes, the most popular ones being injection molding
and extrusion, can produce thermoplastic foams. In the extrusion process, the
extruder offer relevant unit operations for foam production, such as melting, mixing
and metering in continuous mode.

19
Furthermore, processing has become more sophisticated, especially in the area of
producing high-quality surfaces on foam parts. Sandwich molding and coextrusion
are being used to manufacture “foam core” thermoplastic products with low density,
rigidity, and smooth surfaces for a variety of applications.

2.3.1 Blowing agents

The term blowing agent in the broadest sense denotes an inorganic or organic
substance used in polymeric materials to produce a foam structure. There are two
major types of blowing agents: physical and chemical.

Among physical blowing agents, the chlorofluorocarbons (CFCs) used in the past,
such as CFC11 (CCl3F), had several advantages; the heat of fusion of the low boiling
point liquids aided foam temperature control, the low diffusivity of the gases made
stable cell structures easy to achieve, and the gases were non-flammable. In contrast,
pentane and butane are gases at room temperature, flammable, and have a high
diffusivity through molten polyolefins.

When a high melt strength PP was foamed using butane [39] the maximum
expansion ratio was a function of the extrudate temperature; it increased with
temperature in the low temperature range where the expansion was limited by
crystallisation, then decreased at higher temperatures due to butane loss from the
extrudate. The extrudate swelled from the die, then foaming caused further
expansion. Several strategies were used to achieve ultra-low-density PP foams [40]
branched PP prevented cell face fracture, lowering the melt temperature reduced the
gas loss during expansion, and optimisation of the die design avoided too-rapid
crystallisation. Hydrocerol, a mixture of sodium bicarbonate and citric acid which
decomposes to liberate CO2 and a mixture of other products, was used [41]: the CO2
and isobutane acted as blowing agents. The extruder screw speed and hydrocerol
concentration controlled the nucleation density, hence the foam density and mean
cell size. Branched PP had a slightly larger cell size than linear PP when CO2 was
used as the foaming agent, but there were a significant number of open cells in the
foamed linear PP [42].

Sims et al. considered the efficiency of azodicarbonamide and sodium bicarbonate

blowing agents for PE foams made by compression moulding [43]. These systems
generate CO2 gas. Blends of the blowing agents have a reduced exotherm, so are

20
more suitable for polymer systems with that are temperature sensitive, such as
ethylene copolymers.

According to Shutov [44], there are various requirements that have to be met when
choosing a CBA:

• Decomposition temperature of the CBA should be slightly higher than the

melt or processing temperature of the material.

• Gas must be liberated within a narrow temperature range.

• Rate of gas liberation must be sufficient and controllable.

• Gas and decomposition products must be noncorrosive, nontoxic, and

nonflammable.

• CBA must be adequately dispersed in the polymer matrix.

• Polymer matrix should not be destroyed by CBA or heat generated during

decomposition.

• Internal gas pressure should be controlled.

• Diffusion rate of the gases generated by CBA should be adequate for the
chosen polymer matrix.

Due to the fact that, 5-phenyl tetrazole was chosen as the chemical blowing agent in
this thesis study.

2.3.1.1 Physical blowing agents

Physical blowing agents (PBA) are volatile liquids or compressed gases that change
state during processing to form a cellular structure within the plastic matrix. The
gases or low-boiling liquids that are dissolved in the resin, evaporate through the
release of pressure or the heat of processing. The compounds themselves do not
experience any chemical changes. Cell size is influenced by the pressure of the gas,
the efficiency of dispersion, melt temperature, and the presence of nucleating agents.
The most common gases used are carbon dioxide, nitrogen, and air. The liquid
blowing agents are typically solvents with low boiling points, primarily aliphatic
hydrocarbons and their chloro- and fluoro- analogs.

21
The blowing agents should be soluble in the polymer under reasonably achievable
conditions but excessive solubility is not desirable. The permeability of the gas
within the polymer is also significant, as is the volume of gas released per unit
weight of agent. This latter measure is called the blowing agent efficiency, and is an
important yardstick for all types of materials. Effective blowing agents should yield
at least 150 to 200 cm3 of gas (measured at standard temperature and pressure) per
gram of agent [45].

2.3.1.2 Chemical blowing agents

Chemical blowing agents (CBAs) are products that decompose at high temperature.
At least one of the decomposition products is a gas, which expands the plastics
material to give a foam structure. The amount and type of the blowing agent
influencethe density of the finished product and its pore structure. Two types of pore
structures are possible: open and closed cell. Factors that determine the formation of
a fine-celled plastic foam with a regular cell structure are the particle size of the
blowing agent, dispersion properties of the plastics processing machine used,
decomposition rate of the blowing agent, and the melt viscosity of the resin
processed.

CBAs are mainly solid hydrazine derivatives. The gas formation must take place in a
temperature range close to the processing temperature range of the polymer. In
addition, the decomposition products must be compatible with the polymer.
Typically, these additives decompose over a relatively narrow temperature range.
CBAs can be mixed with the polymer at room temperature, requiring no special
processing equipment. In most operations, they are self-nucleating and are stable
under normal storage conditions. In addition, CBAs may be reformulated with such
other additives as blowing agent catalysts or nucleating agents. Blowing agent
catalysts lower the temperature of decomposition for the CBAs while nucleating
agents provide sites for formation of a cell in the foamed plastic.

Blowing agents are used in plastics for several reasons: weight reduction, savings in
cost and material, and achievement of new properties. The new properties include
insulation against heat or noise, different surface appearance, improved stiffness,
better quality (removal of sink marks in injection molded parts), and/or improved
electrical properties. [45].

22
From automotive to medical products, packaging to housing, CBAs are applied in
wide variety of applications within today’s plastics sector. Typically offered as a
powder or a pelletized master batch, CBAs can be added like any other additive to
the process. Less commonly used, but also available, are liquid CBAs where the
powder is let down into a compatible liquid.

CBAs offer various advantages with the most commonly known being weight or
density reduction. This can typically be achieved without entirely compromising the
physical properties of the end product. Some other common uses are as nucleating
agents in direct gas operations and structural foam, and sink mark removal. In some
cases the CBA is used to provide a “spongy” feel to the finished product.

Activated by temperature, the CBA generates gas via a decomposition reaction.

Ideally, this gas is mixed into solution with the polymer melt. When the melt and gas
solution is introduced to a pressure drop, gas pockets or bubbles begin to form within
the polymer matrix. Over time the gas diffuses out of the polymer matrix and is
replaced with air.

There are two basic types of chemical foaming agents, known as endothermic and
exothermic. These two can be blended together to make a third type of foaming agent
known as an endo/exothermic. The decomposition of endothermic foaming agents
absorbs heat and typically generates carbon dioxide and water vapor. Exothermic
foaming agents generate heat upon their decomposition and produce nitrogen and/or
ammonia gas and are typically said to produce higher volumes of gas. The
exothermic decomposition is also known to generate higher pressures than the
endothermic.

The endo/exo blends are used in applications where the properties of both the
endothermic and exothermic are required. An example would be in profile extrusion
of rigid PVC. The exothermic provides a large volume of gas at a high pressure
allowing the gas to enter the PVC matrix, while the endothermic provides gas and
absorbs heat thus preventing distortion in the profile and allowing for faster line
speeds.

The endothermic products typically decompose in the range of 130 - 230 ºC, while
exothermic decomposition typically takes place around 200 ºC. However, particle
size plays an important role in the decomposition rate as well as the decomposition

23
temperature for both. In addition, the decomposition temperature of the exothermic
products can be lowered by adding an “activator” or “kicker.”

Selection of the proper CBA for the application is crucial, and is done based upon
compatibility of the gasses generated with the polymer of interest, as well as
compatibility of the carrier resin (if applicable), desired amount of gas evolution, and
the processing window [38].

Generally CBAs are used for high-density foams. Among them endothermic CBAs
have desirable property for wood polymer composites as during foaming they absorb
heat at decomposition, which cools the polymer, increases the viscosity of the melt,
stabilizes the cellular structure, and reduces cell coalescence [47 - 49].

Exothermic blowing agents

Exothermic foaming agents generate heat upon their decomposition and produce
nitrogen and/or ammonia gas and are typically said to produce higher volumes of
gas.

Azodicarbonamide (AZ), the most widely used exothermic CBA. In its pure state, this
material is a yellow-orange powder, which will decompose at about 390°F. Its
decomposition yields 220 cm3/g of gas, which is composed mostly of nitrogen and
carbon monoxide with lesser amounts of carbon dioxide and, under some conditions,
ammonia. The solid decomposition products are off-white, which not only serves as
an indicator of complete decomposition but also does not normally adversely affect
the color of the foamed plastic. Unlike many other CBAs, AZ is not flammable. In
addition, it is approved by the FDA for a number of food-packaging uses. AZ can be
used in all processes and with most polymers, including PVC, PE, PP, PS, ABS, and
modified polyphenylene oxide (PPO).

Modified AZ systems have been developed which offer improved performance and
increase versatility in a wide variety of applications. Each system has a formulated
cell nucleation system (usually silica) and gas yield is approximately the same as
unmodified AZ. Modified types are also available in several particle size grades.

The simplest form of modified AZ is a paste. It is composed of a plasticizer, which

forms the liquid phase, and may also contain dispersing agents and catalysts. Its
principal field of application is the expansion of PVC plastisols. The agents facilitate

24
the dispersion of the blowing agent when it is stirred into the PVC plastisol, while
catalysts lower the decomposition temperature.

Other modified AZs have been developed for the manufacture of integral-skin foams
by extrusion and injection molding. These contain additives that modify the usual
decomposition process of AZ and suppress the formation of cyanuric acid, which
causes plateout on the surfaces of molds, dies, and screws. The additives used
include zinc oxide and/or silicic acid (a colloidal silica) with a very low water
content. The additives also act as nucleating agents, producing a cell structure that is
both uniform and fine-celled.

There are also grades that have been flow-treated. This type contains an additive to
enhance the flowability and dispersability of the powder. These grades are very
useful in vinyl plastisols, where complete dispersion of the foaming agent is critical
to the quality of the final foamed product.

Another method of modifying AZ is to mix it with such other CBAs as those from
the sulfonyl hydrazide group. These “auxiliary” blowing agents decompose at lower
temperatures than AZ, broadening the decomposition range.

Sulfonyl hydrazides have been in use as CBAs longer than any other type. The most
important sulfonyl hydrazide is 4,4′-oxybis (benzenesulfonyl hydrazide) (OBSH).
OBSH is the preferred CBA for low-temperature applications. It is an ideal choice
for the production of LDPE and PVC foamed insulation for wire where it does not
interfere with electrical properties. In addition, it is capable of cross-linking such
unsaturated monomers as dienes. Additional applications include PVC plastisols,
epoxies, phenolics, and other thermosetting resins. Like AZ, it is approved by the
FDA for food-packaging applications and is odorless, nonstaining, and nontoxic.

Sulfonyl semicarbazides are important CBAs for use in high-temperature

applications. TSS (p-toluene sulfonyl semicarbazide) is in the form of a cream
colored crystalline powder. Its decomposition range is approximately 440 to 450 °F
with a gas yield of 140 cm3/g, which is also a mixture of nitrogen, CO2, CO, and NH3
[50]. TSS is flammable, burning rapidly when ignited and producing a large amount
of residue. TSS is used in polymers processed at higher temperatures such as ABS,
PPO, polyamide (PA), and HIPS.

25
Dinitropentamethylene tetramine (DNPT) is one of the most widely used CBAs for
foamed rubber. Its use is limited in plastics because of its high decomposition
temperature and the unpleasant odor of its residue. DNPT is a fine yellow powder
that decomposes between 266 °F and 374 °F, producing mainly nitrogen and a solid
white residue.

With the increased use of engineering plastics in recent years, the need for chemical
blowing agents having higher decomposition temperatures to match the processing
temperatures of these materials has also grown. In the tetrazole class, 5-
phenyltetrazole is the only available product, which is a white crystalline powder
with a melting point of 212 °C [51]. This high temperature CBA is a solid with a
decomposition temperature range of around 250 °C, and generates 200 cc/grams
(measured at STP) of predominantly nitrogen gas [52]. Its primary area of
application is in polycarbonate, but it may be used in other engineering plastics. It
should be noted that incomplete decomposition of this material will result in a pink
colored intermediate product.

Hydrocarbyl tetrazoles (the class of materials to which 5-PT belongs) may be

synthesized via the reaction of an aromatic amine with a metal azide in the presence
of a Friedel-Crafts catalyst [53]. Hence, 5-PT can be obtained from the reaction of
benzonitrile and sodium azide.

An alternative route to 5-PT has been demonstrated via cyclization of

benzamidrazone with nitrous acid [54].

The most commonly reported solid decomposition product of 5-PT is 3,5-diphenyl-

1,2,4-triazole [51], [54]. Other solid decomposition products claimed are
aminodiphenyltriazole and triphenyl-S-triazine [54].

The decomposition mechanism of 5-PT has not been extensively studied, although
the nature of the decomposition products permits some speculation. Clearly, more
than one reaction pathway is allowed. Also, the decomposition must involve some
interaction between pairs of 5-PT molecules and/or decomposition intermediates. As
is generally the case with this sort of mechanism, the gas yield and the residue
composition can be affected by the conditions under which decomposition occurs
(e.g., heating rate and decomposition media) [55].

26
The main decomposition products of Expandex 5-PT are heterocyclic nitrogen
compounds, such as triphenyl-s-triazine, 3,5-diphenyl-1,2,4-triazole, 4-N-amino-3,5-
diphenyl-1,2,4-triazole as shown in Table-A.1 [56].

Gas pressure development

The pressure exposure during the decomposition is particularly important in regards

to the cooling time, the tendency of uncontrolled post-expansion of the molded parts,
and the cell structure. This can also infl uence the physical properties of the parts,
depending on the grade of expansion rate. It is quite obvious that CBAs that liberate
nitrogen have the highest gas pressure development.

Table 2.3 : Maximum gas pressure at decomposition and remaining pressure in

room temperature for various chemical blowing agents.
Substance Maximum Remaining
Pressure (Bar) Pressure (Bar)
ADC 85.4 30.3
5–PT* 40.6 21.1
ADC/endo 1:1 42.2 15.8
Standard endo 41.6 11.9
ADC/bicarbonate 1:4 28.1 11.2
Bicarbonate 24.2 11.0
*[59]

The chemical blowing agents are added to the polymer pellets in solid form and are
activated through addition of heat, releasing a fluid, mostly nitrogen, carbon dioxide,
or water [60].

Table 2.4 : Properties of chemical blowing agents.

Product Decomposition Gas Evolution
Main Gases
Range (°C) (mL/g)
ADC (ADCA) 200-215 220 CO, CO2, NH3
ADC (ADCA) act. 140-215 130-220 N2, CO, CO2, NH3
DNPT 190-200 190-200 N2, NH3, CH2O
THT 245-285 180-210 N2, NH3
TSH 105-110 115 N2, H2O
OBSH 155-165 110-125 N2, H2O
TSSC 225-235 120-140 N2, CO2, NH3
5-PT 240-250 190-210 N2
NaHCO3 110-150 160-190 CO2, H2O
NaHCO3/citric comp. 130-230 110-180 CO2, H2O

27
However, the appearance of residual products is a disadvantage, given the fact that
they can represent up to 70 % of the fi nal composition of the agent [61], [62]. Their
decomposition can lead to a degradation of the polymer matrix, to a decrease in
mechanical properties, to coloration of the part and to corrosion and contamination of
the mold. For these reasons only a defined amount of foaming agent ought to be
incorporated into the polymer melt when using chemical blowing agents. A list of
chemical blowing agents is provided in Table 2.4 [63].

Endothermic blowing agents

Endothermic CBAs are used primarily in the injection molding of foam where the
rapid diffusion rate of carbon dioxide gas through the polymers is essential. This
allows postfinishing of foamed parts right out of the mold without the need for a
degassing period. Nucleation of physically foamed materials, especially those used
for food packaging, has become a well-established application area for endothermic
CBAs.

Sodium borohydride (NaBH4) is an effective endothermic blowing agent because its

reaction with water produces 10 to 20 times the amount of gas produced by other
CBAs that give off nitrogen. Sodium borohydride must be blended with the polymer
to be foamed to prevent reaction with water during storage.

Sodium bicarbonate (NaHCO3) decomposes between 212 and 284 °F giving off CO2
and H2O and forming a sodium carbonate residue. Its gas yield is 267 cm3/g. At 287
°F or higher, decomposition becomes more rapid, facilitating its use as a blowing
agent for such higher-temperature thermoplastics as styrenic polymers.

Polycarbonic acid decomposes endothermically at approximately 320 °F and gives

off about 100 cm3/g of carbon dioxide. Further heating will release even more gas. In
addition to being used as the primary source of gas for foaming in some applications,
this class of materials is frequently used as a nucleating agent for physical foaming
agents [64].

2.3.1.3 Determining the amount of gas generated

The dimensionless volume Vg0 of gas generated (volume at STP per volume of
LDPE) can be calculated from the concentration of the chemical blowing agent. Lee
and Flumerfelt (1995) found that the solubility of nitrogen in LDPE melts increases

28
with temperature [35]. The relationship between the mass X of nitrogen dissolved,
expressed as g N2/g LDPE, and the pressure p measured in bar, at 135 °C is (2.1)

(2.1)

Since the molar mass of nitrogen is 28 g/mol, and the molar volume of a gas at 135
°C is 31,600 ml/mol, 0.22 volumes of nitrogen dissolve in one volume of LDPE at
135 °C under an absolute pressure of 1 bar. Since the foam relative densities are
typically less than 0.08 in the later stages of expansion, and the gas pressures are less
than 0.2 bar, the fraction of the nitrogen gas dissolved in the LDPE is insignificant.

It is assumed that no gas loss occurs by diffusion through the cell faces to the outside
of the foam. If the foam density is ρ (kg m-3) at the process temperature T, the
dimensionless gas volume Vg(T,p) under the process conditions is (2.2)

(2.2)

The dimensionless LDPE relative volume VP(T) at temperature T °C is given by

Hellwege et al. [65] as (2.3)

(2.3)

The absolute gas pressure p is determined from Vg and Vg0 using the ideal gas laws,
hence the relative gas pressure pr is obtained.

2.3.1.4 Control of cell size and cell stability

Nucleating agents can be used to reduce cell size. Cheung and Park [66] described
the use of talc in PP foam. Talc is more effective than calcium carbonate [67],
probably due to its platelet geometry; the concentration of nuclei appeared to
increase almost exponentially with the concentration of talc, with the smallest
particle size 0.8 µm talc being most effective. Low-density foams of HDPE can be
extruded with fine cells, using CO2 as a blowing agent [68]. The melt temperature
was reduced to the lowest possible value of 121 °C at the die, to avoid cell
coalescence and achieve high expansion ratios. In related research [69], a blend of
LDPE and LLDPE, blown with CO2, was extruded at 220 °C. It was necessary to
cool the extrudate surface to temperatures as low as 0 °C to stabilise the foam.

29
Park and Malone [70] defined a foamability factor F, from the tan δ of the PE melt
(at 190 °C and 1 Hz).

Figure 2.5 : Abnormally large cells, with >20 faces, formed by cell face collapse in
EVA foam of density 150 kg m-3, with a background of normal cells
[71].

The LDPE blown film process is successful, since the melt bubble cooling occurs in
a few seconds, allowing little time for the viscous extensional flow of the
thermoplastic melt. However, due to the low thermal diffusivity of foams, it takes the
order of 20 min for a PE foam melt to cool to the solid state. During this time, the
melt bubbles must remain stable. The typical gel content, from 30 % to 70 %, causes
the low-shear-rate viscosity to be extremely high. However, if gelations were taken
further, the tensile stresses in the expanded foam would be too high.

2.3.2 Production Methods of Polymer Foams

The manufacturing of plastic foams extends to most plastics processing technologies

[57]. Foams can be processed in extrusion, injection molding, compression molding,
blow molding, coating, calendaring, rotational molding, etc.

Regardless of the processing technique, the foaming of polymers by using physical

blowing agents, such as carbon dioxide or nitrogen, relies on the same principles: (1)
the polymer is saturated with the blowing agent at high pressures, (2) the polymer-
gas mixture is quenched into a supersaturated state by reducing the pressure and/or
increasing the temperature, (3) the thermodynamic instability of supersaturation
leads to nucleation of foam cells, (4) the growth of the foam cells, driven by the
diffusion of the blowing agent, proceeds until the cells either stabilize or rupture. The

30
growth rate is primarily controlled by the diffusion rate, the rheological properties of
the polymer, the temperature, the state of supersaturation, and the hydrostatic
pressure applied to the polymer matrix. Although these principles controlling the
foaming behavior are fairly well understood, most commercial thermoplastic foams
are still based on a limited number of polymers such as polystyrene (PS), polyvinyl
chloride (PVC), polyethylene (PE), and polypropylene (PP) [73].

2.3.2.1 Extrusion of thermoplastic foam sheet

Foaming plastics has been developed as an extension of the extrusion application

while extruder evolution is primarily based on its function optimization. Extrusion of
thermolastic foams is largely controlled by the relatively complex rheological
behavior of the polymer melt and physical foaming agent (PFA) mixture [74].

In 1941, the first foam extrusion based product was Styrofoam, created by Dow and
in 1958, the first commercialized LDPE foam was introduced by Dow again [75].

The complexity arises first from the moderate to large plasticization due to the
adequate dissolution of the small molecules of the foaming agent. They act as a
diluent with respect to the polymeric macromolecules, which forms a single phase
(zone #1, Figure 2.6). This solution should remain in that state until the nucleation
step occurs at the die exit, as shown in Figure 2.6. This is usually accomplished by
maintaining a pressure that is sufficiently high inside the extruder, i.e., above the
solubility pressure for such conditions of temperature and PFA concentration,
thereby preventing any phase separation. In the extruder, the deformations occur
mainly in a shearing mode. Elongational and shear flows coexist in the die, where the
PFA should still be kept dissolved in the polymer melt [10].

The melt, leaving a slot-shaped die, spreads on a moving belt. As the foaming
process proceeds, the thermal conductivity of the foam decreases significantly, while
the heat conduction distance increases as the foam sheet thickens. The time scale for
foam expansion is of the same order as that for heat conduction. Gas diffusion
occurs, under the pressure differential from the centre to the surface of the sheet. The
lower pressure in the surface cells could allow these to shrink in size and relieve the
tensile stresses in the oriented faces. Hence the foam density is expected to be higher
near the foam skin. The high tensile viscosity of the molten polymer resists, but does
not prevent, the thinning of cell faces and the drawing of melt from cell edges. If

31
neighbouring cells have different diameters, larger bubbles will try to grow at the
expense of neighbouring smaller bubbles, lessening the overall surface energy of the
system. However, as bubble coarsening is rarely observed, this process must be slow
compared with the solidification process. Occasional large cells in foams appear to
be the result of face fracture followed by a reshaping of the joined cells.

Figure 2.6 : Schematic of the extrusion foam process.

(1) A single-phase, gas-laden melt is pumped toward die exit.

(2) Nucleation occurs outside the die due to the large pressure drop.
(3) Cells expand and the structure stabilizes as the polymer is cooling.

When the melt passes through the short extrusion die, its pressure falls rapidly to
atmospheric and a fine cell size is produced. The process of gas diffusion from the
melt to the bubbles occurs on a time scale of the order of seconds. Faster pressure
reduction allows less time for gas diffusion, so the effective gas diffusion distance is
smaller. This allows new bubbles to nucleate closer to growing bubbles, reducing the
average cell size in the final foam. Shafi et al. [35] predicted cell size distributions
for freely expanded LDPE/nitrogen system from measured parameters. However
they did not predict the mean bubble size in terms of directly measurable process
variables.

2.3.2.2 Compression molding method

Compression molding is a forming process in which a plastic material is placed

directly into a heated metal mold, then is softened by the heat, and forced to conform
to the shape of the mold as the mold closes. The mold is closed with a top force or
plug member, pressure is applied to force the material into contact with all mold
areas, while heat and pressure are maintained to the molding material. The advantage
of compression molding is its ability to mold large, fairly intricate parts. Also, it is

32
one of the lowest cost molding methods compared with other methods such as
transfer molding and injection molding; moreover it wastes relatively little material,
giving it an advantage when working with expensive compounds.

Polymer
Mold

Figure 2.7 : Schematic of the compression molding foam process.

Compression molding was first developed to manufacture composite parts for metal
replacement applications, compression molding is typically used to make larger flat
or moderately curved parts. This method of molding is greatly used in manufacturing
automotive parts such as hoods, fenders, scoops, spoilers, as well as smaller more
intricate parts. The material to be molded is positioned in the mold cavity and the
heated platens are closed by a hydraulic ram. Bulk molding compound (BMC) or
sheet molding compound (SMC), are conformed to the mold form by the applied
pressure and heated until the curing reaction occurs. SMC feed material usually is cut
to conform to the surface area of the mold. The mold is then cooled and the part
removed. Materials may be loaded into the mold either in the form of pellets or sheet,
or the mold may be loaded from a plasticating extruder. Materials are heated above
their melting points, formed and cooled. The more evenly the feed material is
distributed over the mold surface, the less flow orientation occurs during the
compression stage [78].

In compression molding system compression force is applied among molds to get the
desirable shape of molten materials through solidification. In this process good
optimization could be obtained between the flow of material and the mechanical
properties [79]. Meij [80] investigated non-isothermal effects on the flow of Glass
Mat reinforced Thermoplastics (GMT) during moulding and suggested process
control tools.

33
The compression molding processing of cellular samples is based on three sub-
processes which include the processing of the polymer matrix, the processing of the
cellular structure, and the processing of the net shape. The creation of a cellular
structure is achieved by dissolving large gas concentrations into a polymer matrix
and subjecting the saturated system to a rapid thermodynamic state change. This
creates an unstable or supersaturated matrix that drives the nucleation of billions of
microcells. Stable cells then grow as gas diffuses into the cells reducing the bulk
density of the material [81].

In compression molding there are six important considerations that an engineer

should bear in mind.

Determining the proper amount of material.

Determining the minimum amount of energy required to heat the material.

Determining the minimum time required to heat the material.

Determining the appropriate heating technique.

Predicting the required force, to ensure that shot attains the proper shape.

Designing the mold for rapid cooling after the material has been compressed
into the mold.

Commercial moulding prediction tools issued from work on non-isothermal

moulding are available [82 - 84]. It was found that the fiber content and the polymer
viscosity both have a large influence on the work of compression [80]. However, not
much is known about the influence of each of the constituent materials on processing
and about the evolution of the temperature and deformation fields during non-
isothermal flow [86]. During industrial flow molding processing, composites are
preheated and then transported to the mould, which is maintained at a temperature
below the solidification temperature of the matrix. The mould is then closed at a high
speed. When the flow is almost complete, the press is switched from displacement
control to pressure control and a pressure is maintained until the mould is full and the
material inside has cooled sufficiently. The material in the inlay zone cools first and
its rheology and solidification behavior determines the extent of flow in the rest of
the mould. The void content during dwell and initial compression is high due to
lofting of the preforms at preheating. When the hot preform is compressed between

34
the platens, the macro-voids are removed. During the initial phase of flow, some
voids, still remain in the material are rapidly suppressed. The material then flows out
from between the platens and flow ends until the material between the platens is
solidified throughout thickness. However, surface void formation is still a major
problem, especially for application in automotive industry [87]. Such voids require
costly after treatment to enable good appearance after painting.

In compression molding, compounding step can be eliminated and mixing and

molding can be done in one step [88], [89]. This will allow minimizing length
reduction of the fibers and the time the fibers spend at high temperature. In this
method the cellulose fibers get distributed evenly between polymer films and then
the “sandwich” is created by pressing in a compression molder at adequate time and
temperature. Bullions et al. [90], [91] prepared composites of kenaf bast, wood pulp,
and poultry feather fiber by mixing with polypropylene and then passing them
through a hot oven at a fast rate to melt the PP fibers but not degrade the natural
fibers and a formed a prepreg. The prepreg is then compression-molded into laminate
plates under pressure (4.44 MPa) and temperature (180 °C) [92].

Park [93] and Gendron [10] cover the processes for polyolefin foams and the
blowing agents used. The compression moulding of EVA foam shoe midsoles use a
different technology, with crosslinking and expansion in a heated mould. Eaves and
Witten [95] described the Zotefoams process, in which nitrogen is dissolved into
molten crosslinked polyolefin sheets in a high-pressure autoclave, which are then
expanded into foams in two stages. Recent research has concentrated on process
refinement. The development of rotomoulded [96] and microcellular foams [97] are
peripheral to the products discussed.

2.3.2.3 Reaction injection molding of foams

Reaction injection molding is a processing technique for the formation of polymer

parts by direct polymerization in the mold through a mixing activated reaction. A
simplified process schematic is shown in Figure 2.8. Two reactive monomeric
liquids, designated in the Figure 2.8 as A and B, are mixed together by impingement
and injected into the mold. In the mold, polymerization and usually phase separation
occur, the part solidifies, and is then ejected. Primary uses for RIM products include
automotive parts, business machine housings, and furniture [98].

35
 Figure 2.8 : Schematic of the reaction injection molding foam process.

Reaction injection molding is a variation of the standard high pressure molding with
impingement mixing. A very low viscosity mixture is injected into the mold to
produce quickly the final part. RIM differs from regular molding in that the
formulation of the polyurethane system has to be very fast. This is achieved by
replacing the diol crosslinker with diamine crosslinker to obtain polyurea. This
technique can be used to produce ‘structural foams’ (high density rigid foams with a
skin) for auto body parts, dashboards and bumpers and also to obtain elastomers and
microcellular foams. Components are injected in the mixing chamber of the mixing
head under high pressure and mixed by impingement. The piston then injects the
accumulated mass into the mold and cleans the chamber for the new shot. When the
piston is in the down position the polyol and isocyanate components are recycled.
Because of the low viscosity and low pressures RIM technology can be used to mold
large parts with metal inserts. The molds for RIM can be made from steel, aluminum
or zinc alloys. They are cheaper than the molds for injection molding of
thermoplastics. Total consumption of energy is lower than in the competing
techniques, and the investment in equipment is lower.

The most common RIM processable material is polyurethane, [99] but others include
polyureas, polyisocyanurates, polyesters, polyphenols, polyepoxides, and nylon 6.

Reaction injection molding can produce strong, flexible, lightweight parts which can
easily be painted. It also has the advantage of quick cycle times compared to typical
vacuum cast materials. The bi-component mixture injected into the mold has a much

36
lower viscosity than molten thermoplastic polymers, therefore large, light-weight,
and thin-walled items can be successfully RIM processed. This thinner mixture also
requires less clamping forces, which leads to smaller equipment and ultimately
lower capital expenditures. Another advantages of RIM processed foam is that a
high-density skin is formed with a low-density core [100]. The disadvantages are
slow cycle times, compared to injection molding, and expensive raw materials.

If glass fibers are added to get reinforcement, the method is known as RRIM
(Reinforced Reaction Injection Molding). Structural RIM (SRIM) is the process
whereby the reinforcement fabric or mat (glass, carbon) are placed in the mold and
the resin is injected to impregnate the reinforcement [101], [102].

2.3.2.4 Injection molding method

Injection molding is a manufacturing process for producing parts from

both thermoplastic and thermosetting plastic materials. Material is fed into a heated
barrel, mixed, and forced into a mold cavity where it cools and hardens to the
configuration of the cavity [103].

Figure 2.9 : Schematic of the injection molding machine.

The structural foam process is a low pressure injection molding process where an
inert gas is introduced into melted polymer for the purpose of reducing density and
hence weight of the finished product.

Low pressure foams (Figure 2.10/1) have the characteristics of the injection of a
physical blowing agent, usually gaseous nitrogen, into the extruder with the melt.
The charge is collected in an accumulator and injected in the mold at something less

37
than the mold volume through valved injection points called nozzles. The mold is not
filled when the injection phase is complete and the expanding blowing agent
provides the energy to force the polymer to the extremes of the mold cavity [104].

Figure 2.10 : Schematic of the injection molding foam processes.

High or medium pressure foam process (Figure 2.10/2). A chemical blowing agent is
typically used. The blowing agent decomposes under the influence of elevated
temperature over a time to produce a gas or series of gases leaving a small quantity
of a residue. The injected charge is incomplete to fill the mold cavity leaving the
expansion of the chemically liberated gas to provide the energy to fill the mold [105].

The performance advantages of injection molded thermoplastic foams have been

known and exploited for some decades now, but only the recent developments in
processing technologies and blowing agents have given them a steady growth into
new market applications. Automotive products, electric and electronic equipment and
industrial appliances are profiting from the reduction in war-page and shrinkage
associated with foam injection molding, as well as from the diminution in the
required clamping tonnage. An obvious benefit, the potential of material saving, is
gaining relevance in the automotive field, because of the ever tightening
environmental legislations toward the reduction of CO2 emissions. Facing the

38
demand of reducing the vehicles' weight, the implementation of foamed parts stands
as one of the most straightforward answers.

It is however known that the enhancement of the molded part properties has a price
to be paid in terms of mechanical performance. Given the typical structure of a foam
injection molded part, where a compact outer layer surrounds a foamed core, this loss
in properties is caused by an obvious reduction of the stress-bearing area, as well as
by the actuation of the foam cells as stress concentrators. The reduction in properties
has traditionally been studied as a function of the foam density reduction, but there is
little understanding of the effect played by morphological parameters of the foam,
such as cell size distribution, anisotropy or outer layer thickness.

In the injection of thermoplastic foams the morphology can be drastically affected by

the molding parameters, and the change in variables as injection velocity, melt
temperature and mold temperature can deliver, for the same density reduction, a very
dissimilar spectrum of properties [106].

Injection molding in the presence CBAs is the major manufacturing method to

produce high foams. On the other hand, up to 90 % of density reduction versus the
unfoamed polymer can be achieved by low density foaming with PBAs such as
volatile hydrocarbons, CFCs, HCFCs and atmospheric gases [107].

2.3.2.5 Rapid rotational foam molding

Conventional rotational molding, or rotomolding, is a plastics fabrication technology

that is advantageously utilized to manufacture single-piece, hollow or doublewalled,
large-sized, complex-shaped, seamless, stress-free plastic articles. Rotomolding is
best implemented in manufacturing environments that practice medium to low
production runs of large parts; this is due to the intrinsically lengthy cycle time of the
process, as it is required to elevate the temperature of a mold, while rotating it bi-
axially, from room temperature to beyond the melting temperature of the plastic to
allow shaping, and then cool it back to room temperature for part removal [108 -
113].

All rotomolding machines must allow accomplishing four distinct fabrication tasks;
these are: (i) heating, (ii) cooling, (iii) servicing, and (iv) bi-axial rotation during the
first 2 stages.

39
Rapid Rotational Foam Molding (RRFM) is a novel patent-pending process that was
designed and developed to maximize the synergistic effects resulting from the
deliberate combination of extrusion and rotational foam molding and thereby serve
as a time and energy efficient technology for the manufacture of integral-skin
rotationally molded foams of high quality.

Figure 2.11 : Single-charge rotational foam molding processing steps.

In case of the experimental trials could involve a variety of thermoplastics based on

foamable formulations with a chemical blowing agent (CBA) that are compounded
and processed by utilizing an extruder, and are foamed and injected as a foamed
core, instantly, into the cavity of a suitable non-chilled rotationally molded hollow
shell made of non-foamed pulverized thermoplastic polymers.

The investigated mold shapes included a cylindrical shaped mold and a rectangular
flat shaped mold. The obtained moldings are examined for the quality of the skin
surface, the skin-foam interface, and the achieved foam morphologies that are
characterized in terms of foam density, average cell size, and average cell density.

2.4 Properties of Polymer Foams

2.4.1 Foam geometry

When gas bubbles grow in a liquid, the foam goes through a number of stages.
Figure 2.12 shows a two-dimensional view in which the regularly spaced bubbles are
all the same size. As the density of the foam decreases, the bubbles come into

40
contact, forming a closed cell foam. Finally the cell faces burst and liquid drains to
the cell edges leaving an open cell foam. Beyond this the foam collapses back to a
liquid. When plastic foams are examined by scanning electron microscopy (SEM)
two main types are found. If the gas bubbles have grown in highly viscous
thermoplastic melt, the thinning of the cell walls is a slow process, and solidification
can stabilise the closed cell foam.

Figure 2.12: Change in the structure of a foam containing a regular array of

bubbles as the volume fraction of gas increases.

A section through the cell walls of a similar PVC foam shows that the cell faces are
uniformly thick. The faces, rather than the edges, contain most of the polymer. It is
easier to form such foams using glassy polymers, but recently the melt rheology of
polypropylene has been modified to allow stable foams to be formed in the narrow
process temperature window above the melting point of the crystalline phase. It is
also possible to crosslink polyolefins before foaming, which makes the cells more
stable.

When a low viscosity thermoset prepolymer is foamed the polymer can eaily drain
from the cell walls before the crosslinking reaction stabilises the foam cell edges.
Figure 2.2.a shows a polyurethane open cell foam in which only the cell edges
remain. These have three concave sides, the shape being fixed by the surface tension
of the liquid prepolymer.

Microcellular foams differ from classical foams, because of their cell structure,
higher density of the foams, which is typically 200 kg/m3, and the structure of the
matrix. Microcellular foams are foamed segmented elastomers with smaller number
of round cells, unlike polygonal cells with ribs in standard foams. Because of their
superior mechanical properties they are used for shoe soles, car bumpers, etc. [32].

The geometrical parameters are interrelated for a family of polymer foams made by
the same process. For polystyrene bead foam, where the density is determined by the

41
initial mass of beads placed in the mould, the cells become larger and the cell walls
thinner as the density of the foam decreases [13].

2.4.2 Foam density

Cell Density, defined as the number of cells per unit volume with respect to the
nonfoamed composite was determined by (2.4) [119]:

N = [nM2/A]3/2 x ψ (2.4)

Where, N = Cell density (cells/cm3), n = Number of cells, M = Magnification factor,

A = Area of the micrograph (cm2), and Ψ = Expansion factor of foamed sample.

2.4.3 Foam structure

The next parameter used to describe a foam is the fraction of open and closed cells it
contains. The latter are generally measured by comparing the external volume of a
foam specimen to the pressurized gas volume differential measured when the foam is
put in a hermetic chamber. If both volumes are equivalent, the foam has a 100 %
closed cell structure. If these volumes are different, their difference is attributed to
the open-cell fraction, which permits the penetration of the gas into the foam. This
study deals with industrial foams in which a closed-cell morphology predominates.

2.4.4 Cell size distribution

Another very important microstructural parameter required to describe a foam is the

cell size distribution, from which different statistical parameters can be derived. The
cell size distribution is obtained from quantitative observations of foams cells. These
cells are observed on the microtomed or fractured surface of the foam. By image
analysis, the surface area of individual cells, Ai, is measured and the corresponding
cell size, di, is calculated from the equivalent diameter of a circle of area Ai (di = 2√
Ai/π). To reflect the foam microstructure with a good statistical representation, the
number of cells to be measured should be reasonably high, e.g., 200–300.

By plotting the cell size in a histogram, the cell size distribution curve can be
obtained. From such a distribution, the number-average diameter dn and the volume-
average diameter dv can be calculated using (2.5) and (2.6):

42
 (2.5) (2.6)

where di and ni are a measured diameter i and the number of such diameters
measured, respectively.

A cell size distribution that is close to perfectly normal will show very close values
of dn and dv, while other distributions, a bimodal distribution for example, will show
very different values of dn and dv. Thus, the ratio of dv / dn represents a useful tool for
evaluating cell size dispersity, similar to the molecular weight polydispersity used in
polymer chemistry to characterize molecular weight distribution. It is generally
believed that a cell size dispersity ratio close to 1 (e.g., below 1.25) indicates a
statistically normal distribution or a monodisperse distribution. According to the
Schwartz–Saltikov statistical method for the correction of measured diameters [120],
the diameter correction for a monodisperse distribution is given by a constant equal
to 4/π (≈1.27). Since the correction factor is a constant for all foams with cell size
dispersity ratios close to 1, it will not be considered in the morphological
characterization of the foams.

2.4.5 Foam anisotropy

Foams produced as extruded panels generally exhibit morphological anisotropy,

which affects their mechanical behavior. Depending on the application, it could be
necessary to obtain their cell size distribution, average aspect ratio, and orientation in
three orthogonal directions, i.e., in the extrusion or machine direction, in the
direction normal to the machine direction, and in the direction normal to the
thickness of the panels. These three microstructural parameters account for their
morphological anisotropy, which will be reflected in their mechanical anisotropy.
The principal microstructural parameters are summarized in Table 2.5.

2.4.6 Melt Rheology Suitable For Foaming

When low-density foams are produced, the polymer melt undergoes high biaxial
extension to form cell faces. Its flow properties (rheology) must suit the process.
High molecular weight polymer melts are highly viscous, with part of the

43
deformation being elastic. The melt must sustain high tensile stresses without cell
face fracture which would cause neighbouring cells to join. Repeated fracture leads
to very large cells, and eventually to foam collapse. PS melts of high molecular
weight have a relatively low entanglement density [118], so can undergo high biaxial
extensions without fracture. Consequently linear PS can be used for foams. Various
techniques have been used to characterise the rheological differences between these
polymers. Characterisation of melt elasticity using a small oscillatory shear strain to
evaluate the complex shear modulus G* is inappropriate, since it cannot characterise
the high strain response. Consequently, tests subject melt extrudates to large tensile
deformations.

Table 2.5 : Useful microstructural parameters to describe foams.

Foam Characteristics Microstructural Parameters
Amount of material Density, relative density, void fraction
Foam structure Fraction of open and closed cells
Number-average and volume-average
Cell size distribution
diameters, cell size dispersity
Cell size in orthogonal directions, cell
Anisotropy
aspect ratio, and cell orientation*
* Orientation of the maximum cell diameter with respect to a reference direction.

Ruinaard [122] was the latest of many researchers who measured the tensile viscosity
of polyolefin melts. When a PP melt extrudate was stretched at a constant ε the
tensile viscosity η increased with time, as the tensile strain increased, due to the
entanglement network in the melt becoming significantly extended.

Figure 2.13 shows the behavior of a polymer under variations of pressure and
temperature. For example, if the temperature is increased in the system, the velocity
of the molecular movement and the kinetic energy will be increased as well. As a
consequence of this energy increase, the number and frequency of collisions between
molecules will rise, resulting in an increase of the residence volume of the molecules.
On the other hand, the volume of the system will decline due to its compressibility if
the pressure is increased in the fluid phase [63].

44
 T0, p0, V0 T1 > T0, p1 = p0, V1 > V0 T2 = T1, p2 > p0, V2 > V1

Fluid-molecule Residence volume

Figure 2.13 : Impact of temperature and pressure on the blowing agent.

2.5 Characterization Methods of Polymer Foams

Polymeric foams are generally characterized in terms of mechanical performance by

means of different conventional mechanical testing methods. The most popular of
these methods are summarized in Table 2.6.

Table 2.6 : Summary of the most popular mechanical testing methods used for
foams.
Testing Method Designation Test Method Description
Constant section (square or circular)
specimen compressed at constant nominal
Compression strain rate until specimen failure or until
the deformation reaches the nominal void
fraction.
Constant rectangular section beam
Flexural specimen in three- or four- bending until
specimen failure or load plateau.
Clamped plate specimen with a circular rig
impacted by a falling dart equipped with a
Falling dart impact load cell and a displacement transducer
(impact should generate failure of the
specimen).
Constant section (square or circular)
specimen impacted by a plateau at high
Dynamic shock cushioning speed until specimen failure or the
(flat sheet impact) deformation reaches the nominal void
fraction (test may be repeated to obtain
maximum compression or densification).

45
While these mechanical characterization techniques can help to produce a foam that
will perform according to certain functional requirements, additional work still needs
to be done in order to understand the origin of their performance. To achieve this, the
relationship between the morphology of engineering foams and their functional
behavior needs to be defined. Until now, the relationship between morphology and
performance has been discussed according to the approach proposed by Gibson and
Ashby [124], which relates foams’ mechanical properties to their density. However,
this approach, based exclusively on the foam density, does not take into account the
detailed morphological characteristics of foams, such as their cell size distribution
and anisotropy.

In recent years, some attempts at considering detailed morphological foam

characteristics in mechanical behavior analysis have been reported.

Table 2.7 : Characterization methods and standards of rigid cellular plastics [100],
[125].
Subject Standard
Test methods ISO 9054, ISO 7214
Tensile properties ISO 1926, ASTM D 1623,DIN 53430
Flexural properties ISO 1209-1/-2, JIS K 7221
Shear strength ISO 1922, DIN 53427
Compression properties ISO 844, ASTM D 1621, EN 826
Compression creep test ISO 7616, ISO 7850
Thickness measurement EN 12431
Pendulum impact strength ISO 179
Density ISO 845, ASTM D 1622
Dimensions DIN 53570
Tensile strength perpendicular to
faces EN 1607, DIN 53292
Dielectric constant and
dissipation factor ASTM D-1673
Dielectric breakdown and
dielectric strength ASTM D-149
Electrical resistance ASTM D-257

However, this is not intended to provide an exhaustive survey of foam properties, nor
a comparison of the performance of different foams or foamed structures. The
textbook of Gibson and Ashby [124], which provides a very wide survey of foam
structures and properties. A microstructural description of foam materials that takes
into account their detailed morphological characteristics and that can be employed as
a single microstructural parameter to report mechanical properties will be provided.

46
The foam samples could be characterized by the volume expansion ratio and the cell-
population density. The expansion ratio of the foam is determined by measuring the
weight and volume expansion of the sample. The volume of foam sample is
determined by the water displacement method (ASTM D792). The volume expansion
ratio (Ф) is calculated on the basis of the ratio of bulk density of pure material (ρp) to
the bulk density of foam sample (ρf) as follows [126]:

(2.7)

The cell-population density is calculated from the microstructure obtained from the
scanning electron microscope (SEM). SEM pictures are used to investigate
morphology, number and shape of foamed cells/bubbles/voids and whether a cellular
structure is being achieved or not. The foam samples are fractured in liquid nitrogen
and the fractured surface is coated with gold before SEM. The cell density (n) is
defined as the number of cells per unit volume with respect to the unfoamed
polymer. A certain area is chosen in the SEM photograph. The number of cells per
unit volume (3D) is estimated from 2D information, assuming that the cells are in a
spherical shape. It may be noted that it is used the cell-population density defined
with respect to the unfoamed polymer and the volume expansion ratio to better
describe the processing-to-structure relationships. These parameters indicates how
well cell nucleation and expansion are controlled during foam processing [126].

The most popular mechanical testing method used for foams is the compression test.
This testing method [127] consists of compressing a foam specimen and recording
the load reaction as the specimen reduces in thickness as a result of the imposed
displacement. The compressive stress–strain curve is obtained by dividing the load at
any moment during the test by the nominal area and the imposed reduction in
thickness by the initial thickness of the specimen. An illustration of this compressive
stress–strain curve is shown in Figure 2.14. This compressive stress–strain curve
typically shows three stages. The first stage is characterized by a linear elastic or
Hookean behavior where the stress is proportional to the strain, following Hooke’s
law. The compressive modulus of elasticity E* is obtained from the slope of this
initial linear portion of the compressive stress–strain curve. The compressive strength
σy* is obtained from the compressive stress at the yield point if a yield point occurs
before 10 % deformation or, in the absence of such a behavior, from the compressive

47
stress at 10 % deformation. The compressive yield point is defined as the first point
on the compressive stress–strain curve at which an increase in strain occurs without
an increase in stress.

Figure 2.14 : Typical compression stress–strain curve of a low-density elasto-

plastic foam, with compressive modulus of elasticity E*,
compressive strength σy*, and strain at densification εd*.

Starting from the yield point, the second stage of the compressive stress–strain curve
is characterized by an approximately constant compressive stress rate (plateau)
during which the foam undergoes plastic deformation, either by elastic buckling,
plastic yielding, or brittle crushing, depending on the foam behavior. This constant
compressive stress rate stage extends over a certain amount of compressive
deformation and ends at the onset of densification, which defines the third and last
stage of the compressive stress–strain curve. The densification stage is a progressive
one, during which the foam cells collapse completely, resulting in a rapid increase of
the compressive stress as a result of the densification of the foam. The limit of this
densification stage in terms of deformation is set by the amount of material in the
foam, i.e., its density. As a first approximation, this deformation at densification εd*
may be obtained from the void fraction in the foam, given by 1 – ρr (where ρr is the
relative foam density). As the foam is collapsing, the compressive stress–strain curve
progressively tends towards the bulk modulus of the material in the foam.

Other testing methods have also been used to characterize the mechanical
performance of foams. Flexural tests [128], either in three-point or four-point

48
bending configurations, can be performed. The advantage of the latter is that it
permits the researcher to obtain the flexural modulus and the flexural strength, which
are of prime interest in the production of foam cores in sandwich panels, for
example. It also allows one to obtain the mechanical performance of foams under a
positive tensile stress, which is very difficult to obtain for polymeric foams in tensile
testing due to stress concentration effects at the grips used to hold the tensile
specimens. Variations of impact testing, either with a falling dart [129] or a flat sheet
impact (dynamic shock cushioning) [130] are also of interest for quantifying the
foam’s ability to resist high velocity puncture by an object or to absorb dynamic
compressive shocks and retain its properties.

2.6 Application Areas of Polymer Foams

Foams, as engineering materials, are now used in all industrial sectors and represent
an extraordinary class of materials. They are intended for packaging, thermal and
electrical insulation, buoyancy, and structural applications such as decks, road
pavements, sandwich panels, and so on. This extraordinary character comes from
their diverse functionalities — stiffness, strength, impact resistance, dielectric and
thermal resistance, and permeability, among others — which can be customized to
obtain properties ranging beyond the limits of all other classes of engineering
materials. A great challenge in engineering foams is to address parameters such as
specific weight and cost while answering functional requirements.

Lower density plastic foams, i.e., up to ≈ 300 [kg/cm3], are used in a variety of
applications; these include: comfort cushioning (automotive, transportation, and
furniture); floatation (in-place floatation for small vessels, marine life vests, pool
accessories, child toys); shock mitigation (food packaging, construction and
transportation crash barriers); and thermal shielding (industrial coolants, appliances,
insulative packaging) [131].

Higher density plastic foams, i.e., above ≈ 300 [kg/cm3], in opposition, are used to
serve the following applications: furniture (frames, tables); materials handling
(pallets, milk and soda cases, containers); industrial (battery cases, trash containers,
electrical housings); automotive (decorative paneling, glove box door, instrument
panels, fender liners, vehicle crash barriers); and marine (seats, fish boxes, cabin
structures) [131].

49
 Table 2.8 : Typical markets for low-density foams [131].
Market Application
Automotive, transportation, and furniture
Comfort Cushioning seating, mattresses, bedding and carpet
underlay
Marine buffers, marine life vests, pool
Flotation
accessories, toys
Package protection for light bulbs, eggs,
Shock Mitigation fruit, electronics, furniture, and machinery,
surface protection as overwrap
Sidewall and roofing insulation, industrial
insulation for coolers, tanks, and
Thermal Barrier
reservoirs, appliance and hot water
insulation

Table 2.9 : Typical markets for high-density foams [131].

Market Application
Panels, frames, tables, seating, bed
Furniture
structures
Cabinetry Stereo components, equipment housings
Material Handling Pallets, milk and soda cases, containers
Battery cases, underground conduits,
Industrial
transformer housings
Toys, coolers, totes, mirror and picture
Consumer
frames
Construction Shutters, shingles, windows, doors
Appliances Washer tops and doors, tubs and bases
Decorative paneling, glove box door, seat
Automotive
frames
Marine Fascia, seating, fish boxes, cabin structure

Composite sandwich structures consisting of thermoplastic skins and foamed core

are finding increasing use in a variety of applications such as mass transit and
automotive structures [132], [134 - 137]. In many cases, thermoplastic sandwiches
offer many advantages compared to traditional materials, such as steel, aluminum,
and thermoset composites, due to their high-specific strength, good damping
capacity, corrosion resistance, superior impact resistance, and ease of shaping and
recycling [138]. Moreover thermoplastic sandwiches are characterized by other
physical properties, such as thermal and acoustic insulating properties, making these
structures an attractive alternative to more traditional solutions. The design of such
structures requires the knowledge of different mechanical parameters due to their
intrinsic nonhomogeneity. Among other requirements, skin and core stiffness and
also skin–core adhesion characteristics are important. An example for composite

50
structure of a thermoplastic sandwich panel used in insulating walls of containers for
food transportation [139] is that foamed poly(ethylene terephtalate) (PET) core (100
mm thick) with polypropylene (PP)/glass fiber skin sandwich (4 mm thick).

2.7 Literature Review of PET Foams

R. G. (Dick) Angell, Jr. [140], of Union Carbide Corporation described the structural
foam process. The article in its introduction stated; “With the structural foam
molding process a product with a cellular core and integral solid skins is molded in
a single operation. Almost any thermoplastic resin can be used. This structure is
tough, rigid, light in weight, and impervious to gases and liquids at moderate
pressures.”

Xanthos et al. [141] evaluated extrusion foamability of a variety of PET resins with
different rheological characteristics using several CBAs and found that an
exothermic CBA (Expandex 5-PT) performed better than two other endothermic
ones. They produced high to medium density PET foams ( > 0.6 g/cc). The foam
densities varied with respect to the material variables (type and concentration of
CBA) and the operational variables (die set temperature and screw rpm). In order to
obtain improved foamability of PET with PBA, they suggested the use of PET with
modified viscoelastic characteristics.

Baldwin et al. [142 - 143] performed microcellular foaming with a commercial PET.
They used cell density as a representative variable to describe the foam
characteristics, and the higher cell densities of 1010 ~ 1012 cells/cc were obtained with
the semi-crystalline PET rather than APET (amorphous PET) or CPET (nucleated
PET).

The published information on foaming of aromatic polyesters is mostly about PET

foaming rather than PBT. This may also be related to the lower cost of the PET resin
vs. PBT and the recent penetration of PET foams in competitive packaging markets
that are currently served by low cost commodity resins [144].

There exist many technical and scientific articles on chain extension/branching used
to modify its structure as well as applications of the modified PET in extrusion
foaming. PET modifiers and examples of their use have been reviewed [145 - 146].
By its versatility, the reactive modification of PET has been applied to recycled post-

51
consumer PET with the intent of producing extrusion foamed products. Xanthos et.
al. [147 - 148] showed the improvement of foamability of the recycled PET by
rheological modification with pyromellitic dianhydride (PMDA) in a comparative
study of unmodified and modified (post-consumer) PET using physical blowing
agents. They delineated the rheological characteristics of the modified PET as higher
MFI, higher melt viscosity, early shear thinning with high shear sensitivity, and
higher extrudate swell ratio as compared to the unmodified PET. They could obtain
low density foams (< 0.5 g/cc) with the modified PET, while foams with density
below 0.7 g/cc could not be achieved with the unmodified polymer.

Japon et al. [149] used a tetraepoxide to reactively modify recycled PET. They
obtained branched structures with broadened MWD, and highly increased
elongational viscosity. Their application of the modified PET to extrusion foaming
with PBA resulted in foams with high density of 0.85 ~ 1.0 g/cc.

Xanthos et. al. [150] showed that glycidyl functionalized additives such as a
diepoxide and an ethylene-glycidyl methacrylate (E-GMA) copolymer reacted
readily with the functional groups of PET, acting as chain extending/branching
agents. The modified product showed promising rheological characteristics for low
density foaming. They also found that the diepoxide had higher reactivity than E-
GMA and could be used at much lower concentrations to produce resins with the
desired characteristics.

Dhavalikar and Xanthos [151] performed a comparative study of four different multi-
epoxides, N,N’-bis[3(carbo-2’,3’ epoxypropoxy)phenyl] pyromellitimide (BGPM),
glycidyl ether of bisphenol-A (DGEBA), triglycidyl isocyanurate (TGIC) and
triglycidyl glycerol (TGG), as PET rheology modifiers. They found that TGIC and
BGPM were most efficient in the modification reactions; however, a limitation of
BGPM was that it was not commercially available. As shown in their subsequent
work [116], the melt modified PET by TGIC showed an increase in relaxation time
and broadening of relaxation times distribution with corresponding effects on MW
and MWD.

A compherensive comparison study was published by Xanthos et. al. [94]. Low
molecular weight multifunctional anhydrides and epoxides were evaluated as
rheological modifiers for PET by reactive extrusion under controlled conditions. The

52
dianhydrides, used in the study, were: PMDA and 3,3’,4,4’-benzophenone
tetracarboxylic anhydride (BTDA). The multi-epoxides were BGPM, TGIC and
tetraglycidyl diamino diphenyl methane (TGDDM). Correlations of die pressure with
extrudate swell and melt flow index with melt strength by off-line testing showed
that the most reactive modifiers were PMDA, TGDDM, and TGIC.

Crystallinity in MCFs of semicrystalline polymers also plays a role and should be

considered [114]. It thus appears that the specific morphological characteristics of
MCFs have a great influence on their mechanical properties, both at low and high
strain rates, and that the cell size, among other microstructural parameters, plays an
important role in the determination of these properties.

Solubility of CO2, Ar and N2 in different polymer systems has been obtained using
the in-line method developed in a single screw extruder. Carbon dioxide has the
highest solubility in PET, nitrogen has the lowest, and argon somewhere in between
[115]. This trend is consistent with literature results obtained for the same systems
under temperatures below the polymer Tg [33]. Solubility decreases with increasing
temperature for both CO2 and Ar.

Hirai et al., produced modified PET foam with density as low as 0.3 g/cm3 by
extrusion using a saturated hydrocarbon foaming agent. The modified PET had
increased the viscosity and the tensile strength of the PET melt. The modified PET
foams showed higher glass transition temperature and the thermal cracking
temperature compared with those with the unmodified PET [34]. Baldwin et al.
investigated the effects of four major processing variables (gas saturation time, gas
saturation pressure, foaming time, and foaming temperature) on the microcell
nucleation processes of amorphous and semicrystalline PET. They found that the cell
density of PET increased with increasing gas saturation time and pressure, the
foaming time had a relatively weak effect on the cell nucleation, and the foaming
temperature near the glass transition influenced the density of the amorphous PET
[142 - 143].

Guan et al. developed a new method to microcellularly process a PET sheet with a
general hydraulic press above PET’s crystallization temperature and below its
melting temperature within the time of a few minutes [6]. The low melt strength, low
shear and elongational viscosities of conventional PET prevents from being easily

53
foaming. Sorrentino et al. produced high-molecular-weight PET foams, where chain
extension of polymers was used, by the pressure quench method with N2, CO2, and
their 80/20 mixture as blowing agents and correlated to the thermal, rheological,
volumetric, and gas sorption properties [7].

2.8 Polycaprolactone–poly(dimethylsiloxane) Block Copolymers

Copolymers containing poly(dimethylsiloxane) (PDMS) have received considerable

attention due to their unique properties, such as very low glass transition
temperature, low surface energy, low solubility parameter, and physiological
inertness [76 - 77]. Some of their specialty applications are in the fields of
biomaterials [85] and surfactants [72]. Though a variety of synthetic routes have
been used to prepare PDMS containing copolymers, less work has been done
preparing block copolymers of dimethyl siloxane and α,β-unsaturated esters [121].
This is mainly attributed to the limited copolymerizabilities of both monomers in
anionic polymerization [21].

Polysiloxane possesses a unique combination of many interesting properties,

especially a high surface activity and an extremely low solubility parameter. These
properties lead to the thermodynamic incompatibility of polysiloxanes with almost
all other organic polymer systems. One method to overcome this difficulty is by
blending the siloxane-containing copolymers with organic polymers since siloxane
homopolymers can only provide a temporary surface modification to the blend. In
siloxane-containing multiphase, block, segmented, or graft copolymers, siloxane
segments migrate to the air–polymer surface; but the organic segments in the
copolymers act as an ‘‘anchoring group’’ for the siloxane blocks, and then the
permanent surface modification can be achieved. For this purpose, the syntheses of
siloxane-containing copolymers have been studied for about 30 years. In 1964, Jarvis
Fox, and Zisman reported first that the siloxane-containing copolymers were blended
with the base resin to modify the surface [73]. After that, the siloxane copolymers are
used as surface-modifying agents in some important applications, such as paints,
coatings, and textile fiber.

Polydimethylsiloxane (PDMS) containing copolymers display an unusual

combination of properties. These include extremely low glass-transition temperatures
of -120 °C; very low surface energies; good thermal, UV, and flame resistance; water

54
repellancy; hydrolytic stability; and biocompatibility. If the organic blocks and
PDMS segments are properly designed it is possible to use silicone copolymers as
surface-modifying additives for organic polymers. In such systems organic blocks
interact with the base resin through entanglements, cocrystallization, or electrostatic
interaction, such as hydrogen bonding, whereas silicone segments provide the
surface modification.

When such additives are used in small amounts, the change in surface properties is
achieved without influencing the bulk morphology or properties of the base resin. In
view of the preceding observations, it is possible to optimize the application-specific
surface properties of a polymeric system by proper choice of a base resin with the
desired bulk properties and a surface modifying silicone copolymer and blending
them before processing.

Their large molar volumes and low cohesive energy densities result at exceptionally
low surface tensions, surface energies, and solubility parameters. Although PDMS is
a good candidate for modification of other polymer surfaces and interfaces, it is
highly immiscible with almost all other organic polymer systems; and if PDMS is
used by blending, it does not function properly. An effective way to increase
compatibilities is certainly to form their copolymer systems; different block,
segmented, and graft copolymers of siloxanes are already known. ABA-type
siloxane-containing block copolymer, α,ω-dihydroxy polycaprolactone–
poly(dimethylsiloxane), (PCL-PDMS-PCL) triblock copolymer were used in this
work.

55
56
3. EXPERIMENTAL PART

3.1 Chemicals Used

3.1.1 Poly(ethylene terephthalate) (PET)

Poly(ethylene terephthalate) was obtained from AKSOY Plastik Company (Octal

GP01). Its intrinsic viscosity is 0.81 dL/g at 30 °C in Ph/TCE 60:40 (ASTM D4603-
03). Weight of 100 pieces chips are 1.63 g. Melting point of PET is 247 °C.

3.1.2 5-Phenyl-1H-tetrazole (5-PT)

5-Phenyltetrazole was used as an exothermic non-ammonia foaming agent for the

engineering plastic, PET. It has the appearance of white to off-white crystalline
powder. Melting point of 5-PT is 216 °C, and 5-PT decomposes around 250 °C.
Tetrazole is one of a class of organic heterocyclic compounds containing a five-
membered diunsaturated ring structure composed of four nitrogen atoms and one
carbon atom. Its molecular formula is C7H6N4.

Decomposition of 5-PT occurs in 2 first order steps; tale pink intermediate then
decomposition. Blowing gas yield is 200 cm3/g (98 % N2 and 2 % NH3), molecular
weight of 5-PT is 146.15, heat of combustion of 5-PT is -3907 kJ/mol.

5-PT is the product of Sigma Aldrich company with a 99 % purification, was used
without any purification procedure in this study.

3.1.3 Polycaprolactone–poly(dimethylsiloxane), (PCL-PDMS-PCL)

TEGOMER® H-Si 6440 P is a wax type siloxane co-polyester which is in pellet

form. It is the product of Evonik Goldschmidt GmbH with a 99 % purification, was
used without any purification procedure in this study.

57
 HO OH

The α,ω-dihydroxy polycaprolactone–poly(dimethylsiloxane) (PCL-PDMS-PCL)

triblock copolymer used was a commercial product of Evonik (Tegomer H-Si 6440)
with Mn = 6500 (+/- 600); Mw (PDMS) = 3000; and PCL endblocks = 2000 g/mol. It
was dried at 70 °C in a vacuum oven for 48 h before use. This copolymer shortened
as PDMS in results and discussion section.

3.1.4 Paraffin liquid (medium)

Paraffin Liquid (Medium) or mineral oil, is a mixture of heavier alkanes. It has a

density of around 0.8 g/cm3. It was used to wet the surface of the polyester granules
and to occur mixing with dust form of ingredients of the process.

3.2 Equipments Used

3.2.1 Vacuum Oven

In vacuum oven, the heat-treating process takes place inside a vessel that is airtight.
The entire heat-treating process can take place under vacuum with the help of
vacuum pump. The direct contact between the load and the heatable and removable
thermoshelves in the chamber of the vacuum oven ensures rapid and uniform
temperature control without the loss of heat.

Figure 3.1: Vacuum oven instrument and vacuum desiccator.

58
Digital electronic vacuum, temperature, pressure control. Memmert VO 500 model
vacuum oven was used at 130 °C, five hours according to ISO 1133-1 to remove the
moisture from polyester raw material.

3.2.2 Melt flow index device (MFI)

Melt flow index (MFI) is a value that consists of melt flow rate (MFR) and melt
volume rate (MVR) values. It is a measure of the ease of flow of the melt of a
thermoplastic polymer. MFR is the weight of flowed sample in a certain time (g / 10
min) MVR is the volume of flowed sample in a certain time (cm3 / 10 min) under
2.16 kg load. HAAKE Melt Flow MT was used to measure MFR and MVR values of
sample (Figure 3.2).

Measuring piston
and standart weight

MFR device

MT unit

Figure 3.2: “Melt flow index” MFI device.

3.2.3 Hydraulic hot press

Qualitest MHM100 model Hydraulic Molding Test Press was used for compression
molding of PET foam samples. This instrument has a maximum temperature of 300
°C, and maximum pressure of 250 bar. It has the capacity of 10 tons.

59
Figure 3.3: Temperature control panel and pressure gauge of hydraulic hot press
instrument.

The machine is convenient for preparing samples as they ensure uniform process and
save time.

Figure 3.4: Hydraulic hot press machine.

3.2.4 Hydraulic cold press

Qualitest MPM100 model Hydraulic Molding Test Press was used for compression
molding of PET foam samples. This instrument has a water cooling system, and
maximum pressure of 250 bar. The press works under hydraulic system, working fast
and steadily.

60
3.2.5 Mechanical test device

To obtain flexural properties of polyester foams, mechanical test was made by using
Zwick Roell ProLine testing machine. Three-point bending flexural tests of samples
were measured using ASTM D790-10 and ISO 178 represent classical
characterization methods for rigid and semi-rigid plastics. Maximum weight
capacity, pre-load is 2 N, and maximum speed of the device is 1mm/min.

Figure 3.5 : Three-point bending mode flexural test instrument.

Typical test results include the flexural E-modulus, stress at 3.5 % elongation and
strains at yield point and at specimen break. The results of the flexure test show in
particular material behavior near the surface of the specimen. The deflections
measured are approximately four times greater than the extensions recorded in the
tensile test.

3.2.6 Contact Angle Measurement Instrument

CAM 200 (KSV) model Attension THETA Optical Tensiometer with a video camera
based fully computer controlled contact angle meter was used for contact angle
measurements of PET foam samples at room temperature. Digital video camera 60
fps (frames per second) including zoom and camera stage. One touch manual
dispenser movement (OTD), and software trigger to enable automatic contact angle
measurement versus time or versus location with only one push of the dispenser level
per drop. Software trigger takes measurement after predefined time delay after push
of the dispenser lever. Operation sequence: create drop - push - move sample -
create. Automatic single liquid dispenser for dynamic contact angle and surface
tension measurements by pendant drop method. PC control of dispensing operation.

61
Hamilton 1 mL syringe C205A with tubing and dispensing gauge 22 needle C209-
30. Dispensing resolution 0.1 µL manual single liquid dispenser syringe.

Basic frame with back light and control electronics and an interface for extra light
source and temperature control options. Software for determination of: 1) Contact
angle by sessile/raising drop method with automatic base line detection, 2)
Surface/interfacial tension by pendant/raising drop method, surface tension and
contact angle by liquid meniscus method, 3) Image fittings, polynomial, tangent,
circular fit, Young-Laplace, including autobaseline algorithm, 4) Surface free energy.

Figure 3.6 : Contact angle measurement instrument.

The contact angle is the angle at which a liquid/vapor interface meets a solid surface.
The equilibrium contact angle is specific for any given system and is determined by
the interactions across the three interfaces. A single system of drop/medium
(air/surface) has a spectrum of contact angles ranging from the so-called advancing
(maximal) contact angle to the receding (minimal) contact angle.

3.2.7 Calliper

The precision of length measurements may be increased by using a device that uses a
sliding vernier scale. The instrument has a main scale (in millimetres) and a sliding
vernier scale. This instrument may be used to measure outer dimensions of objects
(using the main jaws), inside dimensions (using the smaller jaws at the top), and
depths (using the stem).

62
Vernier callipers can be used to determine dimensions of ≥30 mm on plastics and
rubbers (ISO 178, ISO 4648, ASTM D 3767, DIN 53534), and dimensions ≥10 mm
of rigid cellular plastics (DIN 53570).

3.2.8 Thermogravimetric (TGA) and differential thermal (DTA) analysis

instrument

Thermogravimetric analysis (TGA) is a thermal analysis technique which measures

the weight change in a material as a function of temperature and time, in a controlled
environment.

Figure 3.7 : Linseis STA PT 1750 model TGA/DTA combined instrument.

This can be very useful to investigate the thermal stability of a material, or to

investigate its behavior in different atmospheres (e.g. inert or oxidizing). It is suitable
for use with all types of solid materials, including organic or inorganic materials
[118].

Differential thermal analysis (DTA) is a calorimetric technique, recording the

temperature and heat flow associated with thermal transitions in a material. This
enables phase transitions to be determined (e.g. melting point, glass transition
temperature, crystallization etc.).

Linseis STA PT 1750 model TGA/DTA combined instrument was used for the
thermal characterization. (Figure 3.7) The measurements were applied via aluminum
crucibles within 20 mg sample weight, at the speed of 10 °C/min in nitrogen

63
atmosphere. The instrument measurement temperature range starts from -150 up to
1750 oC.

3.3 Experimental Procedure

3.3.1 Preparation of the mixture

All PET pellets were dried in vacuum oven at 130 °C for 5 hours, after they have
taken out from there, they were put into vacuum desiccator.

In all experiments, approximately 0.1 g Paraffin were used because of the size
differences between granules of PET and powders of CBA. 5-phenyl tetrazole
powder was stuck on the surface of PET granules, but sometimes they were
cumulated when exposed to paraffin.

Figure 3.8 : Charging of the mold within PET mixture into hot press instrument.

A commercial-grade PET granules were mixed with 5-PT and PDMS, and were
placed in a 120 X 120 X 2 mm3 mold between Teflon sheets in 1.0 mm thicknesses,
and were loaded into a hydraulic hot press in which the experimental conditions had
adjusted before. Under heating and pressure, the foaming reagent 5-PT decomposes
to produce nitrogen gas at elevated temperatures.

3.3.2 Production of cellular structure

Compression molding was used for processing of thermoplastic material, PET.

Initially, PET was mixed with weighed amounts of CBA and PDMS filler. Then, the
process was ready for the four main stages of compression molding process:

1) mold charging, 2) compressing, 3) cooling, and 4) part removal.

64
First, between the preheated hot platens in a hydraulic press was put the mold which
was charged with material. Second, the mold was compressed to melt the material
and flow to fill the cavity of the mold. Some of CBA may start decomposing during
this process. Certain residence time is required to get homogeneous bubble size
distribution. Third, the mold was cooled down to solidify the product. Fourth, the
mold was decompressed, and the product was released. Amorphous structures of the
products were observed owing to fast cooling procedure by Cold Press instrument.

3.3.2.1 Heating process in hydraulic hot press

Polymer foams were prepared by using hydraulic hot press instrument with the
processing temperature and pressure in the ranges of 255 - 275 oC and 10 - 100 bar,
respectively. The amount of 5-PT was around 0.10 % and 0.20 % (wt). The PCL-
PDMS-PCL was added in between 0.050 % and 0.300 % (wt). Foaming time were
taken from 6 to 22 minutes.

3.3.2.2 Cooling process in hydraulic cold press

Cooling period of molten product was maintained in hydraulic cold press instrument.
Cold press instrument pressure adjustment was 50 Bar, and the total processing time
was 5 minutes. Amorphous structure of product because of fast cooling by cold press
instrument.

3.4 Tests and Analysis

The prepared closed cell PET foams were characterized morphologically, physically
and mechanically in terms of contact angle measurement (ASTM D5946, ASTM
D5725), apparent density calculation (ASTM D1622-08), cell density measurement
and 3-point bending test (ASTM D790-10).

3.4.1 Melt flow index

The melt flow properties of the PET samples were determined by calculating the
values of MFR and MVR. PET samples were dried at 130 oC, 5 hours in vacuum
oven according to ASTM D1238 standard before the tests. The determination of the
melt flow rate, MFR, measurements followed ISO 1133-1 with MVR test

65
temperature at 280 oC under 2.16 kg load. The MFR and MVR measurements were
done, and the MFR value was found as 86.29 g/10 min for PET.

3.4.2 Mechanical test

The three point bending mode flexural test provides values for the modulus of
elasticity in bending Ef, flexural stress σf, flexural strain εf and the flexural stress-
strain response of the material.

Figure 3.9 : The three point bending flexural test layout, loading.

The main advantage of a three point flexural test is the ease of the specimen
preparation and testing. However, this method has also some disadvantages: the
results of the testing method are sensitive to specimen and loading geometry and
strain rate. From the measured stress, strain values; elastic modulus, maximum stress,
and stress at break were calculated from the average of at least four (4) specimens
tested.

To make a comparison for the mechanical improvements of PET foam samples,

flexural properties of PET foams were considered, measured, and calculations were
done. 1 mm/min test speed were used for the measurements.

A brittle material will deform reversibly to a small amount and then fracture. A
ductile material will also deform reversibly up to a certain amount and then yield and
flow under the applied force until it begins to harden under load and then fail. Up to
the elastic limit, the material will return to its former shape and size when the force is
removed. Beyond this point deformation is irreversible i.e. creep has occurred.

3.4.3 Contact angle analysis

If the molecules of a liquid are strongly attracted to the molecules of a solid (for
example water on a strongly hydrophilic solid) then a drop of the liquid will
66
completely spread out on the solid surface, corresponding to a contact angle of 0°.
Less strongly hydrophilic solids will have a contact angle up to 90°. On many highly
hydrophilic surfaces, water droplets will exhibit contact angles of 0° to 30°. If the
solid surface is hydrophobic, the contact angle will be larger than 90°. On highly
hydrophobic surfaces the surfaces have water contact angles as high as ~120° on low
energy materials e.g. fluorinated surfaces (Figure 3.10).

Figure 3.10 : Contact angle, hydrophobic and hydrophilic surfaces.

3.4.4 Bulk density analysis

Dimensional analysis(dimensions and volumes of samples) of PET foam samples

were made with the Calliper. Vernier callipers was used to determine dimensions
≥10 mm of rigid cellular plastics (DIN 53570). Density measurements were achied
with Calipper and Balance (mass of samples).

3.4.5 Cell density analysis

The pictures of PET foam samples were taken from Digital video camera 60 fps
(frames per second) including zoom and camera stage. The diameters of bubbles
measured with perfect screen ruler software programme. Conversation factors from
the x and y scale (512 x 480) pixel to (5.883 x 5.506) mm are that x-scale factor is
0.01149, and y-scale factor is 0.01147 used.

The cell density analysis results were evaluated for the cell size distribution, and the
number-average diameter dn and the volume-average diameter dv were calculated due

67
to the equations 2.5 and 2.6 which are stated in section 2.4 properties of polymer
foams.

3.4.6 Thermogravimetric (TGA) and differential thermal (DTA) analysis

Linseis STA PT 1750 model TGA/DTA combined instrument was used for the
thermal characterization. (Figure 3.7) The measurements were applied via aluminum
crucibles within 20 mg sample weight, at the speed of 10 °/min in nitrogen or oxygen
atmosphere. The instrument measurement temperature starts from room temperature
to 300 oC.

5-Phenyl tetrazole shows melting temperature at around 215 °C, and decomposes at
around 250 °C. Nitrogen gas is liberated within the mass by thermal decomposition
of 5-PT, the chemical blowing agent. Poly(ethylene terephthalate) shows melting
range between 230 °C and 260 °C (Figure 3.11).

The measurements via thermogravimetric (TGA) and differential thermal (DTA)

analyses showed that the temperature ranges of 5-PT and PET are overlapping with
each other at around 250 °C (Figure 3.11). Therefore, 5-PT is suitable to work with
PET.

The thermal behaviour of 5-PT with increasing temperature was observed using a lab
scale oven, with ranging temperatures between 200 °C and 300 °C. As stated in
literature, decomposition occurs in two (2) first order steps; telltale pink intermediate
then decomposition (Figure 3.12).

68
 (a)

(b)

(c)

Figure 3.11 : Thermal analysis (TGA and DTA) graphs: (a)DTA graph of PET.
(b)DTA graph of 5-PT blowing agent. (c)TGA graph of 5-PT
blowing agent.

69
 Figure 3.12 : Decomposition behaviour of 5-PT with increasing temperature.

Intermediate decomposition products (typical pink coloured) and residues of 5-PT

are shown in Figure 3.12 at different temperature scales (220 °C, 230 °C, 240 °C,
250 °C, 260 °C, 270 °C, 280 °C).

The most commonly reported solid decomposition product of 5-PT is 3,5-diphenyl-

1,2,4-triazole and the other solid decomposition products claimed are
aminodiphenyltriazole and triphenyl-s-triazine.

70
4. RESULTS AND DISCUSSION

In this work, twenty samples with PCL-PDMS-PCL additive and seven samples
without PCL-PDMS-PCL additive, totally twenty seven poly(ethylene terephthalate)
(PET) foam samples were prepared with a chemical blowing agent and a
poly(dimethyl siloxane) additive. The polymer foams were produced by compression
molding, and they were structurally, morphologically, and mechanically
characterized, respectively. During the production of PET foams, hydraulic hot and
cold press instruments were used with respect to the compression molding process.

PET foam samples were produced based on process parameters that are processing
temperature, processing pressure and foaming time in the ranges of 255 - 275 oC, 10
- 100 bar, and 6 - 22 minutes, respectively. The amount of 5-PT additive as chemical
blowing agent was changed between 0.05 % and 0.25 % (wt) during the preparation
of PET foam mixtures. PCL-PDMS-PCL copolymer as surface modifying agent was
mixed with PET at low concentrations (0.050 % – 0.300 % by weight).

In the first stage of foaming process in hydraulic hot press, PET-additive mixture
was kept for a period of time at certain temperature and pressure. Melt form of PET
was obtained and PET foam samples were produced by decomposition of chemical
blowing agent. In the second stage, the foamed products were cooled in hydraulic
cold press under 50 bar pressure with constant cooling time of 5 minutes to produce
PET foams in amorphous structure with the help of rapid cooling.

The prepared closed cell PET foams were characterized morphologically, physically
and mechanically. The methods used in the characterization were given in ASTM
standards as ASTM D5946 and ASTM D5725 for contact angle measurements,
ASTM D1622-08 for foam density calculations, and ASTM D790-10 for three-point
bending mode flexural tests.

Each sample description refers to a specific composition involving the components

used in the preparation of the samples. An example of sample description is given
below:

71
Where CBA: Chemical blowing agent content (wt %), PDMS: PCL-PDMS-PCL
copolymer content (wt %), T: Processing Temperature in hot press (oC), t: Processing
time (min), P: Processing Pressure in hot press (bar).

Pre-works were done in order to determine the optimum compression molding

conditions in hydraulic hot and cold presses.

4.1 The Optimization of Processing Conditions

Optimization experiments for PET foaming were carried out by using different
temperatures, CBA and PDMS weight percentages, processing times and pressures to
determine optimum conditions in hydraulic hot press for compression molding
method. Homogeneous cell distribution was considered as a main driver for
determining of the optimization conditions during the investigation of polyester
foaming.

The weight optimization was one of the most challenging points. Decomposition of
5-PT at high temperatures generates nitrogen gase which causes volume expansion of
the system inside of the mold. The amount of PET should be determined according to
5-PT decomposition effect and the size of the mold. In ordered to define the right
amount of PET needs to be filled in the mold, several trials were performed. Finally,
the weight of PET was optimized as 35 grams.

The surface deformation of Teflon sheets were another issue needs to be optimized.
The quick closing of the hot press plates generates deformation on the Teflon sheets
closing the bottom and upper surfaces of the mold. To eliminate this negative effect
of the pressure on PET granules and having flat surfaces on the both end of the
product, several different types of Teflon sheets with different thicknesses were used.

72
In addition, Teflon material does not have enough heat conductivity. During the
initial experiments, 240 °C was used and it was not proper temperature. After having
several trials, the optimum process temperature was optimized as 260 °C and the
Teflon sheets thickness was selected as 1 mm to have flat surfaces and to provide
convenient heat conduction into the sample.

The process time period optimization was another major issue. After having melted
form of PET foam samples, a big cavity (center upwards) and a heterogeneous
bubble distribution were observed inside of the product. To eliminate these obstacles,
several different processing time periods were tried and finally, the process time
period was optimized as 10 minutes.

At high temperatures, because of its residues (aminodiphenyl-triazole; 3,5-diphenyl-

1,2,4-triazole; triphenyl-5-triazine), the chemical blowing agent, 5-PT, dark yellow
colour to products. At low temperatures, because of inhomogenious heating and
cooling period of the mold, mixed product structure morphology (crystallize and
amorphous structures) was occurred. PET melted in mold but pink colour on the
middle of the surfaces (up and down) of the product was observed. There were
unmelted PET granules in the inner center of the mold, however all outer surfaces
were in melted form. In the structure of the product, the bubbles were formed with
big cell sizes at higher temperatures and longer processing times.

Consequently, the optimized conditions were determined as 260 °C processing

temperature, under 15 bar pressure, 0.10 % CBA and 0.075 % PDMS with 10
minutes processing time in order to have homogeneous bubble size and distribution.

4.2 Density Analysis Results

4.2.1 Bulk density analysis results

The bulk density measurements of PET foam samples were done according to ASTM
D1622-08 standard. The measurement of dimensions of the samples to calculate their
volumes, a calliper compass was used. The mass of the samples was measured with
the laboratory balance. The bulk densities of the samples were calculated with the
mass of the sample divided by its volume.

73
The bulk density values of PET foam samples are changing between 0.945 g/cm3 and
1.190 g/cm3 with the average of +/- 0.06 standard deviation. These results show that
high density foams were obtained.

The bulk density is changed with the certain parameters. The bulk density of PET
foam samples were decreased with increasing processing time, increasing processing
temperature, decreasing processing pressure and increasing amount of chemical
blowing agent. The effect of foaming time on the bulk density of the PET foam
samples can be seen in Table 4.1.

Table 4.1 : The average cell diameter and the bulk density analysis results of PET
foam samples that are changing with processing time.

Time * Average cell diameter Bulk density

(min) (mm) (g/cm3)
6 0.24 1.165
10 0.27 1.115
12 0.36 1.100
14 0.39 0.990
22 0.44 0.945
* Constants: T = 260 °C, P =15 Bar, 5-PT = 0.10 %, PDMS = 0.075 %.

When the foaming time is more than 6 minutes, the bulk density decreases. This was
because the longer the gas was allowed to diffuse into the cells, the larger the cell
size was. When the foaming time increases, the average cell diameter also increases
(Figure 4.1).

Figure 4.1 : Time versus bulk density graph of PET foam samples.

74
4.2.2 Cell density analysis results

The process variables of gas saturation time, gas saturation pressure, foaming time,
and foaming temperature are important parameters for the explanation of cell
nucleations in polymer foams. In this study, one of the results is having the
transparent PET foam products with amorphous structure due to they were obtained
by rapid cooling of the mold of the foam in cold press instrument. This result is in
compliance with the result of the transparent foamed samples that are considered to
be amorphous if they have less than 10 % crystallinity by mass, and semicrystalline
if they have crystallinities greater than 10 %, when the crystallinities were measured
using differential scanning calorimeter (DSC) analysis with a heat of fusion of 125.6
J/g at a scan rate of 20 °C/min [8].

Cell density measurements were carried out with magnified photos of the PET foam
samples. Conversation factors that are used for the dimensional calculation of the
photos are from x and y scale (512 x 480) pixel to (5.883 x 5.506) mm are that x-
scale factor is 0.0114905, and y-scale factor is 0.0114714, which were used to
calculate the cell size and the cell density of the PET foam samples.

Cell density analysis graphs of PET foam samples are also presented on the basis
with 0.2 mm diameter range versus number of cells with the sample codes (Appendix
A.4).

Table 4.2 : The cell density and cell size dispersity ratio analysis of PET foam
samples.

Cell density Cell size dispersity

Sample ID
(cells/cm3) ratio (dv /dn)

CBA(0.10)-PDMS(0)-T(260)-t(10)-P(15) 4350 0.99

CBA(0.10)-PDMS(0.050)-T(260)-t(10)-P(15) 3280 1.03
CBA(0.10)-PDMS(0.075)-T(260)-t(10)-P(15) 3270 1.12
CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15) 2660 0.90
CBA(0.10)-PDMS(0.125)-T(260)-t(10)-P(15) 2640 1.02
CBA(0.10)-PDMS(0.150)-T(260)-t(10)-P(15) 2590 0.96
CBA(0.20)-PDMS(0)-T(260)-t(10)-P(15) 5960 0.96
CBA(0.20)-PDMS(0.075)-T(260)-t(10)-P(15) 3950 1.01
CBA(0.20)-PDMS(0.100)-T(260)-t(10)-P(15) 2930 0.92
CBA(0.20)-PDMS(0.200)-T(260)-t(10)-P(15) 2160 0.90
CBA(0.20)-PDMS(0.300)-T(260)-t(10)-P(15) 1820 0.91

75
Cell density analysis results were used to calculate the number average diameter and
the volume average diameters by using the equations 2.5 and 2.6 given in section
2.4.4, respectively. The cell density and the cell size dispersity ratio (dv / dn) of PET
foam samples were given in Table 4.2. The cell density analysis were resulted in
between 1740 cells/cm3 and 6220 cells/cm3 having +/-25 cells/cm3 deviations and,
these results prove that conventional foams, in which foam structures with a cell
density less than 106 cells/cm3, were produced.

The ratio of dv / dn represents a useful tool for evaluating cell size dispersity, similar
to the molecular weight polydispersity used in polymer chemistry to characterize
molecular weight distribution. The cell size dispersity ratios of PET foam samples
are calculated, and found to be between 0.90 and 1.12 (Table 4.2). When a cell size
dispersity ratio close to 1 (e.g., below 1.25) indicates a statistically normal
distribution or a monodisperse distribution.

Table 4.3 : The average cell size and density analysis results of cellular PET samples
changing with process variables in terms of temperature and 5-PT %
content.

Temperature * Avg. cell diameter Bulk density Cell density

(°C) (mm) (g/cm3) (cells/cm3)
250 0 1.310 0
260 0.27 1.115 3270
265 0.30 1.110 2440
270 0.37 1.050 2130
275 0.48 0.950 1740
* Constants: P = 15 Bar, t = 10 min, 5-PT = 0.10 %, PDMS = 0.075 %.

5-PT * Avg. cell diameter Bulk density Cell density

(%) (mm) (g/cm3) (cells/cm3)
0.05 0 1.310 0
0.10 0.27 1.115 3270
0.15 0.32 1.010 3310
0.20 0.46 0.965 3950
* Constants: T = 260 °C, P =15 Bar, t = 10 min, PDMS = 0.075 %.

76
 Figure 4.2 : Temperature versus cell density graph of PET foam samples.

The effect of foaming temperature on the mechanical properties occurred in the

temperature range between 250 and 275 °C, as shown in Figure 4.2. When the
foaming temperature was lower than 250 °C, there was no detectable cell structure.

One of the reasons was that the foaming reagent 5-PT could not decompose
completely at lower temperature; hence, there was probably not enough gas
necessary to form cellular PET.

Another reason was that at lower foaming temperatures, the PET matrix stiffness
might have been sufficiently large enough to prevent nucleated cells from growing to
detectable size, even though the allotted foaming time should have allowed all of the
available gas to diffuse into the cells.

Figure 4.3 : CBA percentage versus bulk density graph of PET foam
samples with 0.075 % PCL-PDMS-PCL.

77
The morphologies of the cells were strongly dependent on the foaming temperature,
solubilization pressure and chemical blowing agent content.

Table 4.4 : The average cell size and density analysis results of cellular PET samples
changing with process variable in terms of PCL-PDMS-PCL % content.

PDMS * Avg. cell diameter Bulk density Cell density

(%) (mm) (g/cm3) (cells/cm3)
0.050 0.25 1.120 3280
0.075 0.27 1.115 3270
0.100 0.28 1.100 2860
0.125 0.30 1.090 2640
0.150 0.32 0.965 2590
* Constants: T = 260 °C, P = 15 Bar, t = 10 min and 5-PT = 0.10 %

PDMS * Avg. cell diameter Bulk density Cell density

(%) (mm) (g/cm3) (cells/cm3)
0.100 0.32 1.070 2930
0.200 0.35 1.020 2160
0.300 0.38 0.980 1820
* Constants: T = 260 °C, P = 15 Bar, t = 10 min and 5-PT = 0.20 %

The experimental results of polycaprolactone block poly(dimethyl siloxane) (PCL-

PDMS-PCL) additive on rigid PET foams are presented in Table 4.4. It was observed
that when the PCL-PDMS-PCL additive was increased in the production of PET
foams, the average cell size of the PET foams were increased.

Figure 4.4 : PCL-PDMS-PCL weight percentage versus cell density

graph of PET foam samples.

78
 Table 4.5 : The average cell size and density analysis of PET foam samples
without PCL-PDMS-PCL additive content.

Pressure * Avg. cell diameter Bulk density Cell density

(Bar) (mm) (g/cm3) (cells/cm3)
10 0.29 1.165 2650
15 0.27 1.115 4350
20 0.21 1.095 4980
100 Vague cell structure 0.960 Vague cell structure
* Constants: T = 260 °C, t = 10 min and 5-PT = 0.10 %.

Avg. cell diameter Density Cell density

5-PT (%) *
(mm) (g/cm3) (cells/cm3)
0.10 0.18 1.110 4350
0.20 0.24 1.020 5960
0.25 0.27 0.965 6220
* Constants: T = 260 °C, P = 15 Bar, t = 10 min.

According to the Sanchez–Lacombe equation of state and experimental data from

Sato et al., the solubility of nitrogen in polymers increases linearly with pressure up
to about 25 MPa [16], [46]. Therefore, increasing foaming pressure actually
increased the foaming gas concentration inside of PET, and the net result was a cell-
size decrease (Table 4.5) and a cell density increase.

Figure 4.5 : Pressure versus cell density graph of PET foam samples.

Figure 4.5 shows the effect of foaming pressure on the mechanical properties of PET
foam samples. The tensile strength first increased and then decreased with increasing
foaming pressure, whereas the breaking extension increased all the way.

79
The larger the cell density was, the larger the breaking extension was. This explains
why the breaking extension increased with increasing foaming pressure under our
foaming pressure scope.

Figure 4.6 : CBA % versus cell density graph of PET foam samples.

We know that when the foaming pressure was smaller than 10 MPa, the PET sample
showed no detectable cell structure. This means that the foaming pressure should
exceed 10 MPa if one hopes to obtain microcellular PET foam.

4.3 Contact Angle Analysis Results

The contact angle measurements were done with CAM 200 KSV model Attension
THETA Optical Tensiometer.

The results are presented as right angle and left angle in Table 4.6 according to
whether its upper surface or lower surface.

Due to their outstanding properties, polysiloxanes have low surface energy (i.e. high
surface activity), low glass transition temperature, high chain flexibility, and thermal
and UV stability). These properties lead to the thermodynamic incompatibility of
polysiloxanes with almost all other organic polymers. Using poly(dimethylsiloxane)
(PDMS) copolymer systems overcome their incompatibility. In siloxane containing
copolymers, siloxane segments migrate to the air-polymer surface, whilst the organic
segments in the copolymer act as anchoring groups for the siloxane blocks, which
can result in permanent surface modifications being achieved. The effects of

80
polycaprolactone block poly(dimethyl siloxane) (PCL-PDMS-PCL) additive content
on rigid PET foams were investigated mainly. In Table 4.6, there is an increase in
contact angle values with increase of PCL-PDMS-PCL percentage because of the
migration of PCL-PDMS-PCL molecules to air-polymer surface in PET foam
samples.

Considering PET foam samples, the cell densities change with PCL-PDMS-PCL
weight percentages which is given in Figure 4.4. PCL-PDMS-PCL addition to the
PET foam samples gave increased toughness and better surface properties than those
of the PET foam samples without PCL-PDMS-PCL additive under the same
conditions. The brittleness of the PET foams was also decreased although PCL-
PDMS-PCL was added at very low weight percentages during the preparation of the
PET foam mixture.

Table 4.6 : Contact Angle measurement results of PET foam samples with the
average of +/- 0.19 standard deviation.

Contact Angle (°)

Surface (Up) Surface (Down)

Sample ID 0 (sec) 20 (sec)
0 (sec) 20 (sec)

R.A.* L.A.** R.A. L.A. R.A. L.A. R.A. L.A.

CBA(0.10)-PDMS(0)-
93.4 93.0 87.7 88.8 80.3 80.5 74.4 74.8
T(265)-t(10)-P(15)
CBA(0.20)-PDMS(0)-
92.9 92.2 75.6 74.5 84.1 82.4 60.5 60.2
T(265)-t(10)-P(15)
CBA(0.10)-PDMS(0.050)-
95.6 94.7 84.5 85.5 91.4 93.7 89.3 89.4
T(260)-t(10)-P(15)
CBA(0.10)-PDMS(0.075)-
96.2 96.7 92.7 92.5 90.4 90.6 88.0 87.3
T(260)-t(10)-P(15)
CBA(0.10)-PDMS(0.100)-
96.8 97.2 91.8 92.3 95.8 94.6 83.7 84.9
T(260)-t(10)-P(15)
CBA(0.10)-PDMS(0.125)-
99.7 99.9 93.7 95.3 96.9 96.2 85.9 86.8
T(260)-t(10)-P(15)
CBA(0.10)-PDMS(0.150)-
97.3 96.1 92.3 92.0 88.1 87.2 86.4 86.3
T(275)-t(10)-P(15)
CBA(0.20)-PDMS(0.200)-
102.2 100.5 97.0 97.0 99.4 96.7 90.2 90.3
T(265)-t(10)-P(15)
CBA(0.20)-PDMS(0.300)-
107.4 106.6 99.8 100.4 98.03 98.9 91.4 92.3
T(265)-t(10)-P(15)
*
: R.A. = right angle, **: L.A. = left angle.

81
The experimental results show that the elastic modulus of PET foam increased as
PCL-PDMS-PCL additive increased. Besides, as the foam density increased the
elasticity of the foam was also increased. In general, crystallized products are more
brittle than amorphous products. PCL-PDMS-PCL addition to the PET foam samples
gave increased toughness and better surface properties than those of the PET foam
samples without PCL-PDMS-PCL additive under the same conditions. The weight
reduction of PET was achieved without sacrificing much of the mechanical
properties by introducing cellular structure in thermoplastic materials. It was
observed that the elastic modulus increased nonlinearly as the relative foam density
and PCL-PDMS-PCL additive content increased.

There is an increase in contact angle measurement results with certain amount of

PDMS percentage increasement because of the migration of PDMS molecules to air-
polymer surface in PET foam samples. According to the calculated results, for the
samples, which do not include PCL-PDMS-PCL, showed decrease in elongation at
break. It was observed that when the PCL-PDMS-PCL additive content was
increased, the elastic modulus of PET foams increased, and the elastic modulus was
also increased as the relative foam density was increased.

4.4 Three-Point Bending Mode Flexural Test Results

To obtain flexural properties of polyester foams, mechanical test was made by using
Zwick Roell ProLine testing machine. Because the effects of PCL-PDMS-PCL
additive give remarkable results in three-point bending mode flexural test, this test
was applied to PET foam samples with the reference of ASTM D790-10 and ISO
178 standards. Elastic modulus, yield strength, tensile strength, breaking strength,
strain of break, and toughness at break of PET foam samples were obtained from the
four (4) samples averaged. The calculated results were given in Table 4.7. According
to these values, for the samples which do not include PDMS, decrease in elongation
at break.

When the foaming time was more than 6 minutes, the tensile strength and elongation
at break of cellular PET started to decrease. This was because the longer the gas was
allowed to diffuse into the cells, the larger the cell size was. Therefore, the larger cell
size (larger to some extent) decreased the tensile strength and breaking extension. In
contrast to Baldwin et al. who found that the foaming time had a relatively weak

82
influence on cell nucleation and cell growth for the amorphous and semicrystalline
polyester because the gas in their samples was constant (meaning there was no effect
on the mechanical properties), the foaming time in our experiment did have effects
on the mechanical properties.

Table 4.7 : Three-point bending mechanical test results of PET foam samples with
the average of +/- 0.09 standard deviation.
Elastic Yield Tensile
Sample ID Modulus Strength Strength
(MPa) (MPa) (MPa)
CBA(0.10)-PDMS(0)-T(265)-t(10)-P(15) 2240 70.5 112.0
CBA(0.10)-PDMS(0.050)-T(260)-t(10)-P(15) 2370 76.2 116.4
CBA(0.10)-PDMS(0.075)-T(260)-t(10)-P(15) 2390 70.6 85.2
CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15) 2560 77.1 102.1
CBA(0.10)-PDMS(0.125)-T(260)-t(10)-P(15) 2720 83.4 106.6
CBA(0.10)-PDMS(0.150)-T(265)-t(10)-P(15) 2830 79.5 79.7
CBA(0.20)-PDMS(0)-T(265)-t(10)-P(15) 2070 73.9 106.4
CBA(0.20)-PDMS(0.100)-T(260)-t(10)-P(15) 2140 70.5 75.1
CBA(0.20)-PDMS(0.200)-T(260)-t(10)-P(15) 2500 78.2 101.2
CBA(0.20)-PDMS(0.300)-T(260)-t(10)-P(15) 2890 86.3 106.0

Tensile Breaking Breaking

Sample ID Deflection Strength Deflect.
(mm) (MPa) (mm)
CBA(0.10)-PDMS(0)-T(265)-t(10)-P(15) 10.0 - -
CBA(0.10)-PDMS(0.050)-T(260)-t(10)-P(15) 8.6 - -
CBA(0.10)-PDMS(0.075)-T(260)-t(10)-P(15) 5.5 - -
CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15) 7.0 - -
CBA(0.10)-PDMS(0.125)-T(260)-t(10)-P(15) 6.6 104.0 6.0
CBA(0.10)-PDMS(0.150)-T(265)-t(10)-P(15) 3.5 81.6 4.4
CBA(0.20)-PDMS(0)-T(265)-t(10)-P(15) 8.1 - -
CBA(0.20)-PDMS(0.100)-T(260)-t(10)-P(15) 4.0 64.4 4.7
CBA(0.20)-PDMS(0.200)-T(260)-t(10)-P(15) 6.6 118.0 7.6
CBA(0.20)-PDMS(0.300)-T(260)-t(10)-P(15) 6.2 - -

It was observed that the elastic modulus increased as the relative foam density
increased (Figure 4.7), and when the PDMS additive content increased (Figure 4.8)
the elastic modulus is also increased. The optimum value of the PDMS additive
content is 0.075 %.

Moreover, the mechanical properties of polyester foam samples were increased by

adding PCL-PDMS-PCL additive. Besides, it was observed that crystallized products

83
(produced with slow cooling of the product to room temperature instead of rapid
cooling of the product in cold press) of the PET foam samples are more brittle than
amorphous products.

Figure 4.7 : Bulk density versus elastic modulus graph of PET

foam samples with 0.075 % PCL-PDMS-PCL.

Figure 4.8 : PCL-PDMS-PCL % versus elastic modulus graph of

PET foam samples.

Because of good homogeneous dispersion of CBA in polymer matrix, the mechanical

properties resulted in meaningful values.

When the three-point bending mode flexural test results of PET foam samples are
considered, CBA(0.20)-PDMS(0.300)-T(260)-t(10)-P(15) foam sample indicated the
best mechanical properties among others due to its high elastic modulus value and its
highest PCL-PDMS-PCL content.

84
5. CONCLUSION

In this study, closed cell PET foams were produced by compression molding
technique. The effects of altering processing parameters and PCL-PDMS-PCL
addition of PET foams were investigated with measurements of density, contact
angle, cell density measurements and three-point bending mode flexural tests after
the optimization trials for the production of a homogeneous foam was achieved.

The foaming of thermoplastic polymer was achieved by using a chemical blowing

agent in compression molding process. Compression molding provided a convenient
method for quick evaluation of material formulations instead of material intensive
extrusion processing.

Poly(ethylene terephthalate), as one of the high-temperature-foaming polymers

among other thermoplastic polymers, was foamed with an exothermic type of
chemical blowing agent that is 5-phenyl-1H-tetrazole (5-PT).

The experimental results showed that the elastic modulus of PET foam increased
with the addition of PCL-PDMS-PCL additive. Moreover, the elastic modulus of
foam increased also with increasing foam density. In general, crystalline products are
more brittle than amorphous products. PCL-PDMS-PCL addition to the foamed PET
samples gave increased toughness and better surface properties than those of the
foamed PET samples without PCL-PDMS-PCL additive under the same conditions.
The weight reduction of PET was achieved without sacrificing much of the
mechanical properties by introducing cellular structure in thermoplastic materials. It
was observed that the elastic modulus increased nonlinearly as the relative foam
density and PCL-PDMS-PCL additive content increased.

Polymer foams were prepared by using hydraulic hot press with the processing
temperatures ranging from 250 to 275 oC and pressures ranging from 10 to 100 bars.
The process time for foaming was about 6 to 14 minutes. Although the content of the
chemical blowing agent was kept constant as 0.10 % and 0.20 % in PET foam
samples. 0.10 % CBA content gave the best results in terms of homogeneous cell

85
distribution and cell density. The PCL-PDMS-PCL was added in between 0.050 %
and 0.300 % (wt %).

PET foam samples were prepared by compression molding technique in hot and cold
presses in optimum conditions at 260 °C processing temperature, under 15 bar
pressure, by adding 0.10 % CBA and 0.075 % PCL-PDMS-PCL with a processing
time of 10 minutes. The 27 samples prepared and investigated from structural,
morphological, mechanical and processing points of view. The contact angle
measurements, density calculations, cell size analysis and three-point bending mode
flexural tests were performed on the PET foam samples.

When the foaming time was more than 6 minutes, the tensile strength and elongation
at break values of cellular PET started to decrease. When the foaming time was
increased as long as possible, the gas diffused into the cells easily, so the cell size got
larger. Therefore, the larger cell size (larger to some extent) decreased the tensile
strength and elongation at break. The foaming time had a relatively strong influence
on cell nucleation and cell growth for the amorphous and semicrystalline polyesters.
Similar strong cell-size dependence on foaming time was reported for styrenic resins
[123].

The solubility of nitrogen in polymers was increased linearly with pressure.

Therefore, increasing foaming pressure actually increased the foaming gas
concentration inside the PET. Due to this increment, cell-sizes decreased and cell
densities increased. These results enhanced the elongation at break (εb %) values.
This explains why the elongation at break increased with increasing foaming
pressure under our foaming pressure scope. When the foaming pressure was lower
than 10 MPa, the PET sample showed no detectable cell structure. This means that
the foaming pressure should exceed 10 MPa if one hopes to obtain microcellular PET
foam.

The effect of foaming temperature on the mechanical properties occurred in the

temperature range between 250 and 275 °C. When the foaming temperature was
lower than 250 °C, there was no detectable cell structure. The chosen foaming
reagent 5-PT could not decompose completely at lower temperature; hence, there
was probably inadequate gas necessary to form cellular PET. On the other hand, this
temperature was low for PET foaming production. The PET matrix stiffness might

86
have been sufficiently large enough to prevent nucleated cells from growing to
detectable size, even though the allotted foaming time should have allowed all of the
available gas to diffuse into the cells.

The cell density analysis results are found between 1740 cells/cm3 and 6220
cells/cm3, and these results proved that conventional foams, in which foam structures
having cell densities less than 106 cells/cm3, were produced.

The ratio of dv / dn represents a useful tool for evaluating cell size dispersity. A cell
size dispersity ratio close to 1 (e.g., below 1.25) indicates a statistically normal
distribution or a monodisperse distribution. The cell size dispersity ratios of PET
foam samples were calculated, and found to be in between 0.90 and 1.12,
accordingly.

High-density polymer foams with good mechanical properties were produced as the
bulk density values are in between 0.945 g/cm3 and 1.190 g/cm3. These results show
that high-density foams were formed.

The effects of polycaprolactone block poly(dimethyl siloxane) (PCL-PDMS-PCL)

additive content on rigid PET foams were also investigated. There is an increasing
trend in contact angle measurements with PDMS addition, due to the migration of
PDMS segments to air-polymer surface in PET foam samples. According to the
calculated results, the PCL-PDMS-PCL containing samples showed an increase in
elongation at break with a decrease in brittleness. It was observed that the elastic
modulus of PET foams increased with the PCL-PDMS-PCL addition.

87
88
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98
APPENDICES

APPENDIX A.1 : Exothermic Blowing Agents

APPENDIX A.2 : Properties of PET

APPENDIX A.3 : Bubble Analysis Photos of PET Foam Samples

APPENDIX A.4 : Cell Density Analysis Graphs of PET Foam Samples

APPENDIX A.5 : Water Contact Angle Measurement Photos of PET Foam Samples

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 APPENDIX A.1

Table A.1 : Processing Conditions for Common Exothermic Blowing Agents [57].
Gas
Solid Yield Decomp.
Chemical Gas
Grade Decomp. (cc Temperature
Compound composition
Product gas at Range (°C)
STP)
AZ Azodicarbonamide N2 65% Urazol 220 205 - 215
CO 24% Biurea
CO2 5% Cyamelide
Cyanuric
NH3 5%
Acid
p-Toluene sulfonyl Ditolyl
RA N2 55% 140 228 - 235
semicarbazide disulfide
Ammonium
CO2 37% p-toluene
sulfonate
NH3 3%
CO 2%
p,p'-Oxybis Nonpolar
OT (benzenesulfonyl N2 91% aromatic 125 158 - 160
hydrazide) sulfur-
containing
H2O 9%
polymer
p-Toluene sulfonyl Ditolyl
TSH N2 n/a 115 10 - 120
hydrazide disulfide
p-Tolyl-p-
H2O n/a toluene
thiosulfinate
p-
Toluenesulfin
ic acid
hydrazine
p-
Toluenesulfo
nyl hydrazide
salt
of p-toluene-
sulfonic acid

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APPENDIX A.2

Table A.2 : Properties of PET

PROPERTY PET DATA

Molecular formula (C10H8O4)n

Density amorphous 1.370 g/cm3
Density crystalline 1.455 g/cm3
Young's modulus (E) 2800–3100 MPa
Tensile strength(σt) 55–75 MPa
Elastic limit 50–150%
Notch test 3.6 kJ/m2
Glass temperature 75 °C
Melting point 260 °C
Vicat B 170 °C
Thermal conductivity 0.24 W/(m•K)
Linear expansion coefficient (α) 7×10−5/K
Specific heat (c) 1.0 kJ/(kg•K)
Water absorption (ASTM) 0.16
Refractive Index 1.575
Price 0.5–1.25 €/kg

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APPENDIX A.3

(a) (b)

(c) (d)

(e) (f)
Figure A.3 : Bubble Analysis Photos of PET Foam Samples:
(a)CBA(0.20)-PDMS(0)-T(260)-t(10)-P(15).
(b)CBA(0.10)-PDMS(0)-T(260)-t(10)-P(15).
(c)CBA(0.10)-PDMS(0)-T(260)-t(10)-P(10).
(d)CBA(0.20)-PDMS(0)-T(260)-t(10)-P(10).
(e)CBA(0.15)-PDMS(0.150)-T(260)-t(10)-P(15).
(f)CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15).

102
 (g) (h)

(i) (j)

(k) (l)
Figure A.3 (contd.) : Bubble Analysis Photos of PET Foam Samples:
(g)CBA(0.20)-PDMS(0.200)-T(265)-t(10)-P(15).
(h)CBA(0.20)-PDMS(0.200)-T(260)-t(10)-P(20).
(i)CBA(0.20)-PDMS(0.100)-T(260)-t(10)-P(20).
(j)CBA(0.20)-PDMS(0.300)-T(260)-t(10)-P(15).
(k)CBA(0.10)-PDMS(0.050)-T(260)-t(10)-P(15).
(l)CBA(0.10)-PDMS(0.050)-T(260)-t(22)-P(15).

103
 (m) (n)

(o) (p)

(r) (s)
Figure A.3 (contd.) : Bubble Analysis Photos of PET Foam Samples:
(m)CBA(0.10)-PDMS(0.075)-T(260)-t(10)-P(15).
(n)CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15).
(o)CBA(0.10)-PDMS(0.125)-T(260)-t(10)-P(15).
(p)CBA(0.10)-PDMS(0.150)-T(260)-t(10)-P(15).
(r)CBA(0.20)-PDMS(0)-T(260)-t(10)-P(15).
(s)CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15).

104
APPENDIX A.4

(a) (b)

(c) (d)

(e) (f)

Figure A.4 : Cell density analysis graphs presented on the basis with 0.2 mm
diameter range versus number of cells:
(a)CBA(0.20)-PDMS(0)-T(260)-t(10)-P(15).
(b)CBA(0.10)-PDMS(0)-T(260)-t(10)-P(15).
(c)CBA(0.10)-PDMS(0)-T(260)-t(10)-P(10).
(d)CBA(0.20)-PDMS(0)-T(260)-t(10)-P(10).
(e)CBA(0.15)-PDMS(0.150)-T(260)-t(10)-P(15).
(f)CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15).

105
 (g) (h)

(i) (j)

(k) (l)

Figure A.4 (contd.) : Cell density analysis graphs presented on the basis with 0.2
mm diameter range versus number of cells:
(g)CBA(0.20)-PDMS(0.200)-T(260)-t(10)-P(15).
(h)CBA(0.20)-PDMS(0.200)-T(260)-t(10)-P(20).
(i)CBA(0.20)-PDMS(0.100)-T(260)-t(10)-P(20).
(j)CBA(0.20)-PDMS(0.300)-T(260)-t(10)-P(20).
(k)CBA(0.10)-PDMS(0.050)-T(260)-t(10)-P(15).
(l)CBA(0.10)-PDMS(0.050)-T(260)-t(22)-P(15).

106
 (m) (n)

(o) (p)

Figure A.4 (contd.) : Cell density analysis graphs presented on the basis with 0.2
mm diameter range versus number of cells:
(m)CBA(0.10)-PDMS(0.075)-T(260)-t(10)-P(15).
(n)CBA(0.10)-PDMS(0.100)-T(260)-t(10)-P(15).
(o)CBA(0.10)-PDMS(0.125)-T(260)-t(10)-P(15).
(p)CBA(0.10)-PDMS(0.150)-T(275)-t(10)-P(15).

107
APPENDIX A.5

(a) (b)

(c) (d)

(e) (f)

Figure A.5 : Water contact angle measurement photos of PET foam samples:
(a)Upper surface of CBA(0.20)-PDMS(0)-T(265)-t(10)-P(15) initially.
(b)Upper surface of CBA(0.20)-PDMS(0)-T(265)-t(10)-P(15) finally.
(c)Down surface of CBA(0.20)-PDMS(0)-T(265)-t(10)-P(15) initially.
(d)Down surface of CBA(0.20)-PDMS(0)-T(265)-t(10)-P(15) finally.
(e)Upper surface of CBA(0.20)-PDMS(0.200)-T(265)-t(10)-P(15).
(f)Down surface of CBA(0.20)-PDMS(0.200)-T(265)-t(10)-P(15).

108
CURRICULUM VITAE

Name Surname: Hatice Bilge ÇEBİŞLİ

Place and Date of Birth: Bucak – 29.09.1984

Address: Icerenkoy Mah. Eski Uskudar Yolu

Topcu Ibrahim Sok. No:11/11 Atasehir- Istanbul/ TURKEY

E-Mail: [email protected]

B.Sc.: Chemistry, Izmir Institute of Technology, Science Faculty, Izmir, Turkey

B.Sc Graduation Project: Synthesis & Biological Activities of Flavanone - Stilbene

Complex Derivative (New anti-cancer drug candidate,
molecule design study in organic chemistry, Flavanones,
Chalcones).

Professional Experience: 2010: Technical Specialist (Plastics) in PAGEV.

2011: Project Manager in ASES Aviation.

POSTER PRESENTATION ON THE THESIS

Çebişli H.B., Yalçınyuva T., Uyanık N., 2011: Production & Characterization of
Modified PET Foam. International Congress - Eurofillers 2011, August 21-26, 2011
Dresden, Germany.

109