12 Kalemtas A Ceramics Materials

CERAMIC
MATERIALS I
Asst. Prof. Dr. Ayşe KALEMTAŞ
akalemtas@mu.edu.tr, akalemtas@gmail.com, Phone: 211 19 17

Metallurgical and Materials Engineering Department
INTRODUCTION
MATERIALS
CERAMIC METAL POLYMER COMPOSITE

D
CLAY REFRACTORIES ADVANCED

GLASSES PRODUCTS
ABRASIVES CEMENTS
CERAMICS
Glass-
Glasses
ceramics

INTRODUCTION
HISTORY DEFINITION PROPERTIES APPLICATIONS

INTRODUCTION
Four of the major technological achievements in

glass which have had the most profound impact on
mankind.
 Glass window – which enables sunlight to come into

dwelling unit
 Lenses – opthamics for improved vision, microscope,
telescope optics
 Light bulb envelope - lighting
 Semiconducting glasses – for computer memory,
solar cell, photocopiers

Well Known Glass Products
www.whitersstreetglass.com.au
Glass splashbacks http://www.wickedreport.com
Hirom Glass Violin is a product of Hario
www.toxel.com Glass Co. Ltd., Japan. And also, The
Glass Bathtub world’s first hand made glass violin.
http://freshome.com http://worlds-interior-design.blogspot.com
Superdurable tempered glass Wall-to-wall glass windows

Tempered glass table http://freshome.com

http://www.ifjk.org
www.aarticommercial.com/prod
www.tripadvisor.com ucts.php Heat resistant
Glass sink cabinets in the bathroom Laminated Windscreen Glass glass door

http://www.wolfard.com
Classic Wolfard Oil Lamp
Heat resistant glass

Heat resistant glassware lid
Tempered Glass
(microwave safe) Cutting Board
INTRODUCTION
Any material that exhibits only a short-range order of atoms

or ions is an amorphous material; that is, a noncrystalline
one.
In general, most materials want to form periodic

arrangements since this configuration maximizes the
thermodynamic stability of the material. Amorphous
materials tend to form when, for one reason or other, the
kinetics of the process by which the material was made did
not allow for the formation of periodic arrangements.
Glasses, which typically form in ceramic and polymer

systems, are good examples of amorphous materials.

INTRODUCTION
Definitions of Glass
The origin of the word glass is the late Latin term glæsum used to refer to a
lustrous and transparent or translucent body.
Glassy substances are also called vitreous, originating from the word
vitrum, again denoting a clear, transparent body. Although glass became a
popular commodity in the growth of civilization, perhaps because of its
transparency, luster (or shine), and durability, the current understanding of
glass no longer requires any of these characteristics to distinguish it from other
substances.
Glass can be inorganic (non-carbon based) as well as organic (carbon-

based), and fusion is not the only method to make a glass.
Thus, the old ASTM definition that glass is an inorganic product of fusion which
has been cooled to a rigid condition without crystallizing is not appropriate.
Handbook of Ceramics, Glasses, and Diamonds, Charles A. Harper Editor-in-Chief, Chapter:5, Inorganic Glasses-
Structure, Composition and Properties, Arun K.Varshneya and Thomas P. Seward III, McGRAW-HILL
INTRODUCTION
Methods of Making Inorganic Glasses
The most common method for making glass is to:
 Fuse various raw materials in appropriate proportions together with the application of
heat,
 Gather and form into useful products,
 Cool subsequently at a rate fast enough to avoid distortion of the shape yet slow enough
to avoid cracking.
Inorganic glasses may also be obtained by
 Hydrolyzing an alcoholic solution of an organometallic compound,

 Stirring the hydrolyzed product to allow rapid chelation to a gel state,
 Drying the gel mass to drive off the organics,
 Sintering at an elevated temperature to obtain a compact.
This method, called the sol-gel route to glassmaking, is often used to deposit thin films such as
antiref lection coatings.
The sol-gel process of making a glass avoids the normally high temperatures employed for the
fusion of glass. Chemical vapor deposition is yet another technique which completely avoids
fusion of constituent materials.
INTRODUCTION
The earliest written records of glass making are some
famous clay tablets, dating from around 650 BC, from the
library of Assur-bani-pal, but these are incompletely
understood because we have no dictionary to explain the
technical terms.
Many centuries passed before written accounts of glass

making contained any useful insight besides recipes to be
followed by rote.
The earliest development in glass making of which we have

a reasonably documented description seems to be the
invention of glass of lead by Ravenscroft around 1673-1676.

Glass from Nature
Natural Glass
Probably as early as 75,000 B.C.E., long before human beings had

learned how to make glass, they had used natural glass to fashion knives,
arrowheads, and other useful articles.
The most common natural glass is obsidian, formed when the heat of
volcanoes melts rocks such as granite, which then become glassy upon
cooling. Other natural glasses are pumice, a glassy foam produced from
lava; fulgurites, glass tubes formed by lightning striking sand or sandy
soil; and tektites, lumps or beads of glass probably formed during
http://www.chemistryexplained.com/Ge-Hy/Glass.html#ixzz3G6sDTQBl

Glass from Nature
Obsidian
The first glass, used by early man is obsidian. Ryolite lava flows from volcanoes and swiftly cools, impeding
the formation of crystals and creating absidian glass. This glass has an irregular structure
and, therefore, fractured into smooth curved shapes with finer edges. Around the world, many early cultures
discovered these properties and utilized this glass in weapons, tools, and decoration.
Uses of Obsidian as a Cutting Tool
The conchoidal fracture of obsidian causes it to break into pieces

with curved surfaces. This type of fracturing can produce rock
fragments with very sharp edges. These sharp fragments may
have prompted the first use of obsidian by people.
The first use of obsidian by people probably occurred when a sharp

piece of obsdian was used as a cutting tool. People then
discovered how to skillfully break the obsidian to produce cutting
tools in a variety of shapes. Obsidian was used to make
knives, arrow heads, spear points, scrapers and many other
weapons and tools.
Once these discoveries were made, obsidian quickly became the

raw material of preference for producing almost any sharp object.
The easy-to-recognize rock became one of the first targets of
organized "mining". It is probably a safe bet that all natural obsidian
outcrops that are known today were discovered and utilized by
ancient people.
http://geology.com/rocks/obsidian.shtml Asst. Prof. Dr. Ayşe KALEMTAŞ

Glass from Nature
Obsidian is a popular jewelry stone.
A thin piece of obsidian is often used as a "backing"

material for opal doublets and triplets. The black
obsidian adds stability to the opal and provides a
dark background color that contrasts with the opal's
fire.
Mahogany obsidian and snowflake obsidian

cabochons set in a sterling silver pendants.
Freshly broken pieces of obsidian have a very high luster. Ancient people noticed that they
could see a reflection in obsidian and used it as a mirror.

Glass from Nature
Obsidian in Modern Surgery
Although using a rock as a cutting tool might sound like "stone age
equipment", obsidian continues to play an important role in modern
surgery.
Obsidian can be used to produce a cutting edge that is thinner and

sharper than the best surgical steel.
Today, thin blades of obsidian are placed in surgical scalpels used for
some of the most precise surgery.
In controlled studies, the performance of obsidian blades was equal to or

superior to the performance of surgical steel.

Glass from Nature
magma fulgurite
obsidian
tektites
Manmade (Synthetic) Glass
When, where, or how human beings discovered how to make glass is not known.
Very small dark-colored beads of glass have been dated back to
4000 B.C.E. These may well have been by-products of copper smelting or pottery
glazing.
By 2500 B.C.E. small pieces of true synthetic glass appeared in areas such as
Mesopotamia, but an actual glass industry did not appear until about
1500 B.C.E. in Egypt. By this time various small vases, cosmetic jars, and jewelry
items made of glass had begun to appear.
All the ancient glasses were based on silica (sand), modified with considerable
amounts of various metal oxides, mainly soda (Na2O) and lime (CaO). This is still
the most common glass being used today. It is known as soda lime glass.
However, the ancient glass was usually colored and opaque due to the presence
of various impurities, whereas most modern glass has the useful property of
transparency.
http://www.chemistryexplained.com/Ge-Hy/Glass.html#ixzz3G6so8r7V

GLASS
- 4000: Jewel in molted glass

-(Phoenicia)

GLASS
-1500: Vases and vessels
(Egypt)

GLASS
Egyptians Romans Middle Ages
• First people to • By Roman times • Main achievements

realize what could glass being blown were colored glass
be done with glass and molded, cut and windows.
when it is hot and engraved, and
plastic. painted.
• Made vessels for
cosmetics and
perfumes by forming
molten glass around
a shaped core.

INTRODUCTION
A glass is a solid that possesses no long-range atomic order

and which undergoes the glass transformation from solid to
supercooled liquid on heating.
Crystalline materials have a definite structure, whereas amorphous ones do

not, and therefore only rather general statements can be made about a material
which, when hot, is ductile but when cold is brittle, and fractures if there is a
sudden change of temperature.
No melting
Resemble point,
Amorphous No crystal No long-
“frozen a glass
solids structure range order
liquids” transition
temperature

INTRODUCTION
Glasses do not solidify at an
exact temperature (the
melting temperature, Tm,) as
is known for crystalline
materials, but instead in a
rather broad temperature
range.
Specifically, upon cooling, a

glass becomes increasingly
viscous (like honey).
Concomitantly, the specific

volume, Vs, of the glass (that
is, the volume per unit mass),
decreases continuously upon
cooling whereas for crystalline
Schematic representation of the temperature solids a sudden drop of Vs at
dependence of the specific volume, Vs, for a glass
and a crystalline substance.
the melting temperature is
observed.
Understanding Materials Science, Rolf E. Hummel, Second Edition, Springer, 2004. Asst. Prof. Dr. Ayşe KALEMTAŞ
INTRODUCTION
The contraction of glasses
during cooling is a
combination of two effects.
The first one occurs, as in

most crystalline
substances, by reducing the
interatomic distances.
The second contraction

mechanism is due to a
rearrangement of atoms. As
the glass cools, the atomic
rearrangement becomes
slower until a temperature is
eventually reached at which
Schematic representation of the temperature the viscosity is so high that any
dependence of the specific volume, Vs, for a glass further structural change is
and a crystalline substance. nearly impossible.
INTRODUCTION
Below this temperature, Tg, the
volume of the glass contracts at a
fixed rate that is determined by the
present structure.
The intermediate range between

Tg and Tm is called the glass
transition or glass
transformation range.
Tg is then defined to be that

temperature at which, during
cooling, the Vs versus T curve
reaches an essentially constant
slope.
Above Tg, the material is defined to

be a supercooled liquid, or
Schematic representation of the temperature eventually a liquid.
dependence of the specific volume, Vs, for a glass
and a crystalline substance.
Below Tg, it is a solid (i.e., a glass).
INTRODUCTION
For practical reasons, the
“melting point” of glasses is
defined to be that temperature at
which the viscosity is 10 Pa.s.
The intersection of the two

straight portions of the Vs versus
T curve for glasses is called the
fictive temperature, Tf.
Because of the high viscosity of

most glasses and the
consequential low mobility of the
atoms, any crystallization (called
deglassing or devitrification) is
very sluggish.
Nevertheless, extremely slow
Schematic representation of the temperature cooling rates or prolonged
dependence of the specific volume, Vs, for a glass heating at high temperatures
and a crystalline substance. eventually causes devitrification.
INTRODUCTION
As a matter of fact, glass is a
material that has quite a low linear
expansion coefficient, which is
about 1/5 of that for crystalline
silica.
Incidentally, the expansion

coefficient of crystalline silica
changes abruptly at the
temperature at which the allotropic
transformation between -quartz to -
quartz takes place.
Commercially important is Pyrex, a

borosilicate glass whose thermal Comparison of the linear expansion l/l of
expansion coefficient is only 1/3 of glass, crystalline silica, and a typical metal
that for common soda–lime glass. as a function of temperature
INTRODUCTION
Glass is a very
brittle material
Glass is a linear elastic and

isotropic material with no plastic
behavior at normal
temperatures, which can explain its
brittle fracture. It follows Hooke’s
law.

INTRODUCTION
Glasses  brittle fracture !!!

INTRODUCTION
• Glass has amorphous structure
• Crystalline materials have some periodic crystal structure that results in
long term order
Glass is a state of matter. It is a solid produced by cooling molten material so that the internal
arrangement of atoms, or molecules, remains in a random or disordered state, similar to the
arrangement in a liquid. Such a solid is said to be amorphous or glassy. Ordinary solids, by
contrast, have regular crystalline structures.
http://www.chemistryexplained.com/Ge-Hy/Glass.html#ixzz3G6raJsdx
INTRODUCTION
Two-dimensional illustrations of the structures of (a) crystalline

silica, (b) liquid or glassy silica and (c) glassy or vitreous silica
containing some sodium oxide

General Characteristics of Glasses
Structure is
Short range
isotropic, so the
atomic order but
properties are
no long-range
uniform in all
order
directions
Soften before
Typically good melting, so they
electrical and can be formed
thermal easily by various
insulators forming
techniques

INTRODUCTION
General properties of glasses

 High hardness / brittle
 Low density compared to high strength
 Low thermal expansion coefficient
 Low heat / electrical conductivity
 High melting point
 Good chemical resistance / chemically inert
 Wide range of optical transmission
Transparent
Translucent
Opaque
INTRODUCTION
Advantages Disadvantages
 Inert  Brittle
 Does not corrode  Breakable
 Durable  Heavy
 Optical transparency
 Many forming method
 Many composition
 Cheap

INTRODUCTION
Starting ceramic
Final product
powders
Batching and
mixing of raw Homogenisation
materials
Batch melting Fining

Glass is prepared by
cooling from a liquid
state without
crystallization

GLASS COMPOSITION
1. Glass forming oxides: usually the dominant constituent

SiO2, B2O3, P2O5, etc.
2. Fluxes: reduce melting temperatures
Na2O, PbO, K2O, Li2O, etc.
3. Property modifiers: added to tailor chemical durability,
expansion, viscosity, etc.
CaO, Al2O3, etc.
4. Colorants: oxides with 3d, 4f electron structures; minor additives
(<1 wt%)
5. Fining agents: minor additives (<1 wt%) to help promote bubble
removal
As-, Sb-oxides, KNO3, NaNO3, NaCl, fluorides, sulfates

ORDINARY GLASS FABRICATION
SAND SODA LIME OTHER GLASS
Percentage of Ingredients in Glass

INTRODUCTION
RAW MATERIALS
NETWORK
FORMERS
MODIFIERS INTERMEDIATES

INTRODUCTION
RAW MATERIALS
The most essential component of any glass batch is always the glassformer. Every
glass contains one or more components which serve as the primary source of the
structure. If most of the glassformer present in a specific sample is silica, for example,
NETWORK
that glass is called a silicate. If a significant amount of boric oxide (B2O3) is also
FORMERS
present, in addition to silica, the sample is termed a borosilicate glass. The primary
glassformers in commercial oxide glasses are SiO2, B2O3, and P2O5, which all readily
form single component glasses.
A large number of other compounds may act as glassformers under certain

circumstances, including GeO2, Bi2O3, As2O3, Sb2O3, TeO2, Al2O3, Ga2O3, and
V2O5. With the exception of GeO2 these oxides do not readily form glasses by
themselves unless very rapidly quenched or vapor deposited, but can serve as
INTERMEDIATES
glassformers when mixed with other oxides. The elements S, Se, and Te act as
glassformers in chalcogenide glasses. Although halide glasses can be made in
many systems, with many different compounds acting as glassformers, the two
most common halide glassformers are BeF, and ZrF,.
The degradation in properties is usually countered by addition of property

modifiers, which include the alkaline earth and transition metal oxides. While these
oxides partially counter the reduction in processing temperature obtained by addition
MODIFIERS
of fluxes, they also improve many of the properties of the resulting glasses. The
properties are thus modified, or adjusted, by careful control of the amount and
concentration of these oxides to obtain precisely the desired results.
INTRODUCTION
RAW MATERIALS
Division of the oxides into glass

formers, intermediates, and modifiers
Glass Formers Intermediates Modifiers

B2O3 TiO2 Y2O3
SiO2 ZnO MgO
GeO2 PbO2 CaO
P2O5 Al2O3 PbO
V2O3 BeO Na2O

INTRODUCTION
RAW MATERIALS
COLORANTS AND REFINERS
Colorants are used to control the color of the final glass. In most cases, colorants are oxides of
either the 3d transition metals or the 4f rare earths. Uranium oxides were once used as
colorants, but their radioactivity obviously reduces their desirability for most applications. Gold
and silver are also used to produce colors by formation of colloids in glasses. Colorants are
only used if control of the color of the glass is desired, and are usually present in small
quantities. Iron oxides, which are common impurities in the sands used to produce commercial
silicate glasses, act as unintentional colorants in many products. When colorants are used to
counteract the effect of other colorants to produce a slightly gray glass, they are referred to as
decolorants.
Fining agents are added to glass forming batches to promote the removal of bubbles from the
melt. Fining agents include the arsenic and antimony oxides, potassium and sodium
nitrates, NaCl, fluorides such as CaF,, NaF, and Na,AlF,, and a number of sulfates. These
materials are usually present in very small quantities (< 1 wt%), and are usually treated as if
they have only minor effects on the properties of the final glasses. Their presence, however, is
essential in many commercial glasses, which would be prohibitively expensive to produce
without the aid of fining agents in reducing the content of unwanted bubbles in the final
product.
INTRODUCTION
Important
temperatures
in glasses
can be defined
by viscosity
Logarithm of viscosity versus temperature for fused silica and three silica glasses. (From E. B.
Shand, Engineering Glass, Modern Materials,Vol. 6, Academic Press, New York, 1968, p. 262.) Asst. Prof. Dr. Ayşe KALEMTAŞ
INTRODUCTION
On the viscosity scale, several

specific points that are important
in the fabrication and processing
of glasses are labeled:
1. The melting point

corresponds to the
temperature at which the
viscosity is 10 Pa.s (100 P); the
glass is fluid enough to be
considered a liquid.
2. The working point

represents the temperature at
which the viscosity is 103 Pa.s
(104 P); the glass is easily
deformed at this viscosity.
INTRODUCTION
3. The softening point, the
temperature at which the viscosity is
4x106 Pa.s (4x107 P), is the maximum
temperature at which a glass piece may
be handled without causing significant
dimensional alterations.
4. The annealing point is the

temperature at which the viscosity is
1012 Pa.s (1013 P); at this
temperature, atomic diffusion is
sufficiently rapid that any residual
stresses may be removed within about
15 min.
5. The strain point corresponds to

the temperature at which the
viscosity becomes 3x1013 Pas (3x1014
P); for temperatures below the strain
point, fracture will occur before the
onset of plastic deformation. The glass
transition temperature will be above the
strain point.
INTRODUCTION
Most glass-forming
operations are carried out
within the working range-
between the working and
softening temperatures.
The temperature at which

each of these points
occurs depends on glass
composition.
INTRODUCTION
Three largest consumers
Glass packaging, domestic commodities and construction industry
Glass Consumers
Glass package, 43 %
Sheet glass, 30 %
Housekeeping, 12 %
Electrotechnical needs, 10 %
Plant and cunduits, 5 %

GLASS FAMILIES
Vitreous Commercial glasses are
Silica
Soda-Lime primarily based on
Aluminosilicate
Glass Glass silica, but can include any
of the other common glass
Other Non- formers as well.
Lead Silicate
Silica-Based
Glass
Oxide Glasses The properties of these
glasses cover as wide a
range as those of other
Oxyhalide, Oxynitri Other Silica- major types of
de and Oxycarbide Based Oxide materials, i.e., metals or
Glasses Glasses polymers.
Although soda-lime-silica
Chalcogenide and glasses provide the bulk of
Amorphous
Chalcohalide
Semiconductors
commercial glasses by
Glasses weight, the economic
value of other, more
Borosilicate Halide specialized commercial
Glass Glasses glasses is comparable to
Glassy
Metals that of the generic soda-
lime-silica products.
Fundamentals of inorganic glasses, Arun K. Varshneya, ISBN 0-12-714970-8, 1994 by Academic Press, Inc. Asst. Prof. Dr. Ayşe KALEMTAŞ
Soda-Lime Glass
Soda-lime glass or soda-lime-silicate glass is perhaps the least expensive and the most
widely used of all the glasses made commercially.
Most of the beverage containers, glass windows, and incandescent and fluorescent
lamp envelopes are made from soda-lime glass.
It has good chemical durability, high electrical resistivity, and good spectral transmission
in the visible region.
Because of its relatively high coefficient of thermal expansion (~100x10-7/°C), it is prone

to thermal shock failure, and this prevents its use in a number of applications.
Most of the commercial glass by weight is based on the soda-lime-silica ternary

system, with minor additions of other oxides to adjust the properties for specific
applications.
Large-scale continuous melting of inexpensive batch materials such as soda ash

(Na2CO3), limestone (CaCO3), and sand at 1400-1500°C makes it possible to form the
products at high speeds inexpensively.
Soda-Lime Glass
Development of soda-lime-silica glass compositions represents a

compromise between the outstanding properties of pure silica, and the cost
of producing the massive quantities of glass required for
windows, containers, and electrical lighting.
Addition of soda to silica results in a large decrease in the temperature

required for melting. Unfortunately, large amounts of soda also lead to
unacceptably poor chemical durability of the glass.
Replacement of a portion of the soda by lime (CaO), which is not as

strong a flux as soda, partially offsets the reduction in chemical durability
and results in a glass with a reasonable melting temperature
(~1500C), while maintaining acceptable properties for most consumer
applications.

Borosilicate Glass
Many of these glasses, especially those based on the ternary sodium borosilicate
system, rely on the existence of phase separation for their desirable properties, while
many others are homogeneous.
As a result, the properties of these glasses also vary over a wide range. In
general, however, these glasses are chosen for their applications because they have
either better thermal shock resistance, better chemical durability, or higher electrical
resistivity than soda-lime-silica glasses.
The improvement in thermal shock resistance results from a lower thermal expansion
coefficient, with values for typical borosilicate glasses lying between that of vitreous
silica and those of soda-lime-silica glasses.
The improved chemical durability and higher electrical resistivity of these glasses can
result from either a carefully planned morphology for the phase separated
borosilicate glasses, or the absence of mobile monovalent ions for many of the
homogeneous borosilicate glasses.

Borosilicate Glass
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glass-chromatography-vials img/borosilicate-glass-rod-low-
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Vitreous Silica
Vitreous silica is the most refractory glass in commercial use. In addition to

its refractoriness, it has a high chemical resistance to corrosion (particularly
to acids), a very low electrical conductivity, a near-zero (~5.5 x 10-7/C)
coefficient of thermal expansion, and good UV transparency.
Because of the high cost of manufacture, the uses of vitreous silica are
mostly limited to astronomical mirrors, optical fibers, crucibles for melting
high-purity silicon, and high-efficacy lamp envelopes.
In one technique, the glass is obtained by melting high-purity quartz crystals

or beneficiated sand at temperatures in excess of 2000°C.
In a second technique, SiCl4 is sprayed into an oxy-hydrogen flame or

water-vapour-free oxygen plasma. Silica vapors deposit on a substrate and
are consolidated subsequently at ~ 1800°C.
Vitreous Silica
While vitreous silica has many properties

which make it desirable for application as
a flat, container, or lamp glass, the high
melting temperature required to produce
vitreous silica (> 2000 C) precludes its
application for the more common
consumer products, where cost is a
driving force behind the choice of glass
composition.
Vitreous silica is the generic term used to describe

all types of silica glass, with producers referring to
the material as either Fused Quartz or as Fused
Silica. Originally, those terms were used to
distinguish between transparent and opaque
grades of the material. Fused Quartz products were
those produced from quartz crystal into transparent
ware, and Fused Silica described products
manufactured from sand into opaque ware.
http://www.hebo-glass.com/public/pdf/datasheet_quartz.pdf
http://www.technicalglass.com/product_pages/fused_quartz_labware/labware/fused_quartz_labware.html Asst. Prof. Dr. Ayşe KALEMTAŞ

Vitreous Silica
Fused quartz tubing Fused quartz rod
Microscope Slides and Cover Slips

The quartz heater soaks the shell, the light bulb shell
http://www.technicalglass.com/product_pages/fused_quartz_labware/labware/fused_quartz_labware.html Asst. Prof. Dr. Ayşe KALEMTAŞ
Lead Silicate Glass
This family of glasses contains PbO and SiO2 as the principal components
with small amounts of soda or potash.
These glasses are utilized for their high degree of brilliance (as stemware or
"crystal"), large working range (useful to make art objects and intricate
shapes without frequently reheating the glass), and high electrical resistivity
(e.g., for electrical feedthrough components).
PbO additions increase the fluidity of glass and its wettability to oxide
ceramics.
Hence, high lead borosilicate glasses (generally without any alkali additions)
are used extensively in microelectronics (e.g., for conductor, resistor, and
dielectric pastes).
Lead Silicate Glass
Lead Glass
• Lime and soda replaced with PbO
• High refractive index- clarity sparkle
• Softer –cut and engrave
• Good electrical resistance - electronics
Lead Silicate Glass
Halide Glasses
http://www.horticulturesource.com/faq.php
http://www.totaltackle.com.au/Clothing/Spotters-Pivot-Black-Halide-Glass
http://www.amazon.com/RAB-Lighting-WPTGHN70-PC-
Prismatic/dp/B00415MOSG
http://www.houzz.com/photos/6186239/50W-Metal-Halide-WP1-Glass-Lens-
Wallpack-120V-modern-outdoor-lighting
Chalcogenide and Chalcohalide Glasses
-Low loss robust chalcogenide fibres for fibre

lasers, supercontinuum generation and delivery Chalcogenide glass is glass containing one or more
-Fibre end caps and splicing technology for soft glass fibres chalcogenide elements. Modern chalcogenide
compounds are Ge, Sb and Te used for CD/DVD
http://minerva-project.eu/technology/
http://4textile.blogspot.com.tr/2012/10/226.html
Chalcogenide materials could enable faster data streaming. These materials

promise to bridge the gap between glasses such as fibre optics and semiconductors
such as silicon — potentially resulting in faster data streaming and more efficient
solar cells, among many other applications.
‗With chalcogenides we can form the material into fibres, thin
films, microspheres, nanophotonics — anything that you can make glass in to, but
they also have the electronic properties of semiconductors, so it‘s almost a
marriage of the two worlds,‘
http://www.theengineer.co.uk/more-sectors/electronics/news/chalcogenide-
materials-could-enable-faster-data-streaming/1009575.article#ixzz3KitazK11

OPTICAL FIBRES
Communications are increasingly based on electro-optic

systems in which telephones, television and computers are
linked by fibre optic cables which carry information by light.
Making glass optical fibres is a highly specialised aspect of

glass manufacture. Optical fibres consist of two distinct
glasses, core of highly refracting glass surrounded by a sheath
of glass with lower refractive index between the two glasses, it
is guided by total reflection at the core-sheath interface to the
other end of the fibre.
In theory, a wide range of glasses can be used as long as the

difference in refractive index is appropriate but the higher the
refractive index of the core relative to that of the sheath
glass, the greater the carrying capacity of the fibre. A typical
system available commercially comprises a germanium doped
silica core and a borosilicate cladding.

FLAT GLAS
There are two main flat glass manufacturing methods for producing the
basic glass from which all processed glass products are made:
 the drawn glass process and

 the float glass process.
Since the introduction of the float process in 1959 by Pilkington it has

gradually replaced other processing techniques.
Annealed glass (ordinary glass) is the end product of the float glass process.
It is carefully cooled through the range of temperatures where the glass solidifies
so that no residual stresses develop.
Float glass is made using a bath of molten tin, where molten glass is floated along
the surface. The perfectly flat surface of the tin is transferred to the glass.

FLAT GLAS
DRAWING
A solid metal plate is dipped into a bath of molten glass and then slowly withdrawn from the
melt. This process would present no problems if we were interested in producing a glass rod.
Producing a planar sheet is problematic because the sheet would neck down to a narrow
ribbon. This difficulty is overcome by cooling the sheet as it is drawn. These coolers solidify
the glass and produce a sheet of fixed width.
Drawing from molten glass: (a) a circular rod; (b) problem of pulling a planar sheet; (c) use of a débiteuse
and cooling to allow the formation of a sheet of constant width.

FLOAT GLAS
Float glass can be produced in very large sizes with an extremely high
flatness. Within the production technique the surface finish is improved
and glass sections with visible internal defects are removed.
The production technique requires that residual stresses are introduced.

This creates compressive stresses in surface regions which is an
advantage in practical use.
Float glass has opened the possibility to use glass in new and
demanding applications.
A new series of glass products known as structural glass has been

introduced. This type of glass dominates completely today.

FLOAT GLAS
Based on float glass
various products have • Laminated
glass
been introduced in the
market.
There is a continuous
development regarding • Heat
• Coated
strengthened
glass products to meet glass
glass
new needs on the market.
Some of the mentioned

products have been on
the market for longer
period of time but not
being used in structurally
demanding applications. • Insulating • Toughened
glass glass

FLOAT GLAS
http://educationcenter.ppg.com/glasstopics/learn_about_glass.aspx Asst. Prof. Dr. Ayşe KALEMTAŞ

FLOAT GLAS
More than 90% of the world‘s flat glass is now made by the float process, where
molten glass, at approximately 1000C, is poured continuously from a furnace on to
a large shallow bath of molten tin.
The liquid glass floats on the tin, spreads out and forms a level surface. Since the
melting point of the tin is much less than that for glass, the glass solidifies as it
slowly cools on top of the molten tin.
Thickness is controlled by the speed at which the solidifying glass ribbon is drawn off
the bath. Once the glass solidifies, it is fed into an annealing lehr where it is slowly
cooled in a process where the residual stresses are controlled.
This process results in the production of an annealed float glass with residual
compressive stresses around 8 MPa in the surface. After annealing the glass
emerges as a ―fire‖ polished product with virtually parallel surfaces.
This method, in which the glass pane is formed by floating the melt on a bath of
liquid tin, revolutionized the manufacture of high quality glass and large sizes. Float
glass is available in thicknesses ranging from 2 mm up to 25 mm.

ANNEALED GLAS
Advantages
– Cost
Limitations
– Breaks in sharp pieces
– Not as strong as tempered glass
– Size limitations

ANNEALED GLAS
Images of annealed glass failure (left), heat-strengthened glass failure (centre), and
fully tempered glass failure (right)

TEMPERED GLASS
Tempered glass also know as

toughened glass is made by quickly
cooling the annealed glass when it
is heated near compression is
formed over the glass surface while
tensile formed inside the glass
plate. Shatter pattern of tempered glass
Tempered glass is made by heating

annealed glass to approximately
700C then cooling the outer surfaces
rapidly. This process makes the glass
very strong and shock resistant thus
Crazed fracture pattern on left in
more durable. tempered glass on an elevator
wall. Fracture origin is shown
above.

TEMPERED GLASS
Primary processing is a treatment of the basic glass after its manufacture.
Since surface flaws only lead to fracture when a tensile stress opens
them, any method of putting the glass surface into permanent compression
is advantageous.
An applied tensile stress would have to overcome this built-in compression

before it begins to open up a flaw and hence the glass would be able to
resist higher loads. Toughened glass and heat strengthened glass use this
principle.
The stress distribution in toughened glass enables it to withstand tensile

stresses of much higher levels than ordinary annealed glass. Annealed
glass has a residual surface compression stress of around 8-10
MPa, because of production reasons. Any external stress level has to
exceed this threshold stress to cause a failure which will be time and size
dependent. The thickness of the glass may influence the actual residual
compressive stress.

TEMPERED GLASS
Toughened glass, or tempered glass as it is also known as, is first cut to its
final size and it is edge treated and drilled if required. Afterwards the glass
pane is heated to approximately 650C, at which point it begins to soften. Its
outer surfaces are then cooled rapidly, creating in them a high compression
stress, where the rate of the cooling will determine the amount of built-in
compression stress and hence the final strength of that glass.
Its bending strength is usually increased by a factor of 4 or 5 to that of

annealed glass and hence a new and raised threshold stress has been
achieved. The maximum tensile stress in the middle is half of the surface
compressive stress.
When broken, it fractures into small harmless dice and it is known as safety
glazing material. Heat strengthened glass is similarly produced, but with
strengths approximately half that of toughened glass and without the safety
glazing characteristic. Toughened glass cannot be subsequently surface or
edge worked or cut because this would initiate a failure.

TEMPERED GLASS
• Resists fractures because surface is compressed

• Crumbles when cracked because inside is tense
Advantages
– 4 times the stronger than annealed
– Breaks into small, harmless pieces.
– Qualifies as Safety Glazing
Limitations
– Must be cut to size before tempering
– Optical distortion (roller wave, strain pattern)

TEMPERED GLASS
Tempering glass
– Cool outside of glass quickly, outside stiffens while inside is still hot
– Shrinking inside compresses outside, compressed outside stretches inside

TEMPERED GLASS
Toughened is derived from heating typical flat glass, including patterned, to a

plastic like state of around 600-700 C in a specially designed furnace or oven.
After the desired state is achieved it is rapidly cooled with a burst of air to both
surfaces.
Different types of glass have different recipes to allow it to be toughened.

TEMPERED GLASS
Usage Range of Tempered Glass:
 Construction curtain wall
 Glass doors & windows
Laminated glass is
 Support bar of staircases & escalators widely used for
 Different types of the glass artdecorations
Blaustrading
 Location of near the intense heat and the
Showerscreens
impact severed by the hotcold.
Display Cases
Revolving Doors
Shopfronts
Lifts and Foyers
Partitions
Furniture
Pool surrounds, etc.

LAMINATED GLASS
Laminated glass is a kind of safety glass which is combined
from one or more layers of PVB through heating and pressing
processes by autoclave.
2 sheets of glass are bonded with a thin film of

plastic such as polyvinyl butyrate under
pressure at a temperature of about 100°C
The sandwiched plastic bonds well to the 2

glass surfaces and helps absorb energy in
impacts, stops glass shattering and
disintegrating if stressed to failure so that it
often remains secure and weatherproof.
This provides a high degree of resistance to

injury from flying glass in case of impact.

LAMINATED GLASS
Laminated glass absorbs energy Safety

of the impact
• Ordinary window glass is brittle and
breaks into long sharp pieces
Will not shatter
Holds up against
• hurricanes
• cyclones
• earthquakes

LAMINATED GLASS
Laminated glass
is widely used for
bullet proof
burglar-proof
showcase
counter
aquarium
skylight http://www.livingetc.com
Glass staircase
long corridor
www.aarticommercial.com
sidelite, etc. Laminated Windscreen Glass
If the laminated glass is made from “ordinary” float glass, it is still

workable (cutting and drilling is possible) and the PVB helps the
fractured glass to stay put inside the construction.
LAMINATED GLASS
Sound Control Application

Another important element of laminated
glass is acoustical performance in
commercial applications.
Laminated glass reduces noise

transmission due to sound damping
characteristics of the pvb interlayer.
While glass is inherently a poor acoustical

performer, higher performance levels can
be achieved by using laminated glass http://qddarley.en.made-in-china.com
alone or combined with additional glass

plies to form a sealed insulating glass
unit.

LAMINATED GLASS
UV Protection
With time, sunlight can cause considerable damage to buildings
furnishings, carpets, artwork, photographs, plants and other valuables. These items
need special protection from the damaging effects of the sun's ultraviolet (UV) rays.
Laminated glass made with resin can be effective in screening out the harmful UV
rays, controlling glare and decreasing solar energy transmittance. Glazing solar
control is accomplished in laminated glass by the interlayer ability to reflect and/or
absorb and re-radiate much of the solar UV radiation.
Laminated glass made with resin screens out more than 99% of damaging UV light.
While protecting buildings from harmful and damaging solar UV radiation, laminated
glass made with resin has no adverse affect on the health of indoor plants. In
fact, laminated glass is commonly used in greenhouses and atriums to help protect
flower color and reproductive development from the damaging effects of UV
radiation. Photoreceptors in plants are still able to absorb sunlight the resin
interlayer allows to be transmitted.

LAMINATED GLASS
The City of Arts and Sciences is
an entertainment and educational
complex that is an amazing work
of craftsmanship and design.
Architect Santiago Calatrava

primarily designed this gorgeous
project.
Laminate glass is widely used

not just in the grand windows
and ceilings but also found in
the planetarium’s floor.
The glass floors are four ply

laminated glass that consist of acid
etched, anti-slip, 6 mm tempered
glass on the top with three 10 mm
layers of glass. This keeps right in
line with the modern design of the
building.
www.homedesignfind.com Asst. Prof. Dr. Ayşe KALEMTAŞ

LAMINATED GLASS
BULLETPROOF GLASS
Bulletproof glass is made of laminated glasses

and films which have special shielding capability
towards bullets.
The different levels of bullet proof glasses are

able to shield the bullets from penetration and
www.bmw-security-vehicles.com
prevent the broken parts from injuring people.
They are widely applied in 22-millimetre glass/plastic laminate with a
bank, polycarbonate coating on the inside to prevent flying
splinters. The 22-millimetre glass protects against:
counters of jewelry and gold shops, 
• Blunt instruments
cash trucks and .44 Magnum with full-jacket flat-nose bullets
other regions requiring special safety  .357 Magnum with coned bullets
prevention.  9-millimetre Luger with round-nose bullets

GLASS COMPOSITION
Choice of Glass Compositions
Choosing a glass composition is a more complicated exercise

than may at first appear. One must first establish the properties
important to the final user, next consider those properties
important to the glass maker, then achieve a balance between
these and lastly determine what choice of batch materials will
produce either the best quality or, perhaps, the cheapest glass
meeting the quality requirements.

GLASS COMPOSITION
Properties Important to the User
Which properties are important depends very much on the application. From a designer's point
of view, strength would nearly always be the first to be considered. However, because the
practical strength of glasses is determined more by surface flaws than anything else strength
can generally be taken to be weakly dependent on composition and omitted from the
specification. So far as strength is concerned commercial glasses can usually be considered as
being either pure silica or "the rest" and only two sets of strength data need be considered.
The next most important property, which may not always come immediately to mind, often is
resistance to corrosion. Good glasses are generally stable, already being oxides, but can be
leached by water or other chemicals, something which is only rarely desirable. Chemical
durability is strongly dependent on composition, especially alkali and alumina contents, and
thus should always be included. Next we come to the properties essential for the specific
application. These may include refractive index, electrical resistivity, thermal
expansion, transparency to or absorption of radiation, softening temperature, and so on. These
properties fall into two classes, those for which a specific value is needed, like refractive index
in an optical glass or thermal expansion for a sealing glass, and those that need to be better
than some particular limit, like chemical durability or thermal expansion when thermal shock
resistance is important.

GLASS COMPOSITION
Properties Important to the Glass
Maker
Apart from the criteria set by the final

user, several properties are very important
to the glass manufacturer. The viscosity-
temperature characteristic is crucially
important to efficient forming.
Also the liquidus temperature must be

below the temperature at which the melt
must be held to begin forming operations.
The actual devitrification characteristics
may be less important but it can be useful
to know whether crystal growth may be
rapid if it does occur. The glass
manufacturer also wants to have a glass
as easy as possible to melt, refine, and
homogenize but these factors are not
capable of being specified in terms of
standard properties.

GLASS COMPOSITION
Properties Important to the Glass Maker
Some glasses contain significant proportions of elements which can exist in more than
one valence state and these may need their oxidation states to be controlled. The most
familiar example is the decolorizing of glass in which iron is oxidized, as far as
possible, to the ferric state which gives a paler tint than the same concentration of iron
reduced to ferrous.
On the other hand, to make a heat absorbing glass one would wish to reduce the iron to
ferrous which has a broad absorption peak in the near infrared.
Control of oxidation is generally achieved largely by the selection of oxidizing or

reducing materials added to the batch but partly by control of furnace atmosphere.
In small scale laboratory melting oxidation can be controlled by bringing the melt to
equilibrium with a specific atmosphere but this is not necessary and would be difficult to
achieve in large scale manufacture.

GLASS COMPOSITION
The batch materials can considerably influence ease of melting, degree of

segregation during melting, volatilization losses, refining, and homogeneity
of the glass.
Both control of oxidation and overall melting performance can also be

affected by minor constituents, that is to say cations or anions added at
levels usually below 1%, which control oxidation through mutual interactions
or have beneficial effects on melting, refining, and homogeneity.
The interactions between iron and arsenic, antimony or cerium can play an
important part in decolorizing. Sulfate is the most commonly used refining
agent: arsenic is often efficient but now rarely used because of legal
controls on its use and halides can be effective. The glass maker will usually
expect to be allowed to modify slightly the user's composition specification
to optimize these factors.

GLASS COMPOSITION
Typical composition (wt %) of
some of the common commercial glasses

GLASS-CERAMIC
By definition, glass-ceramics are
materials which are melted and formed
using standard glass manufacturing
techniques, and then heat treated to
produce a highly crystalline material
with properties which are very different
from those of the original glass.
The most common glass-ceramics are

based on either the lithium, sodium, or
magnesium aluminosilicate systems.
Although the best known glass-

ceramics are used for
cookware, applications of glass-
ceramics include other consumer
products such as electric stove tops
Processing cycle for a glass-ceramic
and construction materials, and
specialty applications such as
telescope mirrors, electronic
substrates, and missile radomes. Asst. Prof. Dr. Ayşe KALEMTAŞ
GLASS-CERAMIC
Production of glass-ceramics usually involves a two-step process.
A small amount of a ―nucleating agent‖ is added to the batch. When heat treated at
the proper temperature, this agent will either form very small crystals, i.e., nuclei, or
will induce phase separation.
Once this phase has formed, the material is heated to a higher temperature where a
second, major phase will grow to yield the final product.
In general, a very fine grained microstructure is desired, since such microstructures

produce very strong materials.
Many applications of glass-ceramics are based on their superior resistance to failure

due to thermal shock. Since thermal shock resistance is primarily determined by the
thermal expansion coefficient of a material, the crystalline phase in these materials
should have a low thermal expansion coefficient. A a low thermal expansion
coefficient is obtained by a combination of a low expansion crystalline phase and a
low expansion residual glass.

GLASS-CERAMIC
Glass-Ceramics
• ―Glass-ceramic‖ refers to materials which are fabricated from glass melts by a
process of controlled crystalisation.
• Glass-ceramis is a partially crystalline material which is fabricated by an
incomplete crystallisation (―Ceraming‖) of suitable glasses.
• Brands: Ceran, Zerodur, Robax, Neoceram, Macor

GLASS-CERAMIC

GLASS-CERAMIC

GLASS-CERAMIC
Crystalline phase in these materials is a lithium aluminosilicate, which is either a -quartz solid solution phase
LAS for Vision, or spodumene for Corningware. A mixture of TiO2, and ZrO2, in the batch results in a very efficient
(PYROCERAM nucleation process. Heat treatment below 900C yields very small (<100 nm) particles of the -quartz solid
solution phase, which has a refractive index close to the residual glass (very high silica concentration). The
ZERODUR resulting material is transparent even though it is highly crystalline. Heat treating the same material at a
VISION) temperature > 1000C results in the transformation of the -quartz solid solution. phase into -
spodumene, accompanied by grain growth to produce crystals in the 1 to 2 m range.
Machinable glass-ceramics are derived from the K2O–MgO–Al2O3–SiO2 system containing some
fluorine. In Macor the crystalline phase is potassium fluorophlogopite [KMg3(AlSi3O10F2)].
Phlogopite is a mica mineral and the plate-like mica crystals are randomly oriented in the glass MACOR
phase. Macor can be machined to precise tolerances (±0.01 mm) and into intricate shapes using
conventional steel tools: they can be drilled, cut, or turned on a lathe.
Calcium phosphate, Ca3(PO4)2, glasses can be made into glass-ceramics to form a material resembling the mineral
part of bone. Since bone is porous, the first step is to produce a foam glass. This is achieved by decomposing
APATITE carbonate in the glass melt. The foam glass simultaneously undergoes a controlled crystallization, transforming it into
a porous glass-ceramic. The dimensions of the interconnections between the pores must be sufficient to allow the
ingrowth of living bone tissue, which ensures a permanent joint with the surface of the prosthesis.
Another commercial fluoromica glassceramic called Dicor® has been developed for dental restorations.
Dicor has better chemical durability and translucency than Macor. It is based on the tetrasilicic
mica, KMg2.5Si4O10F2, which forms fine-grained (∼1μm) anisotropic flakes. Dicor dental restorations are DICOR
very similar to natural teeth both in hardness and appearance. They are easy to cast using conventional
dental laboratory methods and offer significant advantages over traditional metal–ceramic systems.

GLASS-CERAMIC
Zerodur mirror substrates for

Glass-ceramic teeth large segmented and monolithic
Macor substrates
astronomical telescopes
From left to right parent glass, glass ceramic The fracture surface of Macor
with 97% crystallinity and glass-ceramic with
50% crystallinity. Grain size is about 20
micrometers.
Edgar Dutra Zanotto, A bright future for glass-ceramics, American Ceramic Society Bulletin, Vol. 89, No. 8
http://www.schott.com/advanced_optics/english/products/optical-materials/zerodur-extremely-low-expansion-glass-ceramic/zerodur/index.html?so=turkey&lang=turkish
http://www.ceramic-substrates.co.uk/machinable-ceramics/macor
THE END
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CERAMIC

akalemtas@mu.edu.tr, akalemtas@gmail.com, Phone: 211 19 17

CERAMIC METAL POLYMER COMPOSITE

CLAY REFRACTORIES ADVANCED

Asst. Prof. Dr. Ayşe KALEMTAŞ

HISTORY DEFINITION PROPERTIES APPLICATIONS

Asst. Prof. Dr. Ayşe KALEMTAŞ

Four of the major technological achievements in

 Glass window – which enables sunlight to come into

Asst. Prof. Dr. Ayşe KALEMTAŞ

Asst. Prof. Dr. Ayşe KALEMTAŞ

Tempered glass table http://freshome.com

Asst. Prof. Dr. Ayşe KALEMTAŞ

Heat resistant glass

Any material that exhibits only a short-range order of atoms

In general, most materials want to form periodic

Glasses, which typically form in ceramic and polymer

Asst. Prof. Dr. Ayşe KALEMTAŞ

Glass can be inorganic (non-carbon based) as well as organic (carbon-

The most common method for making glass is to:

Inorganic glasses may also be obtained by

 Hydrolyzing an alcoholic solution of an organometallic compound,

Many centuries passed before written accounts of glass

The earliest development in glass making of which we have

Asst. Prof. Dr. Ayşe KALEMTAŞ

Probably as early as 75,000 B.C.E., long before human beings had

Asst. Prof. Dr. Ayşe KALEMTAŞ

Uses of Obsidian as a Cutting Tool

The conchoidal fracture of obsidian causes it to break into pieces

The first use of obsidian by people probably occurred when a sharp

Once these discoveries were made, obsidian quickly became the

http://geology.com/rocks/obsidian.shtml Asst. Prof. Dr. Ayşe KALEMTAŞ

A thin piece of obsidian is often used as a "backing"

Mahogany obsidian and snowflake obsidian

http://geology.com/rocks/obsidian.shtml Asst. Prof. Dr. Ayşe KALEMTAŞ

Obsidian in Modern Surgery

Obsidian can be used to produce a cutting edge that is thinner and

In controlled studies, the performance of obsidian blades was equal to or

http://geology.com/rocks/obsidian.shtml Asst. Prof. Dr. Ayşe KALEMTAŞ

Asst. Prof. Dr. Ayşe KALEMTAŞ

- 4000: Jewel in molted glass

Asst. Prof. Dr. Ayşe KALEMTAŞ

Asst. Prof. Dr. Ayşe KALEMTAŞ

Egyptians Romans Middle Ages

• First people to • By Roman times • Main achievements

Asst. Prof. Dr. Ayşe KALEMTAŞ

A glass is a solid that possesses no long-range atomic order

Crystalline materials have a definite structure, whereas amorphous ones do

Asst. Prof. Dr. Ayşe KALEMTAŞ

Specifically, upon cooling, a

Concomitantly, the specific

The first one occurs, as in

The second contraction

The intermediate range between

Tg is then defined to be that

Above Tg, the material is defined to

The intersection of the two

Because of the high viscosity of

Incidentally, the expansion

Commercially important is Pyrex, a

Glass is a linear elastic and

Asst. Prof. Dr. Ayşe KALEMTAŞ

Glasses  brittle fracture !!!