Unit-V

Introduction to glassy materials

• Ceramic composites,
• Glass ceramics,
• Measurement of ceramic properties

Dr. Paresh H. Salame

 Glasses and Glass-ceramics
› Glass is an amorphous material, often, but not always, derived from a molten liquid.
› The term “amorphous” refers to materials that do not have a regular, periodic
arrangement of atoms
Overview

› The fiber optics industry is founded on optical fibers based on high purity silica glass.
› Glasses are also used in houses, cars, computer and television screens, and
hundreds of other applications.
› Glasses can be thermally treated (tempered) to make them stronger.
› Forming glasses and nucleating (forming) small crystals within them by a special
thermal process creates materials that are known as glass-ceramics.
› Zerodur™ is an example of a glass-ceramic material that is used to make the mirror
substrates for large telescopes (e.g., the Chandra and Hubble telescopes).
› Glasses and glass-ceramics are usually processed by melting and casting.
Short range vs long range order
Levels of atomic arrangements in materials:

› (a) Inert monoatomic gases have no regular

ordering of atoms

› (b,c) Some materials, including water vapor,

nitrogen gas, amorphous silicon, and silicate
glass, have short-range order

› (d) Metals, alloys, many ceramics and some

polymers have regular ordering of atoms ions
that extends through the material
 Glasses and Glazes (Amorphous Materials)
› Any material that exhibits only a short-range order of atoms or ions is
an amorphous materials; i.e. a non-crystalline material
• Can be made by restricting
the atoms/ions from
assuming their “regular”
periodic positions

• However, there is always

natural tendency of an
amorphous materials to
crystallize
(thermodynamically stable
phase)
 Atomic Order in SiO2

› Ions in silica (SiO2) glass exhibit only a short-range order in which Si +4

and O-2 ions are arranged in a particular way (each Si +4 is bonded with 4 O-
2 ions in a tetrahedral coordination, with each O -2 ion being shared by two

tetrahedra).

› This order, however, is not maintained over long distances, thus making
silica glass amorphous.

› Amorphous glasses based on silica and certain other oxides form the basis
for the entire fiber-optic communications industry
 Inorganic Glasses
The most important of the non-crystalline materials are glasses, especially
those based on silica. Of course, there are glasses based on other compounds
(e.g., sulfides, fluorides, and various alloys).
› A glass is a metastable material that has
hardened and become rigid without
crystallizing.
› A glass in some ways resembles an undercooled
liquid.
› Below the glass transition temperature “Tg”, the
rate of volume contraction on cooling is reduced,
and the material can be considered a “glass”
rather than an “undercooled liquid.

Joining silica tetrahedra or other ionic groups produces a solid, but non-crystalline, network
structure
 How glass is formed?
› If a liquid is cooled rapidly enough such that the atoms do not have enough
time to rearrange themselves in a crystalline patters before their motion is
arrested, a glass is formed.
› Most liquids, when cooled from the melt, will, at a very well-defined
temperature, namely, their melting point, abruptly solidify into crystalline solids.
› There are some liquids, however, for which this is not the case; when cooled,
they form amorphous solids instead.
› Typically, the transformation of a liquid to a crystalline solid occurs by the
formation of nuclei and their subsequent growth — two processes that require
time.
› Consequently, if the rate of removal of the thermal energy is faster than the time
needed for crystallization, the latter will not occur and a glass will form
How glass a non-crystalline solid is different from any crystalline
solid?
• They have many different properties that crystalline solid do not have, but most importantly, glasses
do not have unique melting points but rather softens over a temperature range.
• Similarly, their viscosity increases gradually as the temperature is lowered
oxides such as silica behave as glass formers, an intermediate oxide (such as lead
oxide or aluminum oxide) does not form a glass by itself but is incorporated into the
network structure of the glass formers
Modified Silicate Glasses
Manufacturing process of glass
The effect of temperature and composition on the viscosity of
glass.
Glasses are manufactured into useful articles at a
high temperature by controlling the viscosity so
that the glass can be shaped without breaking.

1. Liquid range.
• Sheet and plate glass are produced when the
glass is in the molten state. Techniques include
rolling the molten glass through water-cooled
rolls or floating
the molten glass over a pool of liquid tin (next
slide).
• The liquid-tin process produces an exceptionally
smooth surface on the glass.
• The development of the float-glass process was
a genuine breakthrough in the area of glass
processing
 2. Working range

Techniques for forming glass

products: (a) pressing, (b) press and
blow process, and (c) drawing of
fibers.

Working range. Shapes such as those of containers or lightbulbs can be formed by

pressing, drawing, or blowing glass into molds. A hot gob of liquid glass may be pre-
formed into a crude shape (parison), then pressed or blown into a heated die to produce
the final shape. The glass is heated to the working range so that the glass is formable,
3. Annealing range.
Some ceramic parts may be annealed to reduce residual stresses introduced during
forming. Large glass castings, for example, are often annealed and slowly cooled to
prevent cracking. Some glasses may be heat treated to cause devitrification, or the
precipitation of a crystalline phase from the glass.

• Tempered glass is produced by quenching the surface of plate glass with air, causing
the surface layers to cool and contract. When the center cools, its contraction is
restrained by the already rigid surface, which is placed in compression
• Tempered glass is capable of withstanding much higher tensile stresses and impact
blows than untempered glass. Tempered glass is used in car and home windows,
shelving for refrigerators, ovens, furniture, and many other applications where safety is
important.
 Tempering and Annealing of Glasses
› Residual stresses originating during the cooling of glasses, can be dealt by;
› First, we can reheat the glass to a high temperature known as the annealing point
(450°C for silicate glasses with a viscosity of 1013 Poise) and let it cool
slowly so that the outside and inside cool at about same rate.
› The resultant glass will have little or no residual stress. This process is known as
annealing, and the resultant glass that is nearly stress-free is known as “annealed
glass”
› Another option we have in glass processing is to conduct a heat treatment that
leads to compressive stresses on the surface of a glass; this is known as tempering.
The resultant glass is known as “tempered glass”
› Tempered glass is obtained by heating glass to a temperature just below the
annealing point, then, deliberately letting the surface cool more rapidly than the
center.
›
Glass-Ceramics
What is a glass-ceramics??

• Glass-ceramics are polycrystalline materials produced by the

controlled crystallization of glass and are composed of randomly
oriented crystals with some residual glass, typically between 2 and 5
percent, with no voids or porosity
 Processing of Glass-Ceramics………..(in four major steps)

Step-1: Mixing and Melting

Processing of Glass Ceramics

1. Mixing and melting. Raw materials such as quartz, feldspar, dolomite, and
spodumene are mixed with the nucleating agents, usually TiO2 or ZrO2, and melted

A typical Temperature versus time cycle for controlled crystallization of a glass-ceramic body,
 Step-2: Forming
• one of the major advantages of glass-ceramics lies in the fact that they can be
Processing of Glass Ceramics

formed by using conventional glass forming techniques such as spinning, rolling,

blowing, and casting;

• so complex-shaped, pore-free articles can be easily manufactured.

• The cooling rate during the formation process, however, has to be rapid
enough to avoid crystallization or growth
 Step-3: Ceraming
• Once formed, the glass body is heated to a temperature high enough to obtain a
very large nucleation rate
• Efficient nucleation is the key to success of the process.
Processing of Glass Ceramics

• The nucleation is heterogeneous, and the crystals grow on the particles of the
nucleating agents, typicallyTiO2 or ZrO2, that are added to the melt

• To obtain crystals on the order of 1 μm, the density of nucleating agents has to be
on the order of 1012 to 1015 cm-3.

Step-4: Growth

• Following nucleation, the temperature is raised to a point where growth of the

crystallites occurs readily.
• Once the desired microstructure is achieved, the parts are cooled. During this
stage the body usually shrinks slightly — by about 1 to 5 percent
 Properties and Advantages of glass-Ceramics
Glass-ceramics offer several advantages over both the glassy and crystalline
phases, including these:
Properties and Advantages of

1. Ease of processing;

i. Viscous sintering is much easier and faster than solid-state sintering.

glass-Ceramics

ii. The motive for using glass-ceramics is to take advantage of the ease of
processing inherent in the glass to shape and form complex shapes, followed
by transforming the glass phase to a more refractory solid in which the
properties can be tailored by judicious crystallization.

iii. Unlike ceramic bodies made by conventional pressing and sintering, glass-
ceramics tend to be pore-free. This is because during crystallization the glass
can flow and accommodate changes in volume
 2. Improved mechanical Integrity and strength ;

i. Usually the presence of the crystalline phase results in much higher

deformation temperatures than the corresponding glasses of the same
composition.
Properties and Advantages of

ii. For example, many oxides have Tg values of 400 to 450°C and soften readily
at temperatures above 600°C.
glass-Ceramics

iii. A glass-ceramic of the same composition, however, can retain its mechanical
integrity and rigidity to temperatures as high as 1000to 1200°C.

iv. The strength and toughness of glass-ceramics are usually higher than those of
glasses. For example, the strength of a typical glass plate is on the order of
100 MPa, while that of glass-ceramics can be several times higher;

v. Since crystals present in the glass-ceramics tend to limit the size of the flaws
present in the material, increasing its strength
 3. Control over thermal expansion coefficient;

i. As with glasses, the properties — most notably the thermal expansion

coefficients — of glass-ceramics can be controlled by adjusting the
Properties and Advantages of

composition.

ii. In many applications, such as glass-metal seals and the

glass-Ceramics

joining of materials, it is very important to match the thermal expansion

coefficients to avoid the generation of thermal stresses.
Example of Glass-Ceramics
• The most important glass-
ceramic compositions are
probably based on lithium
silicates. The phase diagram of
the Li2O-SiO2 system is shown
in figure.
• The commercial compositions
usually contain more than about
30 percent lithia which upon
crystallization yields Li2Si2O5
as the major phase with some
SiO2 and Li2SiO3.

Figure: LiO2-SiO2 Phase diagram

 Glass ceramics
› Crystallization of glasses can be controlled.
› Materials scientists and engineers, such as “Donald Stookey”, have developed
ways of deliberately nucleating ultrafine crystals in amorphous glasses. The
Overview

resultant materials, known as glass-ceramics, can be made up to 99.9%

crystalline and are quite strong.

› Some glass-ceramics can be made optically transparent by keeping the size of

the crystals extremely small ( ~100 nm).

› The major advantage of glass-ceramics is that they are shaped using glass-
forming techniques, yet they are ultimately transformed into crystalline materials
that do not shatter like glass.
Important points to remember Glass-ceramics
› The term glass-ceramics refers to engineered materials that begin as amorphous glasses and end up
as crystalline ceramics with an ultra-fine grain size.
› These materials are then nearly free from porosity, mechanically stronger, and often much more
resistant to thermal shock.
› Nucleation does not occur easily in silicate glasses; however, we can help by introducing nucleating
agents such as titania (TiO2) and zirconia (ZrO2).

› Engineered glass-ceramics take advantage of the ease with which glasses can be melted and
formed.
› Once a glass is formed, we can heat it to deliberately form ultra-fine crystals, obtaining a material
that has considerable mechanical toughness and thermal shock resistance.
› The crystallization of glass- ceramics continues until all of the material crystallizes (up to 99.9%
crystallinity can be obtained).
› If the grain size is kept small ( 50–100 nm), glass-ceramics can often be made transparent.
› All glasses eventually will crystallize as a result of exposure to high temperatures for long lengths
of times.
Ceramic Composites
 Composites (Ceramic Composites)
› Many of modern technologies require materials with unusual combinations of properties
that cannot be met by the metals, conventional metallic alloys, ceramics, and polymeric
materials, e.g. materials needed for aerospace, underwater, and transportation
applications.
Introduction

› For example engineers working in aircraft industry are looking and searching for
structural materials that have low densities, are strong, stiff, and abrasion and impact
resistant, and are not easily corroded.

› Obviously, this is a rather formidable combination of characteristics.

› Usually strong materials are relatively dense; also, increasing the strength or stiffness
generally results in a decrease in impact strength.
› Therefore, in composites the whole is greater than the sum of the parts (synergy)
 What is a composite?
› A composite is considered to be any multiphase material that exhibits a significant
proportion of the properties of both constituent phases such that a better combination
of properties is realized.

› This is termed as the principle of combined action. According to this principle, better
Introduction

combinations are fashioned by the judicious combination of two or more distinct

materials.

› All composites generally have one thing in common: a matrix or binder combined
with a reinforcing material.

› Obviously, a composite consists of a matrix material, dispersed within which is a

dispersion of one or more phases of another material.
 What is a composite?
• Combinations of different materials which yield a product with superior
properties

• Modern composites, or advanced composites are typically fiber reinforced

plastics
Introduction

Why to choose composite over other materials?

With a knowledge of the various types of composites, as well as an

understanding of the dependence of their behaviours on the characteristics,
relative amounts, geometry/distribution, and properties of the constituent
phases, it is possible to design materials with property combinations that are
better than those found in the metal alloys, ceramics, and polymeric materials.
 Metals vs Composites: Differentiator

• Many metals are mostly “isotropic”, which means it has the same
properties in all directions.
Introduction

• Composites are “anisotropic” which means they have different properties

depending on the direction of the fibers vs. the direction of the applied
loading
 Classification of the composites
Introduction
 Rule of Mixture
Introduction
 Schematic representations of the various geometrical and spatial characteristics of particles of the
dispersed phase that may influence the properties of composites:
(a) concentration, (b) size, (c) shape, (d) distribution, and (e) orientation.
Introduction
 Cermets
Introduction

Polymers
Particulate Abrasives
composite

Electrical
Contacts
 What are the constituent/components of a composite?

• Matrix phase
Introduction

• Dispersed phase
 Functions/Role of The Matrix Material
(Primary Phase)
 Protect phases from environment

 Transfer Stresses to phases

Introduction

 Holds the imbedded phase in place, usually enclosing and often

concealing it

 When a load is applied, the matrix shares the load with the secondary
phase, in some cases deforming so that the stress is essentially born
by the reinforcing agent
Ceramic Matrix composites-Examples