Ceramics and Glasses 3rd Year - Lecture Notes

Ceramics and Glasses 3rd year Lecture notes
Farid 2014-2015
Course 1:
1. Introduction to Ceramics
2. Elementary Crystallography
3. Ceramic Microstructures
4. Traditional vs. advanced Ceramics
5. General Characteristics of Ceramics
6. Silicate Ceramics-a: Clays and Kaolinite
7. Silicate Ceramics-b: Feldspars and Silica
8. Products Classification, Terra cotta
9. Earthenwares vs. Stonewares
10. Porcelains, Vitreous china
11. Alumina Ceramics
12. Mullite, Magnesia, and Spinel
13.
Zirconia, Other oxides
Material
Part 1: The Crystalline State
1
Introduction to Ceramics
2
Elementary Crystallography-1
3
Elementary Crystallography-2
4
Ceramic Microstructures
5
Traditional vs. advanced Ceramics
6
General Characteristics of Ceramics
7
Applications
Part 2: Silicates, Alumina and
Zirconia
8
Kaolinite and Clays
9
Feldspars and Silica
10
Products Classification, Terra cotta
11
Earthenwares
12
Stonewares
13
Porcelains, Vitreous china
14
Alumina Ceramics
15
Mullite, Magnesia, and Spinel
16
Zirconia, Other oxides
Part 3: Sintering and Microstructure
17
Sintering and Microstructure of
Ceramics
18
Thermodynamics of sintering
19
Matter transport
20
Experimental aspects of sintering
21
Solid phase sintering
22
Sintering with liquid phase
23
Sintering additives, Pressure
sintering and Hot Isostatic Pressing
HIP
0
Dr. Saad B. H.
Course 2:
1. Sintering and Microstructure of
Ceramics
2. Thermodynamics of sintering, Matter
transport
3. Experimental aspects of sintering
4. Solid phase sintering
5. Sintering with liquid phase: vitrification
6. Sintering additives, Pressure sintering
and HIP
7. Glass Definition and Transition
temperature
8. Common types of glass
9. Raw Materials and Batch Calculations
10. Viscosity of Glass Forming Melts
11. Thermal Expansion of Glass
12. Vitreous Coating
13. Bio Ceramics, Glasses, and GlassCeramics
Ref. no.
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1:
1:
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1.1, 1.2
1.3
1.3
1.4
1.5
1.6
1.7
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2:
2:
2:
2:
2:
2:
2:
4.3
4.3
4.5
4.5
4.5
4.5
6.1 6.5
6.6 6.7
6.8 6.9
2:
3.1
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2:
2:
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2:
2:
3.2
3.2
3.2
3.5
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Farid 2014-2015
Part 4: Glass and Glass ceramics
24
Glass Definition and Transition
temperature
25
Common types of glass
26
Raw Materials and Batch
Calculations
27
Viscosity of Glass Forming Melts
28
Thermal Expansion of Glass
29
Vitreous Coating
30
Bio Ceramics, Glasses, and GlassCeramics
Dr. Saad B. H.
Wikipedia
3:
Wikipedia
3.2, 3.4
3:
4.
2.; 5
6.
6.2, 6.4, 6.5

6.
4.4; 4.2,4.3
2.6
Course 1
1- Introduction to Ceramics
In metals, the bonding is predominantly metallic, where delocalized electrons provide
the "glue" that holds the positive ion cores together. This delocalization of the bonding
electrons is responsible for properties most associated with metals: ductility, thermal
and electrical conductivity, reflectivity, and other distinctive properties.
Polymers consist of very long, C-based chains to which other organic atoms (for
example; C, H, N, Cl, F) and molecules are attached. The bonding within the chains is
strong, directional, and covalent, while the bonding between chains is relatively weak.
Thus, the properties of polymers as a class are dictated by the weaker bonds, and
consequently they possess lower melting points, higher thermal expansion coefficients,
and lower stiffnesses than most metals or ceramics.
Ceramic materials are inorganic, nonmetallic compounds, usually oxides like SiO 2,
Al2O3 and non-oxides such as carbides, nitrides, and borides. Both ionic and covalent
bonds, or combination of them, can be found in ceramic materials. The dominant
characteristics of ceramics are summarized by the following:
i.
ii.
iii.
iv.
v.
They are stable and resistant to chemical attack.

They are brittle, hard, and wear resistant.
They have high temperature strength.
They are good electrical insulators at room temperature.
Their thermal conductivities lie between those of polymers and of metals.
Ceramic materials may occur in the form of single crystal and in the form of
polycrystalline material (polycrystals). These polycrystals are oriented with respect to
each other in more or less completely random way. They are also called grains. When
the grains have a different composition, the ceramic material is of multiphase. The
grains in the monolithic material are of single phase.
Figure 1 shows a typical cross-section of ceramic material. It
composed of an assembly of irregularly shaped grains and pores. The
solid-solid interfaces are called "grain boundaries" and the solid-gas
interfaces are called "free surfaces". Grain boundaries and free
surfaces constitute the microstructure of the ceramic material.
To obtain polycrystalline ceramic material, a
compressed fine-grained powder is subjected to a high
temperature around (65-75)% of its melting point. The
process is called "sintering"; in which the powder
compact shrinks during heating, and its bulk density
increases to form the ceramic body. The densification
of the powder compact is accompanied by coarsening
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Farid 2014-2015
of primary grains "grain growth" and elimination or
decrease in volume of intergranular voids "pore
shrinkage". The evolution and rate of these
microstructure changes are referred as "microstructure
development" of the sintered ceramic body.
Dr. Saad B. H.
The mechanical and physical properties of ceramics are depending on their microstructure. The mechanical
properties are correlated to the grain size (the diameter of the sphere of the same grain volume) while the
thermal, magnetic and electrical properties are influenced by the existence of the interfaces (grain boundaries
and free surfaces). The correlation between the properties of ceramics and their microstructure reflects the
importance of sintering studies. Normally, these studies attempts to attain high density and controlled grain size
of the product.
Figure
2: The Unit
Cel
Semiconductors are subgroup of ceramics; they are covalently
bonded
solids
that, in
addition to well known Si and Ge, include GaAs, CdTe, and InP etc. Other
semiconductors outside the electronic materials are SiC, TiO2, ZnO, and others.
The arrangement of atoms in solids, in general, and ceramics, in particular, will

exhibit long-range order, only short-range order, or a combination of both. Solids
that exhibit long-range order are referred to as crystalline solids, while those in which
that periodicity is lacking are known as amorphous, glassy, or noncrystalline solids.
2- Elementary Crystallography
A long-range order requires that atoms be arrayed in
a three dimensional pattern that repeats. The simplest
way to describe a pattern is to describe a unit cell within
that pattern. A unit cell is defined as the smallest region
in space that, when repeated, completely describes the
three-dimensional pattern of the atoms of a crystal.
Geometrically, it can be shown that there are only seven
unit cell shapes, or crystal systems, that can be
stacked together to fill three-dimensional space. The
seven systems, shown in Figure 3, are cubic, tetragonal,
orthorhombic, rhombohedral, hexagonal, monoclinic, and
triclinic. The various systems are distinguished from one
another by the lengths of the unit cell edges and the
angles between the edges, known as the lattice
parameters or lattice constants (a, b, c, a, , and in
Figure 2).
Figure 1: Cross section of ceramic
The unit cell has a number of
permutations, primitive, base centered,
body centered, and face centered. However,
symmetry considerations limit the total
number of possible permutations to 14
Bravais lattices. See Figure 3.
material. The dark fields

represent the pores.

Farid 2014-2015
Dr. Saad B. H.
Figure 3: Seven Crystal Systems and 14

Bravais Lattices
3- Ceramic Microstructures
Crystalline solids exist as either single crystals or polycrystalline solids. A single

crystal is a solid in which the periodic and repeated arrangement of atoms is perfect and
extends throughout the entire specimen without interruption. A polycrystalline solid is
comprised of a collection of many single crystals, termed grains, separated from one
another by areas of disorder known as grain boundaries.
Typically, in ceramics the grains are in the range of 1 to 50 m and are visible only
under a microscope. The shape and size of the grains, together with the presence of
porosity, second phases, etc., and their distribution describe what is termed the
microstructure. Many of the properties of ceramics are microstructure-dependent.
4- Traditional Versus Advanced Ceramics
Traditional ceramics, pottery, sculpture, sanitary ware, tiles, etc., are characterized
by mostly silicate-based porous microstructures that are quite coarse, non-uniform, and
multiphase. They are typically formed by mixing clays and feldspars, followed by forming
either by slip casting or on a potter's wheel, firing in a flame kiln to sinter them, and
finally glazing.
In a much later stage of development, other ceramics that were not clay or silicatebased depended on much more sophisticated raw materials, such as binary oxides,
carbides, perovskites, and other completely synthetic materials for which there are no
natural equivalents. The microstructures of these modern or technical ceramics were at
least an order of magnitude finer, more homogeneous, and much less porous than the
traditional.
5- General Characteristics of Ceramics
Ceramic materials are generally:
1. Hard
2. Wear-resistant
3. Brittle
4. Nonmagnetic
5. Intrinsically transparent
6.
7.
8.
9.
Electrically insulative
Thermally insulative
Refractory
Vulnerable (susceptible) to thermal
shock
10. Oxidation-resistant, Chemically
stable
However, there will be exceptions; some ceramics are electrically and thermally quite
conductive, while others are even superconducting. An entire industry is based on the
fact that some ceramics are magnetic.
Why ceramics exhibit these properties?
The answer of this question is one of the goals of the study of the structure and
microstructure of ceramics.
Applications
Ceramic materials have a wide range of applications. Some modern applications are:

Dr. Saad B. H.
Farid 2014-2015
1. Ceramic engines for transportation and turbines for energy production due to the
refractoriness of ceramics and their ability to sustain high loads at high
temperatures, together with their low densities
2. Optical communications such as fiber optics due to optical properties of a glass
3. Electrooptic applications like displays and transparent displays (semiconductive
optical ceramics)
4. Laser materials (the active materials)
5. Substrates in electronic circuits; due to insulative properties, low-loss factors, and
excellent thermal and environmental stability
6. Ceramic capacitors due to exceedingly large dielectric constants of the perovskite
family
7. Magnetic ceramics based on the spinel ferrites
8. Piezoelectric ceramics for sensors and actuators
9. The nonlinear I-V characteristics for circuit protection
10.
Ionically conducting ceramics for use as solid electrolytes in hightemperature fuel cells and as chemical sensors
11.
Electrodes in photoelectrochemical devices or cells PEC, which are solar cells
that produce electrical energy or hydrogen in a process similar to the electrolysis
of water
12.
A new revolution in silicate ceramics (Stone Age materials) is taking place to
make them materials for the future. Alkali-activated cements and mortars (also
called geopolymers) are an example.
In principle, the advantages of an all-ceramic engine are several and include lower
weight, a higher operating temperature that translates to higher efficiencies, and less
pollution. It is also predicted that such engines would not require cooling and maybe not
even any lubrication, which once more would simplify the design of the engine, reducing
the number of moving parts, and lowering the overall weight of the vehicle.

Farid 2014-2015
Some of the common applications are listed in next table:
Property
1. Thermal
Insulation
Refractoriness
Thermal conductivity
2. Electrical and dielectric
Conductivity
Ferroelectricity
Low-voltage insulators
Insulators in electronic
applications
Insulators in hostile
environments
Ion-conducting
Semiconducting
Nonlinear I-V characteristics
Gas-sensitive conduct
3. Magnetic and
superconductive
Hard magnets
Soft magnets
Superconductivity
4. Optical
Transparency
Translucency and chemical
inertness
Nonlinearity
IR transparency
5. Chemical
Catalysis
Anticorrosion
Biocompatibility
6. Biomedical and
Biomaterials
7. Mechanical
Hardness
High-temperature strength and
retention (withstanding)
5
Dr. Saad B. H.
Applications (examples)
High-temperature furnace linings for insulation
(oxide fibers such as SiO2, A12O3, and ZrO2)
High-temperature furnace linings for insulation
and containment of molten metals and slags
Heat sinks for electronic packages (A1N)
Heating elements for furnaces (SiC, ZrO2, MoSi2)
Capacitors (Ba-titanate-based materials)
Ceramic insulation (porcelain, steatite,
forsterite)
Substrates for electronic packaging and
electrical insulators in general (Al2O3, A1N)
Spark plugs (Al2O3)
Sensor and fuel cells (ZrO2, A12O3, etc)
Thermistors and heating elements (oxides of Fe,
Co, Mn)
Current surge protectors (Bi-doped ZnO, SiC)
Gas sensors (SnO2, ZnO)
Ferrite magnets [(Ba, Sr)O6Fe2O3]

Transformer cores [(Zn, M)Fe2O3, with M = Mn,
Co, Mg]; magnetic tapes (rare-earth garnets)
Wires and SQUID magnetometers (YBa2Cu3O7)
Windows (soda-lime glasses), cables for optical
communication (ultra-pure silica)
Heat- and corrosion-resistant materials, usually
for Na lamps (Al2O3MgO)
Switching devices for optical computing
(LiNbO3)
Infrared laser windows (CaF2, SrF2, NaCl)
Filters (zeolites); purification of exhaust gases
Heat exchangers (SiC), chemical equipment in
corrosive environments
Artificial joint prostheses (Al2O3)
Cutting tools (SiC whisker-reinforced A12O3,

Si3N4)
Stators and turbine blades, ceramic engines
(Si3N4)

Dr. Saad B. H.
Farid 2014-2015
Wear resistance
Bearings (Si3N4)
8. Nuclear applications
Fission
Nuclear fuel (UO2, UC), fuel cladding (C, SiC),
neutron moderators (C, BeO)
Fusion
Tritium breeder materials (zirconates and
silicates of Li, Li2O); fusion reactor lining (C, SiC,
Si3N4)
6- Silicate Ceramics-a: Kaolinite and Clays
Kaolinite
1- Structure of Kaolinite
Kaolinite, Si2Al2O5(OH)4 or Al2O3,2SiO2,2H2O, is
the most common among the argillaceous minerals
Figure 4:
used in ceramics. A projection of its crystalline
Projected representation of the
structure is represented in Figure 4. It consists of
structure of kaolinite
an alternate stacking of [Si2O5]2- and [Al2(OH)4]2+
layers, which responsible for the lamellate
character that lead to the development of plates.
The degree of crystallinity of the kaolinite present
in clays is highly variable. It depends largely on the
conditions of formation and the content of
impurities introduced into the crystalline lattice.
2- Evolution of the nature of phases during heat treatment
Figure 5: Differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) of two
kaolinites with different degrees of crystallinity
During the heat treatment, kaolinite undergoes a series of transformations as

indicated in Figure 5. The departure of water, which occurs from 450C onwards, is a
very endothermic phenomenon. The amorphous metakaolin, Al2O3.2SiO2 is then formed.
The exothermic transformation observed between 960 and 990C is a structural
reorganization of the amorphous metakaolin. Phase transformations occur and end into
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Dr. Saad B. H.
Farid 2014-2015
mullite stoichiometry ranging between 3Al2O3.2SiO2 and 2Al2O3.SiO2. During this reaction,
amorphous silica is released. The extra amorphous silica starts to crystallize in the form
of cristobalite from 1,200C onwards.
It should be noted that the impurities present, the degree of crystallinity (see Figure
5), and the heating rate influence these transformations.
Clays (the kaolinite can be one type or component of clays)
1- Common characteristics
i. Clays are hydrated aluminosilicate minerals whose structure is made up of a stacking
of two types of layers containing, respectively, aluminum in an octahedral
environment and silicon in tetrahedral coordination.
ii. The large surface area of clays (10100 m2g-1), their plate-like structure, and the
physicochemical nature of their surface enable clays to form, with water, colloidal
suspensions and plastic pastes.
This characteristic is largely used during the manufacture of silicate ceramics
because it makes it possible to prepare homogenous and stable suspensions, suitable for
casting, pastes easy to manipulate, and green parts with good mechanical strength.
By extension, the term clay is often used to denote all raw materials with proven
plastic properties containing at least one argillaceous mineral. The impurities present in
these natural products contribute to a large extent to the coloring of the product.
2- Classification
The clays are not all the same towards easy manipulation and behavior during firing.
Ceramists distinguish vitrifying plastic clays, refractory plastic clays, refractory clays,
and red clays.
Vitrifying plastic clays
They are generally colored, are used for the remarkable plasticity of their paste. They
are made up of very fine clay particles, organic matter, iron and titanium oxides, illite
(formula Si4xAlx)(Al,Fe)2O10(OH)2Kx(H2O)n) and micaceous (from mica) and/or feldspathic
impurities.
These clays are also characterized by high free silica content. Sand can represent up
to 35% of the dry matter weight. The product called "ball clay" is widely used for its
plasticity and its particularly low mica content.
Although it contains the same argillaceous mineral as kaolin, this clay has much
higher plasticity because of the much smaller size of the kaolinite particles.
Refractory plastic clays
They are rich in montmorillonite (formula (Si4-xAlx)(Alx-vRx)O10(OH)2M2v(H2O)n with R =
Mg, Fe2+ and M = K, Na), kaolinite or halloysite (Si2Al2O5(OH)4(H2O)2).
Refractory clays
They are used in high temperature processes.
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Dr. Saad B. H.
Farid 2014-2015
Their composition is rich in alumina. Kaolins are the most refractory among these
clays. Always purified, they contain little quartz, generally less than 2% alkaline oxides in
combined form, and a small quantity of mica.
Their plasticity is due to the kaolinite and, if necessary, a little smectite or halloysite.
Very low in coloring element, they are particularly suited for the preparation of
products in white color.
Red clays
They are used for the manufacture of terra cotta products.
They have complex composition of actually natural mixtures.
They generally contain kaolinite, illite and/or other clays rich in alkaline, sand, mica
(formula Si3Al3O10(OH)2), goethite (FeO(OH)) and/or hematite (Fe2O3), organic matter and,
very often, calcium compounds. The latter, just like the micas and the other alkaline-rich
compounds that help lower the firing temperature of the product.
7- Silicate Ceramics-b: Feldspars and Silica

The Role of Oxides in Firing of Traditional Ceramics
Acidic Oxides: They are backbone of the ceramic and mainly improve the mechanical
properties.
Formula: MO2, e.g. SiO2, GeO2, TiO2, ZrO2, CrO2 etc
Basic Oxides: They are Fluxes, i.e. reducing firing temperature.
Formula: MO and M2O, e.g. CaO, MgO, Na2O, K2O, Li2O etc
Amphoteric Oxides: They form bridges between acidic and basic oxides and partially
substitute them.
Formula: M2O3 and M2O5, e.g. Al2O3, B2O3, P2O5 etc
Feldspars
Four feldspathic minerals are likely to enter the composition of silicate ceramic
pastes. They are:
orthoclase, a mineral rich in potassium with the composition K2O.Al2O3.6SiO2
albite, a mineral rich in sodium with the composition Na2O.Al2O3.6SiO2
anorthite, a mineral rich in calcium with the composition CaO.Al2O3.2SiO2
petalite, a mineral rich in lithium with the composition Li2O.Al2O3.8SiO2
soda Na2O, sodash
potash
lucite
Orthoclase and albite, which form eutectics with silica at 990 and 1,050C
respectively, are widely used as flux. Anorthite is rather regarded as a substitute to chalk
8

Dr. Saad B. H.
Farid 2014-2015
(CaCO3). There is a limited use of petalite. It is used mainly to improve brightness and its
negative CTE.
Potassic feldspar is particularly appreciated by ceramists because its reaction with
silica leads to the formation of a liquid whose relatively high viscosity decreases slightly
when the temperature increases. This behavior is considered as a guarantee against the
excessive deformation of the pieces during the heat treatment.
In manufacturing of porcelain, the feldspars can be replaced by nepheline syenite
with average composition (Na,K)2O,Al2O3,2SiO2. This rock, made up of nephelite
(composition: K2O.3Na2O.4Al2O3.9SiO2) and a mixture of potassium and sodium feldspars.
It is a powerful flux, which makes it possible to decrease the sintering temperature of
ceramics and increase the alkaline content of the vitreous phases. However, special care
should be taken for homogeneity.
Silica
Silica, SiO2, is a polymorphic raw material found in nature in an amorphous (opal,
pebbles) or crystallized form (quartz, cristobalite and tridymite). Sand contains between
95 and 100% of quartz mass. It is the most frequently used in the ceramic industry to
contribute to the mechanical strength of the parts. In the manufacturing processes of
stonewares and porcelains, it is usual to use relatively fine sand grains (20 to 60 m).
When a ceramic is fired, the sand can react, particularly with the fluxes. This reaction
is not often complete. The transformation of residual quartz into cristobalite can then
start from 1200C onwards. This transformation is enhanced by the rise in temperature,
the use of fine-grained sand, the presence of certain impurities, and the use of reducing
atmosphere.
The form of silica determines the thermal properties of silicate ceramics. For
example, quartz and cristobalite do not have the same influence on the expansion of the
product. Quartz can also cause a deterioration of the mechanical properties of the
finished product owing to the abrupt variation in dimensions (L/L 0.35%) associated, at
573C, with the reversible transformation quartz quartz. As the crystal of cristobalite
formed from the flux are usually small, the transition cristobalite cristobalite,
which occurs at about 220C often causes less damage to the finished product.
Enamel and decorations is outside the scope of this course but worry about it.
8- Products Classification
The materials treated at higher temperatures
or in the presence of a large quantity of flux are
generally the least porous. The porous ceramics
(earthenwares, fired at 900-1200C) can be used
just as they are (bricks and tiles) or be covered
with enamel. The dense products are stonewares
fired at about 1350C. Vitreous china forms an
Need firing
intermediate group between these
two families.
temperatures
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Farid 2014-2015
Terra cotta products
Dr. Saad B. H.
Terra cotta is referring to potteries or construction products such as roof tiles, bricks,
flues, drainage pipes, or some floor tiles. Terra cotta products were obtained a long time
ago by modeling, drying and firing common clays. Nowadays, the compositions are more
complex; they combine clays, additives, and coloring agents, which make it possible to
improve the manufacturing behavior or the final characteristics.
The raw materials are added to water to form a plastic paste whose rheology must be
adapted to the shaping process (extrusion possibly completed by pressing). The raw
parts are dried in a ventilated cell or a tunnel dryer. The temperature at the end of firing
usually ranges between 900 and 1160C.
Terra cotta products are porous and mechanically resistant. They are marketed raw,
enameled or covered with a glaze realized at low temperature, between 600 and 900C,
called varnish. They are appreciated for their esthetic quality, their stability through time
and their hygrothermic and acoustic properties. They represent a highly automated
industrial sector, which is of continual technological developments.
9-a Earthenwares products
Figure 6: Traditional ceramic families
The earthenware are made up of a porous products covered with a glaze. The glazing
makes it possible to change the appearance of the product and to overcome the high
permeability due to the existence of an open porosity (5 20%). earthenwares are used
as crockery, pottery, wall tiles etc.
These products are prepared from one or more clays to which quartz, chalk (Calcite,
CaCO3), feldspar, or ground glass is added. Earthenwares are primarily shaped by slip
casting, jiggering of plastic paste and powder pressing. After drying, the raw product is
subjected to a heat treatment called biscuiting, carried out at a temperature ranging
between approximately 900 and 1,230C. The deformation and the shrinkage of the
product during this stage are limited because of the refractory nature of the raw
materials used.
The porous biscuit obtained is then glazed during glazing firing carried out at a
temperature lower than or sometimes equal to that of biscuiting. The third firing (very
rare), at a lower temperature, is necessary to fix some decorations deposited on the
glaze, in particular those containing gold or platinum and those known as low fire
decorations.
9-b Stonewares products
Stonewares have a vitrified, opaque, colored, and practically impermeable product (0
to 3% open porosity). They are obtained from a mixture of vitrifying plastic clays and
flux, sometimes supplemented by sand or grog. They are formed by extrusion (pipes,
bricks, etc.) or by granulated powder pressing (tiles, slabs, etc.). The firing temperature
generally ranges between 1,120 and 1,300C and it forms a critical parameter. In fact,
sintering at an insufficient temperature (non-firing) results in the persistence of a
significant open porosity and a treatment at too high a temperature leads to the
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Dr. Saad B. H.
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deformation of the pieces because of the excessively large quantity and the low viscosity
of liquid formed. If usage requires it, stonewares can be enameled. A salt glaze during
firing can also be carried out (traditional salt-glazed stonewares).
Stonewares are known for their un-changeability, excellent mechanical performances,
and resistance to erosion and chemical agents.
10-a Porcelains
The porcelain products are white and translucent for pure raw materials and low
thickness. Porcelains do not have open porosity (< 0.5%), but are likely to exhibit some
large closed pores (air holes). Their fractures are brilliant and have a vitreous
appearance. After enameling, the surface of the pieces is remarkably smooth and
brilliant.
When porcelain is fired, a liquid phase surrounds the solid grains and dissolves the
finest of them (< 15 m). During this stage, known as pasty fusion, the viscosity is
sufficiently high for the deformation of the pieces to remain within acceptable limits. The
solidification of the liquid on cooling leads to the formation of a large quantity of vitreous
phase.
The manufacturing processes are changing constantly, Thus, when the geometry of
the parts allows it, pressure casting and shaping by isostatic pressing gradually replace
jiggering and casting in plaster molds. Fast firing techniques are increasingly used for
enamel and decorations. Porcelains improve the quality of the parts by limiting the risks
of deformations. A usual trend is to decrease the sintering temperature.
10-b Vitreous china
The term vitreous china denotes dense products obtained from pastes close to
those used to manufacture feldspathic earthenwares. The feldspar content of these
pastes is increased in order to produce, during the firing, a sufficient quantity of liquid to
eliminate open porosity (< 0.5%). Vitreous china are mainly used to manufacture
sanitary articles and tough crockery (washbasin, crockery for communities), vitreous
materials are in the middle between white paste stonewares and porcelains.
These products are formed by jiggering, casting, or isostatic pressing. A good raw
materials and shaping process is that makes it possible to obtain raw pieces with a
mechanical strength sufficient to withstand the application of an enamel paste. Sanitary
products are generally vitrified and enameled in a single treatment, carried out in
oxidizing atmosphere at a temperature between 1.200 and 1.280C. A twice-firing
treatment is usually used for crockery. The first firing is thus carried out between 900
and 950C. The elimination of open porosity and the formation of the enamel occur
during the second firing at a temperature ranging between 1.200 and 1.250C. The
enamel thus obtained, generally opacified, can allow a large variety of decorations.
11- Alumina Ceramics
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Dr. Saad B. H.
Farid 2014-2015
Alumina is produced primarily from bauxite rocks treated through the Bayer process.
Bauxite rocks contain 40-60% of equivalent alumina, 10-20% iron oxide, and
approximately 5% quartz sand and various impurities.
The Bayer process consists of attacking the rock crushed by a hot caustic detergent
(NaOH solution at a temperature of 150160C, under a pressure of 0.5 MPa) in order to
dissolve alumina in the form of aluminate and to precipitate the impurities (Fe2O3, SiO2,
TiO2). These red deposit are eliminated by filtration and, after cooling, the hydrated
sodium aluminate solution NaAl(OH)4 is seeded with -Al(OH)3 germs which leads to a
massive precipitation of this latter phase.
Heat treatments of Bayer -Al(OH)3 initially cause dehydration, then a
recrystallization to many types of transition aluminas that can be classified under the
name of gamma aluminas.
a- Structural applications of alumina
Alumina ceramics owe to the stability of this oxide and its strong atomic bonds. Their
mechanical and thermal performances, high hardness, high moduli of elasticity,
satisfactory mechanical strength, wear resistance, good tribological properties, and
refractoriness.
Giving accurate values would be useless because mechanical properties are sensitive
properties, which vary with the microstructure, and the hot properties depend highly on
the temperature and chemical reactions when the environment is aggressive. To
illustrate this point, a dense fine-grained alumina ceramic has a Youngs modulus of
400 GPa (twice the modulus of steel), a Poissons ratio of 0.25, a Vickers hardness of
20 GPa and a mechanical bending strength F of 300-500 MPa.
Toughness at 20C is equal to 3.5 MPa m1/2, which is a respectable amount for a
ceramic, but this less than that of metals. Ductility is modest. The coefficient of thermal
expansion is 8.5 10-6 K-1 (20-1,000C, 20-1,000). This relatively high thermal expansion for
a ceramic combines with a high Youngs modulus makes alumina ceramics are not very
resistant to thermal shocks. Alumina has poor creep resistance under substantial load.
Alumina ceramics are best suited for mechanical uses (excluding shocks) or refractory
uses.
b- Functional applications of alumina
Alumina ceramics are widely used by the electric and electronic industries. Spark
plugs for automobiles illustrate the oldest application using 94% Al2O3. Additionally,
alumina is found in a number of insulation products, including those requiring tight
ceramic-metal sealings.
For electronics, the main product is the insulating substrate, on which conducting or
resistive, even capacitive, or inductive, circuits are deposited. The advantage of alumina
is its very high resistivity (it may be recalled that for this it must be very pure, or at least
free from impurities like sodium or transition metals).
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Farid 2014-2015
The three limitations of alumina for the manufacture of dielectric substrates are:
i. a modest thermal conductivity ( 30 W m-1 K-1), which does not facilitate the
dissipation of the heat produced by the Joule effect;
ii. a coefficient of expansion double that of silicon, which generates stresses at the
substrate (chip interfaces);
iii. a marked permittivity ( 10), which induces capacitive couplings and decreases the
transit times.
Aluminum nitride AlN is one of the competitors for the manufacture of high
technology substrates, where it brings improvements with respect to the three
drawbacks mentioned above, but its manufacture is expensive and delicate.
Sapphire and possibly ruby mono-crystals is used due to the remarkable combination
of optical and mechanical performances. Jewelry (jewels, scratch-proof glass for
watches), laser matrices, substrates for certain electronic circuits and waveguides are
the primary applications of sapphire mono-crystals, as well as abrasion-resistant optical
windows: for military use, but also barcode readers in supermarkets.
12- Mullite, Magnesia, and Spinel
Mullite 3Al2O3.SiO2 is the only stable
crystallized compound in the binary phase
diagram of the Al2O3-SiO2. However, mullite
is very rare in the state of natural ore,
except in some places such as the Scottish
island of Mull, which explains its name. Its
mechanical strength drops much less
quickly when the temperature increases
than in the case of alumina: at 1,300C,
most mullite ceramics have a mechanical
strength close to the one at room
temperature, and some mullites with
vitreous segregations even have a peak
mechanical strength at about 1,300C.
These characteristics make mullite a
material of choice for refractory
applications
The majority of magnesia produced is
used for refractories in the iron and steel
industry, where the basic oxide properties
of the material are necessary. Magnesia
withstands the very high temperatures of
converters (1,700C), where it can dissolve
several times its weight of iron oxide
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Farid 2014-2015
without melting and it effectively resists
sealing and the attack of slag.
Dr. Saad B. H.
Spinel MgAl2O4 has given its name to a

crystalline structure adopted by several
mineral phases. Based on the notation
Mg2+Al23+O4, Mg2+, Mg2+ can be replaced by
other divalent cations like Fe2+, Mn2+ or
Zn2+, and Al3+ can be replaced by other
trivalent cations like Fe3+ or Cr3+. The
spinel structure is denoted by AB2X4 (space
group Fd3m).
Dense sintered spinel is transparent in
a broad domain of wavelengths, which
explains its use in the manufacture of
optical windows (military applications in
particular)
13- Zirconia, Other oxides
Zirconia is an oxide with very high melting temperature (T 2,880C), which
solidifies in cubic phase (ZrO2-c, group space Fm 3 m), then transforms (T < 2,370C)
to tetragonal phase ( ZrO2-t, P42/nmc) and finally, below 1,170C, becomes monoclinical (ZrO2-m, P21/c). This last transition tm is accompanied by considerable
dimensional variations (shear strains of 0.16 and increase in volume of 4%), which
largely exceed the maximum stress limit, resulting in a fragmentation of the material. A
sintered zirconia part, say to 1500C, breaks up, and destroyed during cooling. This took
place during the tm transition. This means that pure zirconia can be used only in
powder form (for example, as starting product for the manufacture of ceramic enamels),
and therefore for uses that do not require consolidation into a massive part.
To produce zirconia sintered pieces, ZrO2 must be combined with other oxides known
as stabilizers (MxOy= primarily CaO, MgO, or Y2O3): the ZrO2-MxOy phase diagram is
then modified favorably, which helps preserve (at the stable state or metastable state) a
stabilized zirconia, free from transitions in the entire useful temperature range in
practice from the sintering temperature to room temperature. In the ZrO2-CaO diagram,
for example, it is observed that for 20 mol% CaO, the material remains in cubic phase
from room temperature to practically the melting temperature.
Among the uses of stabilized zirconia, denoted SZ, we can mention four main fields:
1.
2.
the production of mono-crystals for jewelry, because the optical properties of zirconia
are not very different from those of a diamond, at an incomparably lower cost;
the manufacture of crucibles and other refractory parts, because of the high melting
temperature and good resistance to corrosive mediums, including molten glass
(refractories of A-Z-S system: Al2O3-ZrO2-SiO2);
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Farid 2014-2015
3. the manufacture of thermal barriers, for example deposited by plasma spraying using
plasma torches for the internal protection of the combustion chamber of jet engines,
because the thermal conductivity of zirconia is one of lowest ever known among nonmetallic inorganic solids (k 1 W.m-1.K-1, i.e. 30 times lower than alumina);
4. The manufacture of ionic conductors; The introduction of bivalent (CaO and MgO) or
trivalent (Y2O3) metal oxides that are used as stabilizers requires, allows a
considerable mobility of residual oxygen ions, the stabilized zirconia offers properties
of ionic conduction that allow its application as solid electrolyte, particularly in oxygen
sensors and in solid oxide fuel cells.
Ceramic steel
SZ has rather modest mechanical properties, significantly less remarkable compared
to alumina which, associated with higher density, higher thermal expansion
(consequently greater sensitivity to thermal shocks) and markedly increased costs
explain why these stabilized zirconia a priori do not have a mechanical application.
Zirconia can exhibit the high mechanical performances associated with steel, but also
that toughening mechanisms recall those used by steel manufacturers. The tm
transformation of zirconia is a martensitic transformation, in analogy with the
transformation used to obtain martensite in tempered steels, and the role of
microstructural parameters in ZrO2 is similar to what is observed in metals.
In transformation toughening (TT), toughening indicates the increase in toughness as
well as in mechanical strength. We have the following acronyms: ZTC (zirconia
toughened ceramics), Ca-PSZ or Mg-PSZ (partially stabilized zirconia containing 8 mol
% CaO or 9 mol% MgO), TZP (tetragonal zirconia polycrystals, Y-TZP containing
typically 2-3 mol% Y2O3), etc. There are indeed various categories of materials
depending on the nature of the stabilizer, its concentration, microstructure, and various
associated phases: ZTA (zirconia toughened alumina) is for example alumina toughened
by zirconia dispersion, prepared in such a manner that TT mechanisms are operational.
SiO2 and the compositions in the ternary system SiO2-CaO-Na2O are the basic
ingredients in glass industries and that the quaternary system CaO-SiO2-Al2O3-Fe2O3
contains the compositions of cement clinkers. Ceramics for electronics, oxides with
magnetic performances (for example, ferrites with spinel structure) and also barium
titanate BaTiO3 and zinc oxide ZnO, not to speak of beryllium oxide BeO or
superconductive of which YBa2Cu3O7 is the sound example.
Course 2
1- Sintering and microstructure of ceramics
Sintering is at the heart of ceramic processes. However, sintering takes place only in
the last of the three main stages of the process (powders forming heat treatments).
Sintering involves scientific considerations more directly, whereas the other two stages
often stress more technical observations and involve manufacturing secrets. However,
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sintering may be followed by various finishing treatments (rectification, decoration,
deposit of surfacing coatings, etc.). Sintering often reveals defects caused during the
preceding stages, which are generally optimized with respect to sintering, for example,
the granularity of the powders directly influences the densification and grain growth.
Generally, the success of the powder treatment is validated by the performances of the
sintered part.
During sintering, the non-cohesive granular medium becomes a cohesive material;
the consolidation takes place, and organizing the microstructure (size and shape of the
grains, amount and nature of the porosity, etc.). However, the microstructure
determines, to a large extent, the performances of the material. This is the reason why
sintering meets a comprehensive attention. Sintering and microstructure are thus
connected.
Sintering is the basic technique for the processing of ceramics, but other materials
can also use it: metals, carbides bound by a metallic phase and other cermets etc.
2-a Thermodynamics of sintering
i. A powdery agglomerate is often called compact, even though its porosity is typically
40% and therefore its compactness is only 60%.
ii. Sintering is the consolidation, under the effect of temperature, of a compact of a noncohesive granular material. The particles of the starting powder "welding" with one
another to create a mechanically cohesive solid, generally a polycrystal.
iii. The surface of a solid has a surplus (excess) energy (energy per unit area: SV, where
S is for "solid" and V is for "vapor") due to the fact that the atoms here do not have
the normal environment of the solid which would minimize the free enthalpy.
iv. In a polycrystal, the grains are separated by grain boundaries whose surplus energy
(denoted SS, or GB, where SS is for "solid-solid" and GB for "grain boundary") is due
to the structural disorder of the boundary.
v. In general, SS < SV, so a powder lowers its energy when it is sintered to yield a
polycrystal: the thermodynamic engine of sintering is the reduction of systems
interfacial energies.
The interfacial energy has the form G = A, where is the specific interface energy
and A its surface area. The lowering of energy can therefore be achieved in three ways:
i) by reducing the value of ,
ii) by reducing the interface area A, and
iii) by combining these effects.
The replacement of the solid-vapor surfaces by grain boundaries decreases , when
SS is lower than SV. The reduction of A is achieved by grain growth: for example, the
coalescence of n small spheres with surface s and volume v results in a large sphere
with volume V = nv but with surface S < ns. In fact, the term sintering includes four
phenomena, which take place simultaneously and often compete with each other:
consolidation: development of necks that weld the particles to one another;
densification: reduction of the porosity, therefore overall contraction of the part
(sintering shrinkage);
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Farid 2014-2015
grain coarsening: coarsening of the particles and the grains;
physicochemical reactions: in the powder, then in the material under consolidation.
Figure. Sintering of four powder

particles. In general, we want sintering to
be "densifying", in which case the
reduction of porosity implies a shrinkage:
Lfinal= L0 L. Some mechanisms are nondensifying and allow only grain growth.
This diagram shows a two-dimensional
system but the powder is a threedimensional system.
2-b Matter transport
Sintering is possible only if the atoms can diffuse to form the necks that weld the
particles with one another. The transport of matter can occur in vapor phase, in a liquid,
by diffusion in a crystal, or through the viscous flow of a glass. Most mechanisms are
activated thermally because the action of temperature is necessary to overcome the
potential barrier between the initial state of higher energy (compacted powder) and the
final state of lower energy (consolidated material). Atomic diffusion in ceramics is
sufficiently rapid only at temperatures higher than 0.6-0.8 TF, where TF is the melting
point (in K). For alumina, for example, which melts at around 2,320 K, the sintering
temperature chosen is generally around 1,900 K.
3- Experimental aspects of sintering
The parameters available to us to regulate sintering and control the development of
the microstructure are primarily the composition of the starting system and the sintering
conditions:
composition of the system:
i) chemical composition of the starting powders,
ii) size and shape of the particles, and
iii) compactness rate of the pressed powder;
sintering conditions:
i) treatment temperature,
ii) treatment duration,
iii) treatment atmosphere and,
iv) pressure during the heat treatment (for pressure sintering).
Pressureless sintering and pressure sintering
In general, sintering is achieved solely by heat treatment at high temperature, but in
difficult cases it can be assisted by the application of an external pressure:
pressureless sintering: no external pressure during the heat treatment;
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Farid 2014-2015
pressure sintering (under uniaxial load or isostatic pressure): application of an
external pressure during the heat treatment.
Pressure sintering requires a pressure device that withstands the high sintering
temperatures, which is in fact a complex and expensive technique and therefore
reserved for specific cases.
Sintering with or without liquid phase
Sintering excludes a complete melting of the material and can therefore occur
without any liquid phase. However, it can be facilitated by the presence of a liquid
phase, in a more or less abundant quantity. We can thus distinguish solid phase sintering
on the one hand and sintering where a liquid phase is present; the latter case can be
either liquid phase sintering or vitrification, depending on the quantity of liquid.
for solid phase sintering, the quantity of liquid is zero or is too low to be detected.
Consolidation and elimination of the porosity require a disruption (disturbance) of the
granular architecture: after the sintering, the grains of the polycrystal are generally
much larger than the particles of the starting powder and their morphologies are also
different. Solid phase sintering requires very fine particles (micrometric) and high
treatment temperatures; it is reserved for demanding uses, for example, transparent
alumina for public lamps;
for liquid phase sintering, the quantity of liquid formed is too low (a few vol.%) to fill
the inter-particle porosities. However, the liquid contributes to the movements of matter,
mainly due to the phenomena of dissolution followed by reprecipitation. The partial
dissolution of the particles modifies their morphology and can lead to the development
of new phases. A number of technical ceramics (refractory materials, alumina for
insulators, BaTiO3-based dielectrics) are sintered in liquid phase;
lastly, for vitrification, there is an abundant liquid phase (for example, 20 vol.%),
resulting from the melting of some of the starting components or from products of the
reaction between these components. This liquid fills the spaces between the non-molten
particles and consolidation occurs primarily by the penetration of the liquid into the
interstices due to capillary forces, then solidification during cooling, to give crystallized
phases or amorphous glass. This type of sintering is the rule for silicate ceramics, for
example, porcelains. However, the quantity of liquid must not be excessive, and its
viscosity must not be too low, otherwise the object would collapse under its own weight
and would lose the shape given to it.
Sintering with and without reaction
We can speak of reactive sintering for traditional ceramics, where the starting raw
materials are mixtures of crushed minerals that react with one another during sintering.
The presence of a liquid phase often favors the chemical reactions between the liquid
and the solid grains. However, for solid phase sintering, reactive sintering is generally
avoided: either we have the powders of the desired compound already, or sintering is
preceded by calcination, i.e. a high temperature treatment of the starting raw materials
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to allow their reaction towards the desired compound, followed by the crushing of this
compound to obtain the powders that will be sintered:
non-reactive sintering: an example is that of alumina, because the powders of this
compound are available on the market;
calcination and then sintering: an example is barium titanate (BaTiO3). BaTiO3
powders are expensive and some industrialists prefer to start with a less expensive
mixture of barium carbonate BaCO3 and titanium oxide TiO2 (or TiH2-x), the mixture being
initially calcined by a high temperature treatment to form BaTiO3, which is then crushed
to give the powder that will be used for sintering;
reactive sintering: an example is that of silicon nitride (Si3N4), for which one of the
preparation methods consists of treating silicon powders in an atmosphere of nitrogen
and hydrogen, so that the reaction that forms the nitride (3Si + 2N2 Si3N4) is
concomitant (associated) with its sintering. This technique (RBSN = reaction bonded
silicon nitride) makes it possible to avoid the difficulties of the direct sintering of Si 3N4
and offers the advantage of minimizing dimensional variations, but the disadvantage of
yielding a porous material (P > 10%). Mullite and zirconia mullite can also be prepared
by reactive sintering.
Densification: sintering shrinkage
The starting compact has a porous volume (P) of about 40% of the total volume.
However, for most applications, we want relatively non-porous, even dense, ceramics (P
0%). In the absence of reactions leading to an increase in the specific volume,
densification must be accompanied by an overall contraction of the part. Densification
can be characterized by linear shrinkage (dl/l0), this contraction usually exceeds 10%.
The control of the shrinkage is of vital importance for the industrialist: on the one
hand, the shrinkage should not result in distortions of the shape and on the other hand,
it must yield final dimensions as close as possible to the desired dimensions (near net
shape). In fact, an excessive shrinkage would make the part too small, which cannot be
corrected.
As well, an insufficient shrinkage would make the part too large; in this case
machining for achieving the desired dimension must be done by rectification
(refinement, minor adjustment). This is often done by means of diamond grinding wheel.
The finishing treatment becomes more expensive as the volume of matter to be abraded
(grinded) is larger. Finally, it is difficult to control shrinkage with a relative accuracy
higher than 0.5%.
Because of the phenomenon of shrinkage, dilatometry tests are widely used for the
"in situ" follow-up of sintering: starting with the "green" compact to arrive at the fired
product, a heating at constant speed typically comprises three stages:
i) thermal expansion, accompanied by a vaporization of the starting water and a
pyrolysis of the organic binders introduced to support the pressing of the
powder;
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ii) a marked contraction, due to particle rearrangement, the development of
sintering necks and granular changes;
iii) a resumption of the thermal expansion of the sintered product.
Porosity is open as long as it is inter-connected. The material is then permeable to
fluids. Porosity is closed when it is not inter-connected: even if it is not yet dense, the
material can then be impermeable. The porosity level corresponding to the
transformation of open pores to closed pores is about P 10%.
4- Solid phase sintering
The three stages of sintering
Solid phase sintering refers to the case where no liquid phase has been identified
(but observations through electronic microscopy in transmission sometimes show the
presence of a very small quantity of liquid phase, for example due to a segregation of
the impurities along the grain boundaries). Solid phase sintering takes place in three
successive stages:
initial stage: the particle system is similar to a set of spheres in contact, between
which the sintering necks develop. If X is the radius of the neck and R the radius of the
particles, the growth of the ratio X/R in time t, for an isothermal sintering, takes the
form: (X/R)n = Bt/Dm. B is a characteristic parameter of the material and the exponents n
and m vary according to the sintering process that takes place. For example, n = 2 and
m = 1 for viscous flow; n = 5 and m = 3 for volume diffusion; n = 6 and m = 4 for grain
boundary diffusion;
intermediate stage: the system is schematized by
a stacking of polyhedric (from polyhedron) grains
intertwined at their common faces, with pores that form
a canal system along the edges common to three
grains, connected at the quadruple points (see Figure).
The porosity is open. This diagram is valid as long as
the densification does not exceed 90-92%, a
threshold beyond which the interconnection of the
porosity disappears;
final stage: the porosity is closed; only isolated
pores remain, often located at the quadruple points
between the grains ("triple points" on a twodimensional section) but which can be trapped in
intragranular position.
Diagram of the porosity in the form of interconnected canals along the edges of a
polyhedron with 14 faces, typical of the
intermediate stage of sintering
Grain growth
As the energy of the interfaces has the form A, where is the specific energy of the
interface and A is the surface area of the interface, the systems energy can be reduced
using two borderline cases:
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pure densification: the particles preserve their original size, but the solid-gas
interfaces (SG) are replaced by grain boundaries (SS), with a change in the shape of the
particles;
coalescence and pure grain growth: the particles preserve their original form, but
they change in size by coalescence, thus reducing the surface areas.
Pure densification has never been observed: there is always some degree of grain
growth.
In normal grain growth, the average grain size
increases regularly, without marked modification of
the relative distribution of the size; the
microstructure expands homothetically. This type of
grain growth is the one observed in a successful
sintering. The small grains disappear in favor of the
coarser grains, which grow (see Figure).
Secondary recrystallization (or abnormal growth,
or discontinuous grain growth) makes a few grains
grow rapidly, at the expense of the more moderately
sized grains. The final microstructure is very
heterogenous, with coexistence of very coarse grains
and very small grains. This type of microstructure
rarely leads to favorable properties; therefore, it is
generally avoided.
The pressure on the curved interfaces is

such that the boundaries move towards
their center of curvature: the small
convex grains (less than 6 sides)
disappear while the coarse concave
grains (more than 6 sides) grow at the
expense of the neighboring grains
The majority of ceramics are multiphased materials that comprise both crystallized
and vitreous phases. Porcelain thus consists of silicate glass "reinforced" by acicular
crystals of crystallized mullite, but we can also observe millimetric crystal agglomerates
with a very porous microstructure (iron and steel refractory materials), or fine grained
polycrystals (< 10 m) without vitreous phases and with very low porosity (hip
prosthesis in alumina or zirconia). It should be emphasized that, in addition to the
chemical nature of the compound(s) in question, it is the microstructure of the material
(size and shape of the grains, volume and type of porosity, distribution of the phases)
that controls the properties.
5- Sintering with liquid phase: vitrification
Parameters of the liquid phase
In general, the presence of a liquid phase facilitates sintering. Vitrification is the rule
for silicate ceramics where the reactions between the starting components form
compounds melting at a rather low temperature, with the development of an abundant
quantity of viscous liquid. Various technical ceramics, most metals and cermets are all
sintered in the presence of a liquid phase. It is rare that sintering with liquid phase does
not imply any chemical reactions, but in the simple case where these reactions do not
have a marked influence, surface effects are predominant. The main parameters are
therefore:
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i) quantity of liquid phase,
ii) its viscosity,
iii) its wettability with respect to the solid, and
iv) the respective solubilities of the solid in the liquid and the liquid in the solid:
The stages in liquid phase sintering
The shrinkage curve recorded during an isothermal treatment of liquid phase
sintering shows three stages:
viscous flow and grain rearrangement: when the liquid is formed, the limiting
process consists of a viscous flow, which allows the rearrangement of the grains.
The liquid dissolves the surface asperities and dissolves the small particles. The
granular rearrangement is limited to the liquid phase sintering itself, but it can be
enough to allow complete densification if the liquid phase is in sufficient quantity, as is
the case in the vitrification of silicate ceramics;
solution-reprecipitation: the solubility of the solid in the liquid increases at the interparticle points of contact. The transfer of matter followed by reprecipitation in the low
energy areas results in densification;
development of the solid skeleton: the liquid phase is eliminated gradually by the
formation of new crystals or solid solutions; we tend to approach the case of solid phase
sintering and the last stage of the elimination of porosity is similar to this case.
6- Sintering additives, Pressure sintering and hot isostatic pressing HIP
6-a Sintering additives
The impressive effect of the addition of a few hundred ppm of magnesia on the
sintering of alumina is the best example of the role of sintering additives. These
additives help to control the microstructure of the sintered materials; they can be
classified under two categories:
additives that react with the basic compound to give a liquid phase, for example by
the appearance of an eutectic at a melting point less than the sintering temperature.
We then go from the case of solid phase sintering to liquid phase sintering even if the
liquid is very insignificant. Silicon nitride Si3N4 ceramics are an example of where some
sintering additives are selected to react with the silica layer (SiO2) that covers the nitride
grains, in order to produce a eutectic. Thus, magnesia MgO reacts with SiO2 to form the
enstatite MgSiO3, from which we have a liquid phase at about 1,550C. The liquid film
wets the grain boundaries and aids sintering;
additives that do not lead to the formation of a liquid phase. These additives enable
the sintering to take place in solid phase. It alters the values of the diffusion coefficients
and the mobility of the grain boundaries. This is the case of the doping of Al2O3 with a
few hundred ppm of MgO, because the lowest temperature at which a liquid can appear
in the Al2O3-MgO system exceeds the sintering temperature (which, for alumina, does
not go beyond 1,700C).
6-b Applying a pressure during sintering (overview)
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In most cases, ceramics are sintered by pressureless sintering and it is only for very
special applications that we use "pressure sintering" or "hot pressing", which consists of
applying a pressure during the heat treatment itself. The characteristic of pressure
sintering is that the pressures brought into play which are usually about 10 to 70 MPa,
but can exceed 100 MPa have considerable effects and offering four Advantages:
i) thickening of materials whose interfacial energy balances are unfavorable;
ii) rapid densification at appreciably lower temperatures (several hundred degrees
sometimes) than those demanded by pressureless sintering;
iii) possibility of reaching the theoretical density (zero porosity);
iv) possibility of limiting the grain growth;
v) possibility to obtain the sintered part with its exact dimensions (net shape),
without the need for a machine finishing in applications that require high
dimensional accuracy.
Disadvantages of the pressure sintering
On the other hand, (1) the technical complexity of the process and (2) the high costs
acquired, as well as (3) the limitations on the geometry of the parts, which can only have
simple forms and a rather reduced size. (4) We must have pressurization devices
manufactured in materials that resist the temperatures required by sintering
Even if the sintering temperatures are lower compared to those required by
pressureless sintering, they are still high and the chemical reactions between these
materials and the environment must be limited. Examples are oxidation of refractory
metals and the reactions between the mould and the ceramic powder.
One last difficulty: (5) if the manufacture of parts with simple geometry (pellets) can
be done in a piston + cylinder mould (uniaxial pressure pressing), but, obtaining more
complex shapes, in particular undercut parts, cannot be done by pressure sintering. We
must then apply the technique of hot isostatic pressing or "HIP".
In cold isostatic pressing "CIP", the pressure is not transmitted by a piston but by a
gas, hence the hydrostaticity (isostaticity). In HIP, the pressure transmitting fluid is a
liquid and not a gas.
6-c Pressure sintering (experimental view)
Graphite is the most used material for the manufacture of the mould and the piston
of uniaxial pressure sintering equipments. That is because of its exceptional
refractoriness, with this originality that the mechanical strength grows when the
temperature rises (until beyond 2,000C). Also, graphite show easy machinability and
the generally limited speed of the reactions with the ceramic powders often protected
by a fine boron nitride deposit. However, the oxidation ability of the graphite requires a
reducing or neutral processing atmosphere, which is appropriate for non-oxides
(primarily carbides, like hot pressed silicon carbide HPSC, and nitrides, like hot pressed
silicon carbide HPSN). Refractory metals (Mo or W) and ceramics (Al 2O3 or SiC) have also
been used for the piston-cylinder couple of the mould.
23

Dr. Saad B. H.
Farid 2014-2015
The powders to be sintered are generally very fine (< 1 m) and it is not always
necessary for them to contain additives required by pressureless sintering (for example,
MgO for the sintering of Al2O3). The justifiable applications of pressure sintering are, for
example, cutting tools (ceramics or cermets) or optical parts, with the essential
objectives of achieving a 100% densification and/or very fine grains. However, the
microstructure and the crystallographic texture can present anisotropy effects because
of the uniaxial pressing. Alumina for cutting tools, carbides (B4C) or cermets are
examples of materials that can benefit from pressure sintering and HIP. The same is true
for metallic "superalloys" used in the hot parts of turbojets. High temperature composite
materials are another example where the application of a pressure during heat
treatments can be necessary to allow the impregnation of the fibrous wicks and favor
the densification.
Functional ceramics (BaTiO3 or, especially, magnetic ferrites) can gain from very fine
grains and the absence of residual porosity made possible by pressure sintering. As
optical transparency is no doubt the property that is most quickly degraded by the
presence of pores, even in extremely small numbers, perfectly transparent
polycrystalline ceramics (MgAl2O4, Al2O3, Y2O3, etc.) are examples of materials that
benefit from the use of pressure sintering.
As regards the mechanisms, pressure sintering implies:
i) rearrangement of the particles,
ii) lattice diffusion,
iii) grain boundary diffusion,
iv) plastic deformation and a viscous flow.
Pressureless sintering involves much less the effects i and iv. The dominant effects
are ii and iii due to the high level of the mechanical stresses.
6-d Hot isostatic pressing HIP (experimental view)
The pressurization fluid is a liquid for cold isostatic pressing CIP. In HIP, the fluid is a
gas (in general, argon, but reactive atmospheres are also used, for example oxygen) that
provides the pressurization.
We can imagine the risks of destructive explosions (use of a compressible fluid
instead of an incompressible fluid) and the difficulties in ensuring air-tightness as well as
the problems of pollution and control of thermal transfers: under a pressure of 1,000
atmospheres, a gas like argon has a density higher than that of liquid water at 20C! The
two main methods involving HIP are direct consolidation by HIP, and a pressureless
sintering followed by HIP (Figure).
24

Farid 2014-2015
Dr. Saad B. H.
Direct HIP (on the left) and post-sintering HIP (on the right)
Consolidation by HIP
When HIP is used directly to consolidate a powder, the "compact" must be
encapsulated in an envelope in a form homothetic to that of the part to be obtained,
with vacuum evacuation of gases, followed by sealing of the envelope. Soft or stainless
steels can be used as envelope materials for relatively low temperature treatments
(1,1001,200C), whereas it is necessary to use refractory metals (Ta, Mo) for higher
temperatures treatments. As the risks of distortion become higher when the overall
pressing increases, we gain from a powder pressed at a high rate and homogenously (by
CIP primarily). An alternative is to carry out a "pre-sintering" providing sufficient
cohesion to the part to make its handling possible, and then to coat it powdered glass,
which, at sufficient temperature, will become viscous enough to coat the piece with an
impermeable layer. This will make it possible for HIP to take place without the
pressurized gas being able to penetrate the open porosity.
HIP as post-sintering operation
This involves sintering the part until the inter-connected open porosity is eliminated
(which requires a densification of about 95%) and then subjecting this part to a
secondary HIP treatment. The greatest advantage is avoiding the need for an envelope
(cost, complexity, restrictions on the possible forms, necessity to clean the end product
to eliminate the envelope). It is furthermore possible, for manufacturers who do not have
an HIP equipment, to sub-contract this stage to a specialized partner. There are HIP
chambers whose size is more than one meter, which makes it possible to treat large
parts or a great number of small parts.
//
Glass and Glass ceramics
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Dr. Saad B. H.
Farid 2014-2015
7- Glass Definition and Transition temperature
Glass is an amorphous (non-crystalline) solid material, which is often transparent
and has widespread practical, technological, and decorative usage in things like
windowpanes, tableware, and optoelectronics. The most familiar, and historically the
oldest, types of glass are based on the chemical compound silica (silicon dioxide), the
primary constituent of sand. The term glass, in popular usage, is often used to refer only
to this type of material, which is familiar from use as window glass and in glass bottles.
Of the many silica-based glasses that exist, ordinary glazing and container glass is
formed from a specific type called soda-lime glass, composed of approximately 75%
silicon dioxide (SiO2), sodium oxide (Na2O) from sodium carbonate (Na2CO3), calcium
oxide, also called lime (CaO), and several minor additives. A very clear and durable
quartz glass can be made from pure silica; the other compounds above are used to
improve the temperature workability of the product.
The glassliquid transition (glass transition) is the reversible transition in amorphous
materials from a hard and relatively brittle state into a molten or rubber-like state. An
amorphous solid that exhibits a glass transition is called a glass. Super-cooling a viscous
liquid into the glass state is called vitrification.
Despite the massive change in the physical properties of a material through its glass
transition, the transition is not itself a phase transition of any kind; rather it is a
laboratory phenomenon extending over a range of temperature and defined by one of
several conventions.
Definition of glass:
The glass is an amorphous solid completely lacking in long range, periodic atomic
structure, and exhibiting a region of glass transformation (transition) behavior. Any
material, inorganic, organic, or metallic, formed by any technique, which exhibits glass
transformation (transition) behavior, is a glass.
Transition temperature Tg
The most frequently used definition of Tg uses the energy release on heating in
differential scanning calorimetry (DSC, see figure). Typically, the sample is first cooled
with 10 K/min and then heated with the same speed. In this context, Tg is the
temperature corresponding to point A on the curve. The linear sections are below and
above Tg. Tg is the temperature at the intersection of the regression lines. One definition
refers to the viscosity, fixing Tg at a value of 1013 poise (or 1012 Pas).
26

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Dr. Saad B. H.
8- Common types of glass

The following is a list of the more common types of silicate glasses, and their
ingredients, properties, and applications:
1.
Fused quartz, also called fused silica glass, vitreous silica glass, is silica
(SiO2) in vitreous or glass form (i.e., its molecules are disordered and random, without
crystalline structure). It has very low thermal expansion, is very hard, and resists high
temperatures (10001500C). It is also the most resistant against weathering (caused
in other glasses by alkali ions leaching out of the glass, while staining it). Fused quartz
is used for high temperature applications such as furnace tubes, lighting tubes,
melting crucibles, etc.
2.
Soda-lime-silica glass, window glass: silica (SiO2) 72% + sodium oxide (Na2O)
14.2% + lime (CaO) 10.0% + magnesia (MgO) 2.5% + alumina (Al2O3) 0.6%. It is
transparent, easily formed, and most suitable for window glass (flat glass). It has a
high thermal expansion and poor resistance to heat (500600C). It is used for
windows, some low temperature incandescent light bulbs, and tableware. Container
of Tg bythat is a slight variation on flat glass, which uses more
glassRight:
is a Determination
soda-lime glass
dilatometry and
less sodium and magnesium which are more water-soluble.
alumina and calcium,
This
makes it less
to water erosion.
Left: Measurement
of Tg susceptible
by
scanning
calorimetry glass, Pyrex: silica (SiO2) 81% + boric oxide (B2O3) 12% +
3. differential
Sodium
borosilicate
soda (Na2O) 4.5% + alumina (Al2O3) 2.0%. Stands heat expansion much better than
window glass. Used for chemical glassware, cooking glass, car headlamps, etc.
Borosilicate glasses (e.g. Pyrex) have as main constituents: silica and boron oxide.
They have fairly low coefficients of thermal expansion (7740 Pyrex CTE is 3.25106/C
as compared to about 9106/C for a typical soda-lime glass, making them more
dimensionally stable. The lower CTE also makes them less subject to stress caused by
thermal expansion, thus less vulnerable to cracking from thermal shock. They are
commonly used for reagent bottles, optical components, and household cookware.
27

Dr. Saad B. H.
Farid 2014-2015
4.
Lead-oxide glass, crystal glass: silica 59% + lead oxide (PbO) 25% +
potassium oxide (K2O) 12% + soda (Na2O) 2.0% + zinc oxide (ZnO) 1.5% + alumina
0.4%. Because of its high density (resulting in a high electron density) it has a high
refractive index, making the look of glassware more brilliant (called "crystal", though of
course it is a glass and not a crystal). It also has a high elasticity, making glassware
Table:
Some Raw
Materials
for very well.
'ring'. It is also more workable in the factory, but
cannot
stand
heating
Glassmaking
5.
Aluminosilicate glass: silica 57% + alumina 16% + lime 10% + magnesia 7.0%
+ barium oxide (BaO) 6.0% + boric oxide (B2O3) 4.0%. Extensively used for fiberglass,
used for making glass-reinforced plastics (boats, fishing rods, etc.) and for halogen
bulb glass.
6.
Oxide glass: alumina 90% + germanium oxide (GeO2) 10%. Extremely clear glass,
used for fiber-optic waveguides in communication networks. Light loses only 5% of its
intensity through 1 km of glass fiber. However, most optical fiber is based on silica, as
are all the glasses above.
Notes:
i. Another common glass ingredient is crushed alkali glass or "cullet" ready for recycled
glass. The recycled glass saves on raw materials and energy. Impurities in the cullet
can lead to product and equipment failure.
ii.
Fining agents such as sodium sulfate, sodium chloride, or antimony oxide may be
added to reduce the number of air bubbles in the glass mixture.
iii. Glass batch calculation is the method by which the correct raw material mixture is
determined to achieve the desired glass composition.
9- Raw Materials and Batch Calculations
Raw Materials
In general, glasses are produced either from high quality, chemically pure
components, or from a mixture of far less pure minerals. Research specimens, optical
glasses, and many glasses used for low volume, high technology applications are
produced using those chemicals we might routinely encounter in any chemical
laboratory.
Bulk commercial products, on
the other hand, are produced from
minerals, which typically have
names and compositions, which
are not familiar. The names of
many of these minerals and their
compositions are listed in the
adjacent table. Gravimetric
factors, which allow calculation of
the yield of the desired glass
component for each weight unit of
28

Farid 2014-2015
raw material, are also listed in this
table.
Exercise: use a table of atomic
weights and calculate the listed
Gravimetric Factors in the adjacent
table. Hint: List the weights of the
Oxides for yourself to simplify
calculations.
Oxide
BaO
CaO
PbO
Li2O
MgO
K2O
Na2O
ZnO
Fe2O3
MnO
TiO2
P2O5
SrO
ZrO2
H2O
F
B2O3
Al2O3
SiO2
Dr. Saad B. H.
MW
153.4
0
56.10
223.2
0
29.80
40.30
94.20
62.00
81.40
160.0
0
71.00
79.70
142.0
0
103.6
0
123.2
0
18.00
19.00
69.60
102.0
0
60.10
Batch Calculations
Batches containing only oxides
in their exact state as expressed
by the glass formula, for example,
involve very simple calculations,
while batches using a number of
different minerals, where a glass
component may be present in two
or more raw materials, require
much more complicated
calculations.
All batch calculations follow the same procedure. First, determine the weight fraction
of each component required to produce the desired molar composition. Begin by
multiplying the mole fraction of each component by the molecular weight of that
component. Next, total these contributions to determine the molecular weight of the
glass, and then divide each individual contribution by the molecular weight of the glass
29

Dr. Saad B. H.
Farid 2014-2015
to determine the weight fraction of each component. Finally, multiply the weight fraction
of each component by the amount of glass to be produced (Example 3.1). The batch
weight of any component, which decomposes during melting, is adjusted by multiplying
the weight fraction of that component by the appropriate gravimetric factor for the raw
material actually used in the batch (Example 3.2). Use of raw materials, which supply
more than one batch component, requires additional calculations, as illustrated in
Example 3.3.
If we use albite feldspar as the source of alumina, we also obtain some of the soda
and silica needed for the batch. Using the gravimetric factors for albite in the table, we
find that we that 41.89 g of albite will yield the required 8.15 g of alumina. This amount
of albite also yields 4.95 g of soda and 28.89 g of silica (divide the weight of albite by
the gravimetric factor to find the yield for a given amount of albite). After subtracting
these quantities from the required amounts of soda and sand, we find that we must add
14.85 g of soda and 43.11 g of sand. If we use Na2CO3 as the source of the additional
30

Dr. Saad B. H.
Farid 2014-2015
soda, we will require 14.85 x 1.71 = 25.39 g of Na2CO3. Final Batch: Na2CO3 = 25.39 g,
Albite = 41.89 g, Sand = 43.11 g
10- Viscosity of Glass Forming Melts
Viscosity Definitions and Terminology
Viscosity is a measure of the resistance of a liquid to shear deformation, i.e., a
measure of the ratio between the applied shearing force and the rate of flow of the
liquid. If a tangential force difference, F, is applied to two parallel planes of area, A,
which are separated by a distance, d, the viscosity,, is given by the expression:
=Fd/Av, where v is the relative velocity of the two planes. [Pa.s], 1 Pa.s=10 Poise
If the velocity varies directly with the applied shear force, the viscosity is
independent of force and the liquid is said to behave as a Newtonian liquid. At high
shear stresses, many glass forming melts exhibit an apparent decrease in viscosity with
increasing shear stress. This form of non-Newtonian behavior is known as pseudoplastic flow, or shear-thinning, and is important in high shear rate forming processes.
Fluidity is the reciprocal of the viscosity, often used with ordinary liquids.
A number of specific viscosities have
been designated as reference points on
the viscosity-temperature curve for melts.
These particular viscosities have been
chosen because of their importance in
various aspects of commercial or
laboratory processing of glass forming
melts. These reference points are
summarized in the adjacent table, and
are shown on a typical curve of viscosity
versus temperature for a soda-lime-silica
melt in next figure.
Common
Viscosity Measurement Techniques
1. Rotation Viscometers: They are
commonly used at room temperature
to measure the viscosity of a wide
variety of liquids in the range of 1 to l04
Pa.s. Use of these viscometers at
temperatures up to 1600C requires
that the parts exposed to the melt be
constructed of platinum or platinum
alloys. These viscometers consist of a
small cylinder, or spindle, which is
rotated inside a large cylindrical
crucible containing the melt.
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Dr. Saad B. H.
Farid 2014-2015
Alternative designs of these
viscometers enable them to measure
viscosities up to 109 P.s.
2. Falling Sphere Viscometers: Viscosities can be measured directly through the
determination of the resistance of a liquid to the motion of a sphere falling through the
liquid under the influence of gravity. This method yields data in the range 1 to l06 Pas.
3. Fiber Elongation Viscometers: The most widely used viscometers are based on
measurements of the rate of elongation of a fiber of known dimensions under a known
load. This method can be used for viscosities ranging from l05 to 10l2 Pa.s.
4. Beam-Bending Viscometers: Transformation range viscosities of l08 to 1013 Pa.s are
often measured by the beam-bending method, in which a small beam of known crosssectional area, A, is placed in a 3-point bending configuration with a load, M, applied
at the center of the beam.
Temperature Dependence of Viscosity
The viscosity can often be fitted, at least over limited
temperature ranges, by an Arrhenian expression of the
adjacent form:
The o is a constant; H is the activation energy for viscous flow, R is the gas
constant, and T is the temperature in K. In general, Arrhenian behavior is observed
within the glass transformation range (1013 to l09 Pa.s) and at high temperatures where
melts are very fluid.
However, the activation energy for viscous flow is much lower
for the fluid melt than for the high viscosity of the transformation
region. Thus, The Vogel-Fulcher-Tamman VFT equation adds a third
fitting variable, To, to the Arrhenian expression to account for the
variability of the activation energy for viscous flow. In addition, H
is replaced with a new variable, B, as indicated by the adjacent
expression:
Actually, researchers found that B is composition dependent and utilize it to model
composition-viscosity relation at different temperatures. Dr. Saad B. H. Farid published a
complete model for the bioactive glass.
11- Thermal Expansion of Glass
The coefficient of linear thermal expansion
Typical curve for viscosity as a function of

(NIST
temperature
is defined for
asasoda-lime-silica
= [L/L0].T,melt
where
L
Standard No. 710).
is
the change of length of a material of initial length L0 heated to a temperature difference

T. The units of are reciprocal degrees.
The coefficient usually depends upon
temperature, as shown in the figure. Thus, it is
necessary to specify the temperature range
over which L is measured. The usual range is
from 0 to 300C, or from room temperature to
a temperature just below the glass transition
32

Farid 2014-2015
range, where volume changes become
greater.
Dr. Saad B. H.
A volume expansion coefficient can be

defined as [V/V0].T for a volume change V
and initial volume V0. If V is small, as is
usually the case, the volume coefficient equals
3. The density and specific volume V of the
glass at temperatures up to the strain
temperature can be calculated from the
density 0 at 25C and the coefficient of
thermal expansion:
V = [1 / 0] [1 + 3 ( T - 25 )] , = 0 / [1 + 3 ( T 25 )], where T is the temperature
in C.
Thermal shock resistance and the fracture of seals between different materials
depend on thermal expansion. Thus, the expansion of glass as the temperature is
increased is an important measure of its resistance to thermal shock. The higher the
expansion coefficient, the more likely is fracture during rapid heating and cooling. Nonuniform volume changes, resulting from temperature gradients during heating or
cooling, cause stresses that are larger the greater the volume changes. A vitreous silica
beaker heated to 1000C can be dashed into water without breaking it, because it has
the low expansion coefficient of about 0.5 10-6 C-1. On the other hand, a plate of sodalime glass 0.6 cm thick, with a coefficient of about 9 10-6 C-1, can be cracked with a
temperature difference between faces of about 50C.
Matching of expansion coefficients of two materials being sealed together is essential
to prevent fracture in the seal during heating or cooling. A difference in coefficients of
less than about 0.2 10-6 C-1 is optimum for glass sealing, although acceptable seals
can often be made with differences up to about 0.5 10-6 C-1. The greater the
difference, the more likely is failure of the seal. Other factors that influence the strength
Fractional change in length plotted against
of a seal are its geometry, the completeness of removal
of residual
stressesglass
by
temperature
for an annealed
annealing, and differences in strain temperatures in sealing two glasses. Special seal
designs allow materials with large differences in coefficients of thermal expansion to be
sealed together.
The change in length of a glass rod can be measured with a dilatometer, in which the
increase in length of a glass rod is compared to that of a vitreous silica rod. Both rods are
held in the same furnace and heated together at a constant rate, and the difference in
their lengths is measured with a differential sensor.
The coefficient of thermal expansion also is a function of composition. This is
extremely important to learn for the designers of glazes, enamels, dental porcelains
(special types of enamels and glazes for synthetic dents), metal seals etc. Usually,
each composition material has linear contribution to the thermal expansion of glass, but
33

Dr. Saad B. H.
Farid 2014-2015
anomalies are frequently found especially with the contribution of alkalis. Again, a work
published by Dr. Saad B. H. Farid explains this anomaly for the (sodium-potassiumborate) solder glass.
The next table is a simple example of the composition dependence of both Tg and the
coefficient of thermal expansion. The values of the coefficient of thermal expansion
displayed in the tables are multiples of 10-7 C as usually found in glass industry
documentations.
12- Vitreous Coating

Definition of the Vitreous Coating
Vitreous Coating includes coating of a ceramic part (glazing) and coating of metallic
part (enamel). Coating includes physical and chemical adhesion; in addition, matching
thermal expansion and attaining the correct coating temperature are of prime
importance. Actually, in synthetic dental coating, it is known that the difference in
thermal expansion should not exceeds +0.310-6C-1 and coating temperature of +50C
of the coat compared with the coated surface.
General Description of the Vitreous Coating
1. The glaze layer deposited on the part generally has a thickness ranging between 0.15
and 0.5 mm. Its purpose is to mask the porosity and/or the color of the part, to make
the surface of the piece smooth and brilliant and to improve the chemical resistance
of the ceramic.
2. This layer, transparent or opaque, white or colored, is obtained from a silica-rich
ceramic composition capable of developing glass during the heat treatment.
3. The composition of the glaze also contains many other constituents, in particular
alkaline and alkaline earth oxides. They help to adjust the melting point, the thermal
34

Dr. Saad B. H.
Farid 2014-2015
expansion coefficient, the surface tension, and the viscosity to the glazing conditions,
and ensure the wetting and adhesion of the glaze on the part.
4. The enamels used for sheet enameling have many common points with those
described here.
Composition of the Vitreous Coating
1. The properties of the coat are often analyzed by considering that it is made up of a
combination of acid oxides responsible for the vitreous structure (mainly SiO 2 and
B2O3), amphoteric oxides (Al2O3), and basic oxides (K2O, Na2O, CaO, MgO, PbO).
2. It should be noted that the role of flux, traditionally reserved for basic oxides, is now
increasingly played by acid or amphoteric oxides, such as B2O3 or Bi2O3.
3. Vitreous coat is obtained from a mixture of raw materials mineral and/or ground frits.
The raw materials used are mainly feldspars, kaolin, quartz and chalk CaCO3 or
dolomite CaMg(CO3)2.
4. Frits are mixtures of components prepared by melting several compounds at high
temperature (T > 1,400C). After quenching in air or water, the product, which is
markedly vitreous in character, is ground.
5. In order to improve frit layer adhesion to the surface of the part, water-soluble salts,
kaolin, or volatile oxides can be used without harm in the composition of the coat.
6. We can distinguish raw vitreous coat formed only from natural raw materials and fired
vitreous coat. Fired vitreous coat are particularly suitable for low temperature
applications that require flux bases, richer in basic elements, which are non-existent
in nature.
7. The role of ground frits in the composition of the vitreous coat is mostly to reduce the
firing temperature and shorten the heat treatment. Ground frits are widely used for
the glazing of the tiles in the fast sintering process (one step sintering and glazing
process).
8. It is customary to classify the various types of vitreous coat, based on the nature of
the flux used. Thus, we can distinguish lead vitreous coat (PbO rich), boron oxide,
alkaline, alkaline earth, zinc oxide, and bismuth oxide vitreous coat.
9. Lead vitreous coats, historically the oldest, were the most commonly used for a long
time. Because of the toxicity of lead, there is a trend to be replaced by vitreous coat
containing a very small quantity of bismuth oxide (< 5% mass) and, especially by
alkaline borosilicate products.
10. Porcelain enamel ground coats contain adherence oxides, while cover coat
enamels do not. The most essential property of a ground coat is adherence to the
metal substrate. While the cover coat serve for appearance and chemical resistance
etc.
Porcelain enamel
1. The adherence of the ground coat is accomplished via adding certain metallic oxides
to the enamel formulation to promote this bonding process. Chief among these
adherence oxides is cobalt oxide. Normally 0.01 to 0.02 molar ratio is considered
necessary. Second in importance is nickel oxide, which may be used in molar ratio of
0.02 to 0.04. To a lesser degree, cupric oxide, manganese oxide, and iron oxide may
35

Dr. Saad B. H.
Farid 2014-2015
be used. The specific amounts depend upon details of the enamel's total formulation,
processing, and service requirements.
2. Porcelain enamel cover coats are designed to provide specific color and appearance
characteristics combined with resistance to atmospheric and liquid corrosion, surface
hardness, abrasion resistance, and resistance to heat and thermal shock, as required.
Cover coat formulations are available to provide a wide variety of appearance
properties. They range from opaque whites through pastels and medium-strength
colors to strong, dark colors. A wide selection of glosses is also available, ranging
from the high-gloss sanitary ware finishes to the full-matte architectural enamels.
3. Porcelain enamel cover coats are classified as opaque (by ZrO2, antimony oxides
SbO, TiO2, semi-opaque, and clear. Opaque enamels are used for white and pastel
(muted vivid) cover coats, semi-opaque enamels are used for most of the medium
strength colors, and clear enamels are necessary to produce bright (by alkalis
especially Li2O), strong colors.
13- Bioactive Glasses and Glass-Ceramics
Introduction
Glass-ceramics are an important class of materials that have been commercially
quite successful. They are polycrystalline materials produced by the controlled
crystallization of glass. They are composed of randomly oriented crystals with some
residual glass, typically between 2 and 5 percent, with no voids or porosity. Glass
ceramics found wide applications as dielectric materials, machinable materials,
biomaterials etc.
Ceramics, glasses, and glass-ceramics include a broad range of inorganic/nonmetallic
compositions. In the medical industry, these materials have been essential for
eyeglasses, diagnostic instruments, chemical ware, thermometers, tissue culture flasks,
and fiber optics for endoscopy. Insoluble porous glasses have been used as carriers for
enzymes, antibodies, and antigens, offering the advantages of resistance to microbial
attack, pH changes, solvent conditions, temperature, and packing under high pressure
required for rapid flow. Ceramics are also widely used in dentistry as restorative
materials such as in gold-porcelain crowns, glass-filled ionomer cements, and dentures.
This section focuses on ceramics, glasses, and glass-ceramics used as implants.
Although dozens of compositions have been explored in the past, relatively few have
achieved clinical success. The science and practice of biomaterials examines differences
in processing and structure, describes the chemical and microstructural basis for their
differences in physical properties, and relates properties and tissue response to
particular clinical applications.
It is essential to recognize that no one material is suitable for all biomaterial
applications. As a class of biomaterials, ceramics, glasses, and glass-ceramics are
generally used to repair or replace skeletal hard connective tissues. Their success
depends upon achieving a stable attachment to connective tissue.
36

Dr. Saad B. H.
Farid 2014-2015
Types of Bioceramics Tissue Attachment
The mechanism of tissue attachment is directly related to the type of tissue response
at the implanttissue interface. No material implanted in living tissue is inert because
all materials obtain a response from living tissues. There are four types of implant-tissue
response:
1. Biocompatibility is lacking: in this case, the materials cause tissue reactions, which
may be systemic or local. Systemic responses can be toxic or allergic and triggered by
the products of metallic corrosion and polymer degradation, release of micro particles
from materials, and the presence of contaminants.
2. Biocompatible / Bioinert / Biotolerant: If the material is nontoxic and biologically
inactive (nearly inert), then, fibrous tissue of variable thickness forms.
3. Bioactive: If the material is nontoxic and biologically active, an interfacial bond
forms.
4. Bioresorbable: If the material is nontoxic and dissolves, the surrounding tissue
replaces it. I.e. the material is gradually resorbed before they finally disappear, and is
totally replaced by new tissues in vivo.
There are four different types of attaching prostheses (an artificial body part) to the
skeletal system. Types of bioceramic-tissue attachment and their classification are:
Type of attachment
Example
Dense, nonporous, nearly inert ceramics attach by

bone growth into surface irregularities by cementing
the device into the tissues or by press-fitting into a
defect {termed "morphological fixation")
A12O3 (single crystal and

polycrystalline)
For porous inert implants, bone ingrowth occurs that

mechanically attaches the bone to the material
(termed "biological fixation"). Hydroxyapatite-coated
porous metals
A12O3 (polycrystalline)
3.
. Dense, nonporous surface-reactive ceramics,

glasses, and glass-ceramics attach directly by
chemical bonding with the bone (termed "bioactive
fixation")
Bioactive glasses
Bioactive glass-ceramics
Hydroxyapatite HA
4.
Dense, nonporous, (or porous) resorbable ceramics

are designed to be slowly replaced by bone.
1.
2.
Calcium sulfate (plaster of

paris)
Tricalcium phosphate
Calcium-phosphate salts
Bioactive Glasses and Glass Ceramics

Certain compositions of glasses, ceramics, glass-ceramics, and composites have
been shown to bond to bone. These materials have become known as bioactive
ceramics. Some even more specia1ized compositions of bioactive glasses will bond to
soft tissues as well as bone. A common characteristic of bioactive glasses and bioactive
ceramics is a time dependent kinetic modification of the surface that occurs upon
37

Dr. Saad B. H.
Farid 2014-2015
implantation. The surface forms a biologically active carbonated HA layer that provides
the bonding interface with tissues.
Bioactive materials develop an adherent interface with tissues that resist substantial
mechanical forces. Bonding to bone was first demonstrated for a compositional range of
bioactive glasses that contained SiO2, Na2O, CaO, and P2O5 in specific proportions. There
are three key compositional features to these bioactive glasses, which distinguish them
from traditional soda-lime-silica glasses:
1. Less than 60 mol% SiO2
2. High Na2O and CaO content
3. High CaO/P2O5 ratio
These features make the surface highly reactive when it is exposed to an aqueous
medium.
Many bioactive silica glasses are based upon the formula called 45S5, signifying 45
wt% SiO2 (S the network former) and 5:1 ratio of CaO to P2O5. Glasses with lower ratios
of CaO to P2O5 do not bond to bone. However, substitutions in the 45S5 formula of 5-15
wt% B2O3 for SiO2 or 12.5 wt% CaF2 for CaO or heat-treating the bioactive glass
compositions to form glass-ceramics have no measurable effect on the ability of the
material to form a bone bond but only lowering the melting temperature and increase
the microstructure homogeneity. However, adding as little as 3 wt% A12O3 to the 45S5
formula prevents bonding to bone.
38

Ceramics and Glasses 3rd Year - Lecture Notes

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Zirconia, Other oxides