Cătălin CROITORU

E-mail: [email protected]
Office: Colina UnitBv, room GI23
 Ceramic materials
• Inorganic compounds consisting of a metal (or semi-metal) and one or more
nonmetals
• Examples:
• Silica - silicon dioxide (SiO2), the main ingredient in most glass products
• Alumina - aluminum oxide (Al2O3), used in various applications from abrasives to artificial bones
• More complex compounds such as hydrous aluminum silicate (Al2Si2O5(OH)4), called kaolinite,
the main ingredient in most clay products

Properties of Ceramic Materials

• High hardness, electrically and thermally insulating, chemically stable, and high
melting temperatures
• Brittle, virtually no ductility - can cause problems in both processing and performance
of ceramic products
• Some ceramics are translucent, window glass (based on silica) being the clearest
example
 Ceramic Materials

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics

-optical -whiteware -bricks for -sandpaper -composites -engine

-composite -structural high T -cutting -structural rotors
reinforce (furnaces) -polishing valves
-containers/ bearings
household -sensors
 Ceramic Products
• Clay construction products - bricks, clay pipe, and building tile
• Refractory ceramics - capable of high temperature applications such as furnace walls, crucibles,
and molds
• Cement in concrete - used for construction and roads
• Whiteware products - pottery, stoneware, fine china, porcelain, and other tableware, based on
mixtures of clay and other minerals
• Glass - bottles, glasses, lenses, window pane, and light bulbs
• Glass fibers - thermal insulating wool, reinforced plastics (fiberglass), and fiber optics
communications lines
• Abrasives - aluminum oxide and silicon carbide in grinding wheels
• Cutting tool materials - tungsten carbide, aluminum oxide, and cubic boron nitride
• Ceramic insulators - applications include electrical transmission components, spark plugs, and
microelectronic chip substrates
• Magnetic ceramics – computer memories
• Nuclear fuels based on uranium oxide (UO2)
• Bioceramics - artificial teeth and bones
Three Basic Categories of Ceramics
1. Traditional ceramics - clay products such as pottery, bricks, common
abrasives, and cement
2. New ceramics - more recently developed ceramics based on oxides,
carbides, etc., with better mechanical and/or physical properties than
traditional ceramics
3. Glasses - based primarily on silica and distinguished by their noncrystalline
structure and transparency
 Strength Properties of Ceramics
• Theoretically, the strength of ceramics should be higher than metals because
their covalent and ionic bonding types are stronger than metallic bonding
• But metallic bonding allows for slip, the mechanism by which metals
deform plastically when stressed
• Bonding in ceramics is more rigid and does not permit slip under stress
• The inability to slip makes it much more difficult for ceramics to absorb stresses
• The frailties that limit the tensile strength of ceramics are not nearly so
operative when compressive stresses are applied
• Ceramics are substantially stronger in compression than in tension
• For engineering and structural applications, designers have learned to use
ceramic components so that they are loaded in compression rather than
tension or bending
Physical Properties of Ceramics
• Density – most ceramics are lighter than metals but heavier than
polymers
• Melting temperatures - higher than for most metals
• Some ceramics decompose rather than melt
• Electrical and thermal conductivities - lower than for metals; but the
range of values is greater, so some ceramics are insulators while others
are conductors
• Thermal expansion - somewhat less than for metals, but effects are
more damaging because of brittleness
 Traditional Ceramics
• Based on mineral silicates, silica, and mineral oxides found in nature
• Glass is also a silicate and is sometimes included among the traditional ceramics
• Primary products are fired clay (pottery, tableware, brick, and tile), cement,
and natural abrasives such as alumina
• Products and the processes to make them date back thousands of years
Raw Materials for Traditional Ceramics

Mineral silicates, such as clays and silica, are among the most abundant substances in
nature and are the principal raw materials for traditional ceramics
Another important raw material for traditional ceramics is alumina
These solid crystalline compounds have been formed and mixed in the earth’s crust over
billions of years by complex geological processes
Clay as a Ceramic Raw Material

• Clays consist of fine particles of hydrous aluminum silicate

• Mostly based on kaolinite, (Al2Si2O5(OH)4) – white when pure, reddish-brown
when impurified with iron oxides
• Mixed with water, clay becomes a plastic substance that is formable and
moldable
• When heated to a sufficiently elevated temperature (firing), clay fuses
into a dense, strong material
• Thus, clay can be shaped while wet and soft, and then fired to obtain the final
hard product
Silica as a Ceramic Raw Material
• Available naturally in various forms, most important is quartz (SiO2)
• Main source of quartz is sandstone
• Low cost
• Hard and chemically stable
• Principal component in glass, and an important ingredient in other
ceramic products including whiteware, refractories, and abrasives
Alumina as a Ceramic Raw Material
• Bauxite - most alumina is processed from this mineral, which is an
impure mixture of hydrous aluminum oxide (Al2O3) and aluminum
hydroxide (Al(OH)3) plus similar compounds of Fe or Mn
• Bauxite is also the principal source of aluminum
• Corundum - a more pure but less common form of Al2O3, which
contains alumina in massive amounts
• Alumina ceramic is used as an abrasive in grinding wheels and as a
refractory brick in furnaces
New Ceramics
• Ceramic materials developed synthetically over recent decades
• Also refers to improvements in processing techniques that provide greater
control over structures and properties of ceramic materials
• New ceramics are based on compounds other than variations of aluminum
silicate
• New ceramics are usually simpler chemically than traditional ceramics; for
example, oxides, carbides, nitrides, and borides
 Oxide Ceramics
• Most important oxide ceramic is alumina Al2O3
• Although included among traditional ceramics, alumina is also produced
synthetically from bauxite
• Through control of particle size and impurities, refinements in processing
methods, and blending with small amounts of other ceramic ingredients,
strength and toughness of alumina are improved substantially compared to
its natural counterpart
• Alumina also has good hot hardness, low thermal conductivity, and good
corrosion resistance
Products of Oxide Ceramics
• Abrasives (grinding wheel grit)
• Bioceramics (artificial bones and teeth)
• Electrical insulators and electronic components
• Refractory brick
• Cutting tool inserts
• Spark plug barrels
• Engineering components

White parts are Al2O3

Black parts are SiC and Si3N4
Carbide Ceramics

• Includes silicon carbide (SiC), tungsten carbide (WC), titanium carbide

(TiC), tantalum carbide (TaC), and chromium carbide (Cr3C2)
• Production of SiC dates from a century ago, and it is generally included
among traditional ceramics
• WC, TiC, and TaC are hard and wear resistant and are used in
applications such as cutting tools
• WC, TiC, and TaC must be combined with a metallic binder such as cobalt or
nickel in order to fabricate a useful solid product
 Nitrides

• Important nitride ceramics are silicon nitride (Si3N4), boron nitride

(BN), and titanium nitride (TiN)
• Properties: hard, brittle, high melting temperatures, usually electrically
insulating, TiN being an exception
• Applications:
• Silicon nitride: components for gas turbines, rocket engines, and melting
crucibles
• Boron nitride and titanium nitride: cutting tool materials and coatings
 Glass
• A state of matter (amorphous) as well as a type of ceramic
• As a state of matter, glass refers to an amorphous (noncrystalline)
structure of a solid material
• The glassy state occurs when insufficient time is allowed during
cooling from the molten state to form a crystalline structure
• As a type of ceramic, glass is an inorganic, nonmetallic compound (or
mixture of compounds) that cools to a rigid condition without
crystallizing
 Why So Much SiO2 in Glass?
• Because SiO2 is the best glass former
• Silica is the main component in glass products, usually comprising 50% to 75% of
total chemistry
• It naturally transforms into a glassy state upon cooling from the liquid, whereas most
ceramics crystallize upon solidification

Other Ingredients in Glass

• Sodium oxide (Na2O)
• Calcium oxide (CaO)
• Aluminum oxide (Al2O3)
• Magnesium oxide (MgO)
• Potassium oxide (K2O)
• Lead oxide (PbO)
• Boron oxide (B2O3)
Glass Products
• Window glass
• Containers – cups, jars, bottles
• Light bulbs
• Laboratory glassware – flasks, beakers, glass tubing
• Glass fibers – insulation, fiber optics
• Optical glasses – lenses
• Gorilla glass – cover glass in smart phones and TV screens
Glass-Ceramics

• A ceramic material produced by conversion of glass into a

polycrystalline structure through heat treatment
• Proportion of crystalline phase = 90% to 98%, remainder vitreous
(glassy) material
• Grain size significantly smaller than conventional ceramics, which
makes glass-ceramics much stronger than the glasses from which they’re
made
• Due to crystal structure, glass-ceramics are opaque (usually grey or
white), not clear
Vitroceramic products
Processing of Glass Ceramics

• Heating and forming techniques used in glassworking create

product shape
• Product is cooled and then reheated to cause a dense network
of crystal nuclei to form throughout
• Nucleation results from small amounts of nucleating agents, such
as TiO2, P2O5, and ZrO2
• Once nucleation is started, heat treatment is continued at a higher
temperature to cause growth of crystalline phases
Elements Related to Ceramics
• Carbon
• Two alternative forms of engineering and commercial importance: graphite
and diamond
• Silicon and Boron
• Carbon, silicon, and boron are not ceramic materials, but they
sometimes
• Compete for applications with ceramics
• Have important applications of their own
Graphite

• Form of carbon with a high content of crystalline carbon in

the form of layers
• Bonding between atoms in layers is covalent and strong, but
parallel layers are bonded to each other by weak van der Waals
forces
• Structure makes graphite properties anisotropic
• As a powder it is a lubricant, but in traditional solid form it is a
refractory
• As a fiber, it is a high strength structural material (e.g., fiber reinforced
plastics)
Diamond

• Carbon with a cubic crystalline structure with covalent bonding

between atoms for high hardness
• Applications: cutting tools and grinding wheels for machining hard,
brittle materials or materials that are very abrasive; also used in
dressing tools to sharpen grinding wheels that consist of other
abrasives
• Synthetic diamonds date back to 1950s
• Fabricated by heating graphite to around 3000C under very high
pressures
Silicon

• Semi-metallic element in the same periodic table group as carbon

• One of the most abundant elements in Earth's crust, comprising 
26% by weight
• Occurs naturally only as chemical compound - in rocks, sand, clay,
and soil - either as silicon dioxide or as more complex silicate
compounds
• Properties: hard, brittle, lightweight, chemically inactive at room
temperature, and classified as a semiconductor
Applications and Importance of Silicon
• Greatest use in manufacturing are as ceramics (SiO2 in glass and
silicates in clays) and alloying elements in steel, cast iron, aluminum,
and copper
• Pure silicon is of significant technological importance as the base
material in semiconductor manufacturing in electronics
• The vast majority of integrated circuits produced today are made
from silicon
 Boron
• Semi-metallic element in same periodic group as aluminum
• Comprises only about 0.001% of Earth's crust by weight, commonly
occurring as minerals borax (Na2B4O7-10H2O) and kernite
(Na2B4O7-4H2O)
• Properties: lightweight, semiconducting properties, and very stiff (high
modulus of elasticity) in fiber form
• Applications: B2O3 in certain glasses, as a nitride (cBN) for cutting
tools, and in nearly pure form as a fiber in polymer matrix composites
Characteristics of Ceramics Processing
Steps in Making Ceramic Parts
Slip-casting a Ceramic Part

Sequence of operations in slip-

casting a ceramic part. After the
slip has been poured, the part is
dried and fired in an oven to give
it strength and hardness.
Shrinkage of Wet Clay

Shrinkage of wet clay caused by the removal of water during drying. Shrinkage may be as
much as 20% by volume.
Float Method

The float method of forming sheet glass

Drawing Process and Rolling Process

(a) Drawing process for drawing sheet glass from a molten bath. (b) Rolling process.
 Glass Tubing Manufacturing

Manufacturing process for glass tubing. Air is blown through the mandrel to keep the tube
from collapsing. Glass tubes for fluorescent light bulbs are made by this method.
Steps in Manufacturing Glass Bottles

Stages in manufacturing an ordinary glass bottle

Manufacturing Glass by Casting

Manufacturing a glass item by pressing glass into a mold.

Centrifugal casting of glass. Large

telescope lenses and television-tubes are
Pressing glass into a split mold made by this process
 Heat Treatment: Annealing of Glass
▪ Heating to elevated temperature and holding to eliminate stresses and temperature gradients;
then slow cooling to suppress stress formation, then more rapid cooling to room temperature
▪ Annealing temperatures ~ 500C
▪ Same function as in metalworking: stress relief
▪ Annealing is performed in tunnel-like furnaces, called lehrs, in which products move
slowly through the hot chamber on conveyors

Tempering of Glass
▪ Heating to a temperature somewhat above annealing temperature into the plastic range, followed
by quenching of surfaces, usually by air jets
▪ Surfaces cool and harden while interior is still plastic
▪ As the internal glass cools, it contracts, putting the hard surfaces in compression
▪ Tempered glass is more resistant to scratching and breaking due to compressive stresses on its
surfaces
▪ Products: windows for tall buildings, all-glass doors, safety glasses
Case Study: Automobile Windshields
▪ When tempered glass fails, it shatters into many small fragments
▪ Automobile windshields are not made of tempered glass, due to the
danger posed by this fragmentation
▪ Instead, conventional glass is used; it is fabricated by sandwiching
two pieces of glass on either side of a tough polymer sheet
▪ Should this laminated glass fracture, the glass splinters are retained
by the polymer sheet and the windshield remains relatively
transparent
Residual Stresses in Tempered-Glass Plate

-- Result: surface crack growth is suppressed.

Residual stresses in tempered-glass plate, and the stages involved in inducing

compressive surface residual stresses for improved strength.
• Heat-strengthened glass is typically used when additional strength is
needed to resist wind pressure, thermal stress or both. Another
advantage of heat-strengthened glass is that when broken, the glass
fragments have more rounded (less sharp) corners. Although heat-
strengthened glass is NOT shatter-proof, this breakage pattern prevents
the glass from falling and injuring someone.

Non heat-treated glass vs. treated glass

Ion-Exchange Process
▪ Starting material: thin sheets of aluminosilicate glass
containing significant amounts of sodium oxide (Na2O)
▪ Sheets are immersed in a hot potassium (K) salt bath at
~400C
▪ Na ions in sheet surfaces are replaced by K ions in bath
▪ K ions are larger than Na ions and take up a greater volume to
create a state of compression in the surface as the glass cools,
making the surface resistant to damage (similar effect as
tempered glass).
▪ Through this ion-exchange process the so-called gorilla glass
is obtained (hard, scratch- and crack-resistant)