MCS3202 - Material Technology

Chapter 4: Ceramics
Introduction

Ceramic materials were discussed briefly in Chapter 1, which noted that they are
inorganic and non-metallic materials. Most ceramics are compounds between metallic
and non-metallic elements for which the interatomic bonds are either totally ionic, or
predominantly ionic but having some covalent character. The term ceramic comes
from the Greek word keramikos, which means “burnt stuff,” indicating that desirable
properties of these materials are normally achieved through a high-temperature heat
treatment process called firing.

Mechanical Properties

Prior to the Bronze Age, human tools and vessels were primarily made of stone (a
ceramic). After that, metals came into widespread use because of their toughness that
is derived from their ductility. For most of that history, ceramic materials were
somewhat limited in applicability because of their brittle nature. Although many
new composites and other multiphase ceramics with useful toughness are being
developed (often mimicking naturally occurring composite ceramics such as
seashells), the bulk of ceramic materials currently in use are brittle.

Brittle Fracture of Ceramics

At room temperature, both crystalline and noncrystalline ceramics almost always

fracture before any plastic deformation can occur in response to an applied tensile
load. The brittle fracture process consists of the formation and propagation of cracks
through the cross section of material in a direction perpendicular to the applied load.
The measure of a ceramic material’s ability to resist fracture when a crack is present
is specified in terms of fracture toughness. The plane strain fracture toughness K Ic, is
defined according to the expression

K Ic =Yσ √ πa

crack geometries, 𝜎 is the applied stress, and a is the length of a surface crack or half
where Y is a dimensionless parameter or function that depends on both specimen and

of the length of an internal crack. The K Ic pf some materials is given in Table 1 below

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Table 1: Fracture Toughness of some selective materials

Material Fracture Toughness K Ic(MPa√ m¿

Concrete 0.2-1.4
Soda-lime glass 0.7-0.8
Aluminum Oxide 2.7-5.0

Fractography of Ceramics

It is sometimes necessary to acquire information regarding the cause of a

ceramic fracture so that measures may be taken to reduce the likelihood of future
incidents. A failure analysis normally focuses on determination of the location, type,
and source of the crack-initiating flaw.
A fractographic study is normally a part of such an analysis, which involves
examining the path of crack propagation, as well as microscopic features of the
fracture surface. It is often possible to conduct an investigation of this type using
simple and inexpensive equipment—for example, a magnifying glass and/or a low-
power stereo binocular optical microscope in conjunction with a light source. When
higher magnifications are required, the scanning electron microscope is used.
After nucleation and during propagation, a crack accelerates until a critical (or
terminal) velocity is achieved; for glass, this critical value is approximately one-half
of the speed of sound. Upon reaching this critical velocity, a crack may branch (or
bifurcate), a process that may be successively repeated until a family of cracks is
produced. Typical crack configurations for four common loading schemes are shown
in Figure 1.

Figure 1: For brittle ceramic materials, schematic representations of crack origins and configurations that
result from (a) impact (point contact) loading, (b) bending, (c) torsional loading, and (d) internal pressure.

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Stress-strain behaviour

Flexural Strength

The stress–strain behavior of brittle ceramics is not usually ascertained by a tensile

test as outlined in chapter 2, for three reasons. First, it is difficult to prepare and test
specimens having the required geometry. Second, it is difficult to grip brittle materials
without fracturing them. Third, ceramics fail after only about 0.1% strain, which
necessitates that tensile specimens be perfectly aligned to avoid the presence of
bending stresses, which are not easily calculated. Therefore, a more suitable
transverse bending test is most frequently used in which a rod specimen having either
a circular or rectangular cross section is bent until fracture using a three- or four-point
loading technique. The three-point loading scheme is illustrated in Figure 2.

Figure 2: A three-point loading scheme for measuring the stress–strain behavior and flexural strength of
brittle ceramics

The stress at fracture using this flexure test is known as the flexural strength, modulus

brittle ceramics. For a rectangular cross section, the flexural strength 𝜎fs is given by
of rupture, fracture strength, or bend strength, an important mechanical parameter for

3 Ff L
σ fs = 2
2bd

where Ff is the load at fracture, L is the distance between support points, and the other
parameters are as indicated in Figure 2. When the cross section is circular, then

Ff L
σ fs = 3
πR

where R is the specimen radius.

Characteristic flexural strength values for several ceramic materials are given in Table
2.

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Table 2: Tabulation of Flexural Strength (Modulus of Rupture) and Modulus of Elasticity for Ten Common
Ceramic Materials

Elastic Behavior of ceramics

The elastic stress–strain behavior for ceramic materials using these flexure tests is
similar to the tensile test results for metals: a linear relationship exists between stress
and strain. Figure 3 compares the stress–strain behavior to fracture for aluminum
oxide and glass. Again, the slope in the elastic region is the modulus of elasticity; the
range of moduli of elasticity for ceramic materials is between about 70 and 500 GPa,
being slightly higher than for metals. Table 2 lists values for several ceramic
materials. Also, from Figure 3 note that neither material experiences plastic
deformation prior to fracture.

Figure 3: Typical stress– strain behavior to fracture for aluminum oxide and glass.

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Mechanisms of Plastic Deformation

Although at room temperature most ceramic materials suffer fracture before the onset
of plastic deformation, a brief exploration into the possible mechanisms is
worthwhile. Plastic deformation is different for crystalline and noncrystalline
ceramics; each is discussed below

Crystalline Ceramics

For crystalline ceramics, plastic deformation occurs, as with metals, by the

motion of dislocations. One reason for the hardness and brittleness of these materials
is the difficulty of slip (or dislocation motion). For crystalline ceramic materials for
which the bonding is predominantly ionic, there are very few slip systems
(crystallographic planes and directions within those planes) along which dislocations
may move. This is a consequence of the electrically charged nature of the ions. For
slip in some directions, ions of like charge are brought into close proximity to one
another; because of electrostatic repulsion, this mode of slip is very restricted, to the
extent that plastic deformation in ceramics is rarely measurable at room temperature.
By way of contrast, in metals, because all atoms are electrically neutral, considerably
more slip systems are operable and, consequently, dislocation motion is much more
facile.
However, for ceramics in which the bonding is highly covalent, slip is also
difficult, and they are brittle for the following reasons: (1) the covalent bonds are
relatively strong, (2) there are also limited numbers of slip systems, and (3)
dislocation structures are complex.

Non-Crystalline Ceramics

Plastic deformation does not occur by dislocation motion for noncrystalline ceramics
because there is no regular atomic structure. Rather, these materials deform by
viscous flow, the same manner in which liquids deform; the rate of deformation is
proportional to the applied stress. In response to an applied shear stress, atoms or ions
slide past one another by the breaking and re-forming of interatomic bonds. However,
there is no prescribed manner or direction in which this occurs, as with dislocations.
Viscous flow on a macroscopic scale is demonstrated in Figure 4.

Figure 4: Representation of the viscous flow of a liquid or fluid glass in response to an applied shear force.

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The characteristic property for viscous flow, viscosity, is a measure of a

originates from shear stresses imposed by two flat and parallel plates, the viscosity 𝜂
noncrystalline material’s resistance to deformation. For viscous flow in a liquid that

is the ratio of the applied shear stress 𝜏 and the change in velocity d𝜐 with distance dy
in a direction perpendicular to and away from the plates, or

τ F
η= =
dv /dy dv /dy

The units for viscosity are poise (P) and pascal-seconds (Pa·s); 1 P = 1 dyne·s/cm 2,
and 1 Pa·s = 1 N·s/m2. Conversion from one system of units to the other is according
to

10 P = 1 Pa·s

Liquids have relatively low viscosities; for example, the viscosity of water at room
temperature is about 10−3 Pa·s. However, glasses have extremely large viscosities at
ambient temperatures, which are accounted for by strong interatomic bonding. As the
temperature is raised, the magnitude of the bonding is diminished, the sliding motion
or flow of the atoms or ions is facilitated, and subsequently there is an attendant
decrease in viscosity.

Miscellaneous Mechanical Considerations

Influence of Porosity

Some ceramic fabrication techniques, the precursor material is in the form of a

powder. Subsequent to compaction or forming of these powder particles into the
desired shape, pores or void spaces exist between the powder particles. During the
ensuing heat treatment, much of this porosity will be eliminated; however, often this
pore elimination process is incomplete and some residual porosity will remain (Figure
5). Any residual porosity will have a deleterious influence on both the elastic
properties and strength. For example, for some ceramic materials the magnitude of the
modulus of elasticity E decreases with volume fraction porosity P according to
2
E=E0 (1−1.9 P+ 0.9 P )

where E0 is the modulus of elasticity of the nonporous material.

Porosity is deleterious to the flexural strength for two reasons: (1) pores
reduce the cross-sectional area, across which a load is applied, and (2) they also act as
stress concentrators—for an isolated spherical pore, an applied tensile stress is
amplified by a factor of 2. The influence of porosity on strength is rather dramatic; for
example, 10 vol% porosity often decreases the flexural strength by 50% from the
measured value for the nonporous material. Experimentally, it has been shown that
the flexural strength decreases exponentially with volume fraction porosity (P) as

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Figure 5: Scanning electron micrograph of an aluminum oxide powder compact that was sintered at 1700°C
for 6 min. 5000×

σ fs =σ 0 exp (−nP)

where 𝜎0 and n are experimental constants.

Hardness

Accurate hardness measurements are difficult to conduct inasmuch as ceramic

materials are brittle and highly susceptible to cracking when indenters are forced into
their surfaces; extensive crack formation leads to inaccurate readings. Spherical
indenters (as with Rockwell and Brinell tests) are normally not used for ceramic
materials because they produce severe cracking. Rather, hardnesses of this class of
materials are measured using Vickers and Knoop techniques that use indenters having
pyramidal shapes Vickers is widely used for measuring hardnesses of ceramics;
however, for very brittle ceramic materials, Knoop is often preferred. For both
techniques, hardness decreases with increasing load (or indentation size), but
ultimately reaches a constant hardness plateau that is independent of load; the value of
hardness at this plateau varies from ceramic to ceramic. An ideal hardness test would
be designed so as to use a sufficiently large load that lies near this plateau, yet of a
magnitude that does not introduce excessive cracking.

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Possibly the most desirable mechanical characteristic of ceramics is their

hardness; the hardest known materials belong to this group. A listing of a number of
different ceramic materials according to Vickers hardness is contained in Table 3.
These materials are often utilized when an abrasive or grinding action is required.

Creep
Often, ceramic materials experience creep deformation as a result of exposure to
stresses (usually compressive) at elevated temperatures. In general, the time–
deformation creep behavior of ceramics is similar to that of metals however, creep
occurs at higher temperatures in ceramics. High-temperature compressive creep tests
are conducted on ceramic materials to ascertain creep deformation as a function of
temperature and stress level.

Table 3: Vickers (and Knoop) Hardnesses for Eight Ceramic Materials

Applications and Processing of Ceramics

Introduction

In chapter one, the brief introduction about properties of materials have demonstrated
that there is a significant disparity between the physical characteristics of metals and
ceramics. Consequently, these materials are used in completely different kinds of
applications and, in this regard, tend to complement each other and also the polymers.
Most ceramic materials fall into an application–classification scheme that includes the
following groups: glasses, structural clay products, whitewares, refractories,
abrasives, cements, ceramic biomaterials, carbons, and the newly developed advanced
ceramics. Figure 6 and 7 present taxonomy of types and fabrication; processing of
ceramics;

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Types of Ceramic

Figure 6: Classification of ceramic materials on the basis of application.

Fabrication and Processing of Ceramics

Figure 7: classification scheme for the ceramic forming techniques

NOTE: I encourage you to study these taxonomies, not

necessarily for exams but for knowledge seeking.

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