CHAPTER 14

OVERVIEW OF CERAMIC MATERIALS,

DESIGN, AND APPLICATION
R. Nathan Katz
Department of Mechanical Engineering
Worcester Polytechnic Institute
Worcester, Massachusetts

1 INTRODUCTION 419 4.4 Passive Electronics 430

4.5 Piezoceramics 431
2 PROCESSING OF ADVANCED 4.6 Transparencies 432
CERAMICS 420
5 INFORMATION SOURCES 433
3 BRITTLENESS AND BRITTLE 5.1 Manufacturers and Suppliers 433
MATERIALS DESIGN 422 5.2 Data 433
5.3 Standards and Test Methods 434
4 APPLICATIONS 423 5.4 Design Handbooks 435
4.1 Ceramics in Wear
Applications 423 6 FUTURE TRENDS 435
4.2 Thermostructural Applications 427
4.3 Corrosion Resistance 429 REFERENCES 436

1 INTRODUCTION
Engineering ceramics possess unique combinations of physical, chemical, elec-
trical, optical, and mechanical properties. Utilizing the gains in basic materials
science understanding and advances in processing technology accrued over the
past half century, it is now frequently possible to custom tailor the chemistry,
phase content, and microstructure to optimize, applications-specific combina-
tions of properties in ceramics (which includes glasses, single crystals, and coat-
ings technologies, in addition to bulk polycrystalline materials). This capability
in turn has led to many important, new applications of these materials over the
past few decades. Indeed, in many of these applications the new ceramics and
glasses are the key enabling technology.
Ceramics include materials that have the highest melting points, highest elas-
tic modulii, highest hardness, highest particulate erosion resistance, highest ther-
mal conductivity, highest optical transparency, lowest thermal expansion, and
lowest chemical reactivity known. Counterbalancing these beneficial factors are
brittle behavior and vulnerability to thermal shock and impact. Over the past
three decades major progress has been made in learning how to design to mit-
igate the brittleness and other undesirable behaviors associated with ceramics

Handbook of Materials Selection, Edited by Myer Kutz

ISBN 0-471-35924-6 䉷 2002 John Wiley & Sons, Inc., New York

419
420 OVERVIEW OF CERAMIC MATERIALS

and glasses. Consequently, many exciting new applications for these materials
have emerged over the past several decades.
Among the major commercial applications for these materials are:

● Passive electronics (capacitors and substrates)

● Optronics/photonics (optical fibers)
● Piezoceramics (transducers)
● Mechanical (bearings, cutting tools)
● Biomaterials (hard tissue replacement)
● Refractories (furnace linings, space vehicle thermal protection)
● Electrochemical (sensors, fuel cells)
● Transparencies (visible, radar)

This chapter will provide a brief overview of how ceramics are processed and
the ramifications of processing on properties. Next a short discussion of the
special issues that one encounters in mechanical design with brittle materials is
provided. Short reviews of several of the above engineering applications of ce-
ramics and glasses, which discuss some of the specific combinations of prop-
erties that have led design engineers to the selected material(s), follow. A section
on how to obtain information on materials sources and information is provided.
Tables listing typical properties of candidate materials for each set of applica-
tions are included throughout. Finally, some areas of future potential will be
discussed.
2 PROCESSING OF ADVANCED CERAMICS
The production of utilitarian ceramic artifacts via the particulate processing route
outlined in Fig. 1 actually commenced about 10,000 years ago.1 Similarly, glass
melting technology goes back about 3500 years, and as early as 2000 years ago
optical glass was being produced.1 While many of the basic unit processes for
making glasses and ceramics are still recognizable across the millennia, the level
of sophistication in equipment, process control, and raw material control have
advanced by ‘‘lightyears.’’ In addition, the past 50 years has created a fun-
damental understanding of the materials science principles that underlie the
processing–microstrucure–property relationships. Additionally, new materials
have been synthesized that possess extraordinary levels of performance for spe-
cific applications. These advances have led to the use of advanced ceramics and
glasses in roles that were unimaginable 50 or 60 years ago. For example, early
Egyptian glass ca. 2000 BC had an optical loss of ⬃107 dB/km, compared to an
optical loss of ⬃10⫺1 in mid-1980s glass optical fibers,2 a level of performance
that has facilitated the fiber-optic revolution in telecommunications. Similarly,
the invention of barium titanate and lead zirconate titanate ceramics, which have
much higher piezoelectric moduli and coupling coefficients than do naturally
occurring materials, has enabled the existence of modern sonar and medical
ultrasound imaging.3
The processing of modern ceramics via the particulate route, shown in Fig.
1, is the way that ⬃99% of all polycrystalline ceramics are manufactured. Other
techniques for producing polycrystalline ceramics, such as chemical vapor dep-
2 PROCESSING OF ADVANCED CERAMICS 421

POWDER

Raw powder POWDER METAL TECHNOLOGY

DRY POWDER CONSOLIDATION
PLASTIC TECHNOLOGY
AND
WET SHAPING TECHNOLOGY CERAMIC TECHNOLOGY

GREEN CERAMIC BODY

HOT
PRESSING HEAT

Formed product

DENSIFIED AND BONDED

GLAZE CERAMIC

HEAT MACHINING

FINISHED PRODUCT FINISHED PRODUCT

Sintered product

Fig. 1 Processing of polycrystalline ceramics via the particular route.

osition4 or reaction forming5 are of growing importance but still represent a very
small fraction of the ceramic industry. There are three basic sets of unit processes
in the particulate route (and each of these three sets of processes may incorporate
dozens of subprocesses). The first set of processes involve powder synthesis and
treatment. The second set of processes involve the consolidation of the treated
powders into a shaped perform, known as a ‘‘green’’ body. The green body
typically contains about 50 vol % porosity and is extremely weak. The last set
of unit processes utilize heat, or heat and pressure combined, to bond the indi-
vidual powder particles, remove the free space and porosity in the compact via
diffusion, and create a fully dense, well-bonded ceramic with the desired mi-
crostructure.6 If only heat is used, this process is called sintering. If pressure is
also applied, the process is than referred to as hot pressing (unidirectional pres-
sure) or hot isostatic pressing [(HIP), which applies uniform omnidirectional
pressure].
Each of the above steps can introduce processing flaws that can diminish the
intrinsic properties of the material. For example, chemical impurities introduced
during the powder synthesis and treatment steps may adversely effect the optical,
magnetic, dielectric, or thermal properties of the material. Alternatively, the im-
purities may segregate in the grain boundary of the sintered ceramic and nega-
tively effect its melting point, high temperature strength, dielectric properties, or
optical properties. In green-body formation, platey or high aspect ratio powders
may align with a preferred orientation, leading to anisotropic properties. Simi-
larly, hot pressing may impose anisotropic properties on a material. Since ce-
ramics are not ductile materials, they can (usually) not be thermomechanically
modified after primary fabrication. Thus, the specific path by which a ceramic
component is fabricated can profoundly effect its properties. The properties en-
countered in a complex shaped ceramic part are often quite different than those
422 OVERVIEW OF CERAMIC MATERIALS

encountered in a simply shaped billet of material. This is an important point of

which a design engineer specifying a ceramic component needs to be constantly
mindful.
3 BRITTLENESS AND BRITTLE MATERIALS DESIGN
Even when ceramics are selected for other than mechanical applications, in most
cases some level of strength and structural integrity are required. It is therefore
necessary to briefly discuss the issue of brittleness and how one designs with
brittle materials before proceeding to discuss applications and the various ce-
ramic and glass materials families and their properties.
The main issues in designing with a brittle material are that a very large
scatter in strength (under tensile stress), a lack of capacity for mitigating stress
concentrations via plastic flow, and relatively low energy absorption prior to
failure dominate the mechanical behavior. Each of these issues is a result of the
presence of one or more flaw distribution within or at the surface of the ceramic
material and/or the general lack of plastic flow available in ceramics. As a
consequence, ceramic and glass components that are subjected to tensile stresses
are not designed using a single valued strength (deterministic design) as com-
monly done with metals. Rather, ceramic components are designed to a specified
probability of failure (probabilistic design) that is set at acceptably low values.
The statistics of failure of brittle materials whose strength is determined by a
population of varying sized flaws is similar to modeling the statistics of a chain
failing via its weakest link. The statistics utilized are known as Weibull statistics.
A Weibull probability of failure distribution is characterized by two parameters,
the characteristic stress and the Weibull modulus.7 Computer programs for in-
corporating Weibull statistical distributions into finite-element design codes have
been developed that facilitate the design of ceramic components optimized for
low probabilities of failure.8 The effectiveness of such probabilistic design meth-
odology has been demonstrated by the reliable performance of ceramics in many
highly stressed structural applications, such as bearings, cutting tools, turbo-
charger rotors, missile guidance domes, and hip prosthesis.
Flaws (strength-limiting features) can be intrinsic or extrinsic to the material
and processing route by which a test specimen or a component is made. Intrinsic
strength-limiting flaws are generally a consequence of the processing route and
may include features such as pores, aggregations of pores, large grains, agglom-
erates, and shrinkage cracks. While best processing practices will eliminate or
reduce the size and frequency of many of these flaws, it is inevitable that some
will still persist. Extrinsic flaws can arise from unintended foreign material en-
tering the process stream, i.e., small pieces of debris from the grinding media
or damage (cracks) introduced in machining a part to final dimensions. Exposure
to a service environment may bring new flaw populations into existence, i.e.,
oxidation pits on the surface of nonoxide ceramics exposed to high temperatures
or may cause existing flaws to grow larger as in the case of static fatigue of
glass. In general, one can have several flaw populations present in a component
at any time, and the characteristics of each population may change with time.
As a consequence of these constantly changing flaw populations, at the present
time the state of the art in life prediction of ceramic components for use in
extreme environments significantly lags the state of the art in component design.
4 APPLICATIONS 423

As in most fields of engineering, there are some rules of thumb that one can
apply to ceramic design.9 While these are not substitutes for a carefully executed
probabilistic finite-element design analysis, they are very useful in spotting pit-
falls and problems when a full-fledged design cannot be executed due to financial
or time constraints.

Rules of Thumb for Design with Brittle Materials

1. Point loads should be avoided to minimize stress where loads are trans-
ferred. It is best to use areal loading (spherical surfaces are particularly
good); line loading is next best.
2. Structural compliance should be maintained by using compliant layers,
springs or radiusing of mating parts (to avoid lockup).
3. Stress concentrators—sharp corners, rapid changes in section size, un-
dercuts and holes—should be avoided or minimized. Generous radiuses
and chamfers should be used.
4. The impact of thermal stresses should be minimized by using the smallest
section size consistent with other design constraints. The higher the sym-
metry the better (a cylinder will resist thermal shock better than a prism),
and breaking up complex components into subcomponents with higher
symmetry may help.
5. Components should be kept as small as possible—the strength and prob-
ability of failure at a given stress level are dependent on size; thus min-
imizing component size increases reliability.
6. The severity of impact should be minimized. Where impact (i.e., partic-
ulate erosion) cannot be avoided, low angle impacts (20⬚ –30⬚) should be
designed for. Note this is very different than the case of metals, where
minimum erosion is at 90⬚.
7. Avoid surface and subsurface damage. Grinding should be done so that
any residual grinding marks are parallel, not perpendicular, to the direc-
tion of principal tensile stress during use. Machining induced flaws are
often identified to be the strength-limiting defect.
4 APPLICATIONS
The combinations of properties available in many advanced ceramics and glasses
provide the designers of mechanical, electronic, optical, and magnetic systems
a variety of options for significantly increasing systems performance. Indeed, in
some cases the increase in systems performance is so great that the use of
ceramic materials is considered an enabling technology. In the applications ex-
amples provided below the key properties and combinations of properties re-
quired will be discussed, as well as the resultant systems benefits.
4.1 Ceramics in Wear Applications
In the largest number of applications where modern ceramics are used in highly
stressed mechanical applications, they perform a wear resistance function. This
is true of silicon nitride used as balls in rolling element bearings, silicon carbide
journal bearings or water pump seals, alumina washers in faucets and beverage
424 OVERVIEW OF CERAMIC MATERIALS

dispensing equipment, silicon nitride and alumina-based metal cutting tools, zir-
conia fuel injector components, or boron carbide sand blast nozzles, to cite some
typical applications and materials.
Wear is a systems property rather than a simple materials property. As a
systems property, wear depends upon what material is rubbing, sliding, or rolling
over what material, upon whether the system is lubricated or not, upon what the
lubricant is, and so forth. To the extent that the wear performance of a material
can be predicted, the wear resistance is usually found to be a complex function
of several parameters. Wear of ceramic materials is often modeled using an
abrasive wear model where the material removed per length of contact with the
abrasive is calculated. A wide variety of such models exist, most of which are
of the form:

V ⬀ P 0.8KIc⫺0.75H⫺0.5N (1)

where V is the volume of material worn away, P is the applied load, KIc is the
fracture toughness, H is the indentation hardness, and N is the number of ab-
rasive particles contacting the wear surface per unit length. Even if there are no
external abrasives particles present, the wear debris of the ceramics themselves
act as abrasive particles. Therefore, the functional relationships that predict that
wear resistance should increase as fracture toughness and hardness increase are,
in fact, frequently observed in practice.
Even though the point contacts that occur in abrasive wear produce primarily
hertzian compressive stresses, in regions away from the hertzian stress field
tensile stresses will be present and strength is, thus, a secondary design property.
In cases where inertial loading or weight is a design consideration, density may
also be a design consideration. Accordingly, Table 1, lists the fracture toughness,
hardness, Young’s modulus, four-point modulus of rupture (MOR) in tension,
and the density for a variety of advanced ceramic wear materials. Several suc-
cessful applications of ceramics to challenging wear applications are described
below.
Bearings
Rolling element bearings, for use at very high speeds or in extreme environ-
ments, are limited in performance by the density, compressive strength, corrosion
resistance, and wear resistance of traditional high-performance bearing steels.
The key screening test to assess a material’s potential as a bearing element is

Table 1 Key Properties for Wear-Resistant Ceramics

Material KIc(MPa 䡠 m1 / 2) H (kg / mm2) E (GPa) MOR (MPa) ␳ (g / cm3)
Al2O3 99% 3.9–4.5 1900 360–395 350–560 3.9
B4C — 3000 445 300–480 2.5
Diamond 6–10 8000 800–925 800–1400 3.5
SiC 2.6–4.6 2800 380–445 390–550 3.2
Si3N4 4.2–7 1600 260–320 450–1200 3.3
TiB2 5–6.5 2600 550 240–400 4.6
ZrO2 (Y-TZP) 7–12 1000 200–210 800–1400 5.9
4 APPLICATIONS 425

rolling contact fatigue (RCF). RCF tests on a variety of alumina, SiC, Si3N4,
and zirconia materials, at loads representative of high-performance bearings,
demonstrated that only fully dense silicon nitride (Si3N4) could out-perform bear-
ing steels.10 This behavior has been linked to the high fracture toughness of
silicon nitride, which results from a unique ‘‘self-reinforced’’ microstructure,
combined with a high hardness. Additionally, the low density of silicon nitride
creates a reduced centrifugal stress on the outer races at high speeds. Fully dense
Si3N4 bearing materials have demonstrated RCF lives 10 times that of high-
performance bearing steel. This improved RCF behavior translates into DN
(DN ⫽ bearing bore diameter in millimeters ⫻ shaft rpm) ratings for hybrid
ceramic bearings (Si3N4 balls running in steel races, the most common ceramic
bearing configuration), about 50% higher than the DN rating of steel bearings.
Other benefits of silicon nitride hybrid bearings include an order of magnitude
less wear of the inner race, excellent performance under marginal lubrication,
survival under lubrication starvation conditions, lower heat generation than com-
parable steel bearings, and reduced noise and vibration.
Another important plus for Si3N4 is its failure mechanism. When Si3N4 rolling
elements fail, they do not fail catastrophically; instead they spall—just like bear-
ing steel elements (though by a different microstructural mechanism). Thus, the
design community only had to adapt their existing practices, instead of devel-
oping entirely new practices to accommodate new failure modes. The main com-
mercial applications of silicon nitride bearing elements are listed in Table 2.
Cutting Tool Inserts
While ceramic cutting tools have been in use for over 60 years, it is only within
the past two decades that they have found major application, principally in turn-
ing and milling cast-iron and nickel-based superalloys and finishing of hardened
steels. In these areas ceramics based on aluminum oxide and silicon nitride
significantly outperform cemented carbides and coated carbides. High-speed cut-
ting tool tips can encounter temperatures of 1000⬚C or higher. Thus, a key prop-
erty for an efficient cutting tool is hot hardness. Both the alumina and Si3N4
families of materials retain a higher hardness at temperatures between 600 and
1000⬚C than either tool steels or cobalt-bonded WC cermets. The ceramics are
also more chemically inert. The combination of hot hardness and chemical in-
ertness means that the ceramics can run hotter and longer with less wear than

Table 2 Commercial Applications of Si3N4 Hybrid Bearings

Machine tool spindles
Turbomolecular pump shaft
Dental drill shaft
Aircraft wing flap actuators
In-line skates / mountain bikes
Space Shuttle main engine
oxygen fuel pump
The first and largest application, its main benefits are higher
speed and stiffness, hence greater throughput and tighter toler-
ances
Presently the industry standard, the main benefits are improved
pump reliability and marginal lubrication capability, which
provides increased flexibility in pump mounting orientation
The main benefit is sterilization by autoclaving
Wear and corrosion resistance are the main benefits
Wear and corrosion resistance are the main benefits
Here, the bearing is lubricated by liquid oxygen. Steel bearings
are rated for one flight; Si3N4 hybrid bearings are rated for
five.
426 OVERVIEW OF CERAMIC MATERIALS

the competing materials. Historic concerns with ceramic cutting tools have
focused on low toughness, susceptibility to thermal shock, and unpredictable
failure times. Improvements in processing, together with microstructural modi-
fications to increase fracture toughness have greatly increased the reliability of
the ceramics in recent years
Alumina-based inserts are reinforced (toughened) with zirconia, TiC, or TiN
particles or SiC whiskers. The thermal shock resistance of alumina–SiCw is
sufficiently high, so that cooling fluids can be used when cutting Ni-based alloys.
Silicon-nitride-based inserts include fully dense Si3N4 and SiAlON’s, which are
solid solutions of alumina in Si3N4. Fully dense Si3N4 can have a fracture tough-
ness of 6–7 MPa 䡠 m1 / 2, almost as high as cemented carbides (⬃9 MPa 䡠 m1 / 2),
a high strength (greater than 1000 MPa) and a low thermal expansion that yields
excellent thermal shock behavior. Silicon nitride is the most efficient insert for
the turning of gray cast iron and is also used for milling and other interrupted
cut operations on gray iron. Because of its thermal shock resistance, coolant
may be used with silicon nitride for turning applications. SiAlON’s are typically
more chemically stable than the Si3N4’s but not quite as tough or thermal shock
resistant. They are mainly used in rough turning of Ni-based superalloys.
Ceramic inserts are generally more costly than carbides (1.5–2 times more),
but their metal removal rates are ⬃3–4 times greater. However, that is not the
entire story. Ceramic inserts also demonstrate reduced wear rates. The combi-
nation of lower wear and faster metal removal means many more parts can be
produced before tools have to be indexed or replaced. In some cases this en-
hanced productivity is truly astonishing. In the interrupted single-point turning
of the outer diameter counterweights on a gray cast-iron crankshaft a SiAlON
tool was substituted for a coated carbide tool. This change resulted in the metal
removal rate increasing 150% and the tool life increasing by a factor of 10. Each
tool now produced 10 times as many parts and in much less time. A gas turbine
manufacturer performing a machining operation on a Ni-based alloy using a
SiAlON tool for roughing and a tungsten carbide tool for finishing required a
total of 5 h. Changing to SiC-whisker-reinforced alumina inserts for both op-
erations reduced the total machining time to only 20 min. This yielded a direct
savings of $250,000 per year, freed up 3000 h of machine time per year, and
avoided the need to purchase a second machine tool.
Ceramic Wear Components in Automotive and Light-Truck Engines
Several engineering ceramics have combinations of properties that make them
attractive materials for a variety of specialized wear applications in automotive
engines.
The use of structural ceramics as wear components in commercial engines
began in Japan in the early 1980s. Table 3, lists many of the components that
have been manufactured, the engine company that first introduced the compo-
nent, the material, and the year of introduction. In some of these applications
several companies have introduced a version of the component into one or more
of their engines.
Many of these applications are driven by the need to control the emissions
of heavy-duty diesels. Meeting current emissions requirements creates conditions
within the engine fuel delivery system that increase wear of lubricated steel
4 APPLICATIONS 427

Table 3 Ceramic Wear Components in Automotive and Light-Truck Engines

Engine Engine Year of
Component Manufacturer Type Ceramic Introduction
Rocker arm insert Mitsubishi SI Si3N4 1984
Tappet Nissan Diesel Si3N4 1993
Fuel injector link Cummins Diesel Si3N4 1989
Injector shim Yanmar Diesel Si3N4 1991
Cam roller Detroit Diesel Diesel Si3N4 1992
Fuel injector timing plunger Cummins Diesel ZrO2 1995
Fuel pump roller Cummins Diesel Si3N4 1996
SI ⫽ spark-ignited engine.

against steel. One of these conditions is increased injection pressure, another is

an increase in the soot content of engine lubricating oils. Strategic utilization of
ceramic components within the fuel delivery systems of many heavy-duty truck
engines has enabled the engines to maintain required performance for warranties
of 500,000 miles and more. The fuel injector link introduced by Cummins in
1989 is still in production. Well over a million of these components have been
manufactured. And many of these have accumulated more than a million miles
of service with so little wear that they can be reused in engine rebuilds. In a
newer model electronic fuel injector, Cummins introduced a zirconia timing
plunger. The part has proved so successful that a second zirconia component
was added to the timing plunger assembly several years later. Increasingly strin-
gent emissions requirements for heavy diesels has increased the market for ce-
ramic components in fuel injectors and valve train components. Many of these
heavy-duty engine parts are manufactured at rates of 20,000 up to 40,000 per
month.
Perhaps the largest remaining problem for this set of applications is cost.
Ceramic parts are still more expensive than generally acceptable for the auto-
motive industry. Reluctance of designers to try ceramic solutions still exists, but
it is greatly diminishing thanks to the growing list of reliable and successful
application of structural ceramic engine components.
4.2 Thermostructural Applications
Due to the nature of their chemical bond, many ceramics maintain their strength
and hardness to higher temperatures than metals. For example, at temperatures
above 1200⬚C, silicon carbide and silicon nitride ceramics are considerably
stronger than any superalloy. As a consequence, structural ceramics have been
considered and utilized in a number of demanding applications where both me-
chanically imposed tensile stresses and thermally imposed tensile stresses are
present. One dramatic example is the ceramic (silicon nitride) turbocharger that
has been in commercial production for automobiles in Japan since 1985. Over
one million of these have been manufactured and driven with no recorded failure.
This is a very demanding application, as the service temperature can reach
900⬚C, stresses at ⬃700⬚C can reach 325 MPa, and the rotor must also endure
oxidative and corrosive exhaust gases that may contain erosion inducing rust
and soot particles. Silicon nitride gas turbine nozzle vanes have been flying for
 428 OVERVIEW OF CERAMIC MATERIALS

several years in aircraft auxiliary power units. Other applications include heat
exchangers, and hot gas valving. Recently, ceramic matrix composites have been
introduced as disks for disk breaks in production sports cars by two European
manufacturers. A major future market for structural ceramics may be high-
performance automotive valves. Such valves are currently undergoing extensive,
multiyear fleet tests in Germany.
This class of applications requires a focus on the strength, Weibull modulus,
m (the higher the m, the narrower the distribution of observed strength values),
thermal shock resistance, and often the stress rupture (strength decrease over
time at temperature) and/or creep (deformation with time at temperature) be-
havior of the materials. Indeed, as shown in Fig. 2, the stress rupture perform-
ance of current structural ceramics represents a significant jump in materials
performance over superalloys.
The thermal shock resistance of a ceramic is a systems property rather than
a fundamental materials property. Thermal shock resistance is given by the max-
imum temperature change a component can sustain, ⌬T.

␴ (1 ⫺ ␮) k
⌬T ⫽ S (2)
␣E rmh

where ␴ is strength, ␮ is Poisson’s ratio, ␣ is the coefficient of thermal expansion

(CTE), E is Young’s modulus, k is thermal conductivity, rm is the half-thickness
for heat flow, h is the heat transfer coefficient, and S is a shape factor totally
dependent on component geometry.11 Thus it can be seen that thermal shock
resistance, ⌬T, is made up of terms wholly dependent on materials properties,
dependent on heat transfer conditions, and on geometry. It is the role of the
ceramic engineer to maximize the former and of the design engineer to maximize
the later two terms. It has become usual practice to report the materials-related
thermal shock resistance as the instantaneous thermal shock parameter, R, which
is equal to

LIVE GRAPH
Click here to view
200
100 Hot-Pressed Si3N4 (High-Time Dependence)
Hi-Perf
Stress, ksi

Ceramics at
Sintered SiC (Low-Time Dependence) 2200°F
10 2000°F
Hi-Perf-NiCo
2100°F
Superalloys
(i.e. , René-80,
B-1900)
1
0.1 1 10 100 1000
Time, h
Fig. 2 Stress rupture performance of nonoxide structural ceramics compared to superalloys
(oxidizing atmosphere).
4 APPLICATIONS 429

Table 4 Calculated Thermal Shock Resistance of Various Ceramics

Material ␴ (MPa) ␮ CTE (cm / cm K) E (GPa) R (K)
Al2O3 (99%) 345 0.22 7.4 ⫻ 10-6 375 97
AlN 350 0.24 4.4 ⫻ 10⫺6 350 173
SiC (sintered) 490 0.16 4.2 ⫻ 10⫺6 390 251
PSZ 1000 0.3 10.5 ⫻ 10⫺6 205 325
Si3N4 (sintered) 830 0.3 2.7 ⫻ 10⫺6 290 742
LAS (glass CERAMIC) 96 0.27 0.5 ⫻ 10⫺6 68 2061
Al-titanate 41 0.24 1.0 ⫻ 10⫺6 11 2819

␴(1 ⫺ ␮)
R⫽ (3)
␣E

The value of R for selected ceramics is presented in Table 4. Another frequently

used parameter is R⬘, the thermal shock resistance where some heat flow occurs:
R⬘ is simply R multiplied by the thermal conductivity, k. For cases where heat
transfer environments are complex, Ref. 12 lists 22 figures of merit for selecting
ceramics to resist thermal stress.
4.3 Corrosion Resistance
Many advanced structural ceramics such as alumina, silicon nitride, or SiC have
strong atomic bonding that yields materials that are highly resistant to corrosion
by acidic or basic solutions at room temperature (the notable exception being
glass or glass-bonded ceramics attacked by HF). This corrosion resistance has
led to many applications. Carbonated soft drinks are acidic, and alumina valves
are used to meter and dispense these beverages at refreshment stands. The chem-
ical industry utilizes a wide variety of ceramic components in pumps and valves
for handling corrosive materials. For example, the outstanding corrosion resis-
tance of fully dense SiC immersed in a variety of hostile environments is given
in Table 5. There are many cases where corrosion and particulate wear are
superimposed, as in the handling of pulp in papermaking or transporting slurries
in mineral processing operations, and ceramics find frequent application in such
uses.

Table 5 Weight Loss of Fully Dense SiC in Acids and Bases

Reagent (wt %) Test Temperature (⬚C) Weight Loss (mg / cm2 yr)
98% H2SO4 100 1.5
50% NaOH 100 2.5
53% HF 100 ⬍0.2
85% H3PO4 100 ⬍0.2
45% KOH 100 ⬍0.2
25% HCl 100 ⬍0.2
10% HF ⫹ 57% HNO3 25 ⬍0.2
Specimens submerged 125 to 300 h, continuously stirred.
Data Courtesy of ESK-Wacker, Adrian, MI.
430 OVERVIEW OF CERAMIC MATERIALS

4.4 Passive Electronics

The role of passive electronics is to provide insulation (prevent the flow of
electrons) either on a continuous basis (as in the case of substrates or packages
for microelectronics) or on an intermittent basis as is the case for ceramic ca-
pacitors (which store electric charge and hence need a high polarizability). These
two applications constitute two of the largest current markets for advanced ce-
ramics. For electronic substrates and packages key issues include the minimi-
zation of thermal mismatch stresses between the Si (or GaAS) chip and the
package material (so the CTE will be important) and dissipation of the heat
generated as electrons flow through the millions of transistors and resistors that
comprise modern microelectronic chips; hence the thermal conductivity is a key
property. All other things being equal, the delay time for electrons to flow in
the circuit is proportional to the square root of the dielectric constant of the
substrate (or package) material. Additionally, the chip or package must maintain
its insulating function, so resistivities of ⬎1014 are required. Most high-
performance packages for computer chips are alumina. With the advent of mi-
crowave integrated circuits (e.g., cell phones) aluminum nitride substrates are
beginning to be utilized for high thermal conductivity. The environmental draw-
backs to machining BeO has tended to favor the use of AlN to replace or avoid
the use of BeO. Synthetic diamond is an emerging substrate material for special
applications. Isotopically ‘‘pure’’ synthetic, single-crystal diamond has values of
thermal conductivity approaching 10,000 W/mK. Typical values of the above
properties for each of these materials is given in Table 6, along with selected
properties of silicon for comparison. For design purposes exact values for spe-
cific formulations of the materials should be obtained from the manufacturers.
Over a billion ceramic capacitors or multilayer ceramic capacitors (MLCC)
are made every day.13 Since electrons do not flow through capacitors, they are
considered passive electronic components. However, the insulators from which
ceramic capacitors are made polarize thereby separating electric charge. This
separated charge can be released and flow as electrons, but the electrons do not
flow through the dielectric material of which the capacitor is composed. Thus,
the materials parameter, which determines the amount of charge that can be
stored, the dielectric constant, k, is the key parameter for design and application.
Table 7 lists the approximate dielectric constant at room temperature for several
families of ceramics used in capacitor technology. The dielectric constant varies

Table 6 Key Properties for Electronic Substrates and Packages

Therm. Cond. Dielectric
Material CTE (10⫺6 / K) (W / mK) Resistivity Const.
Al2O3 (96%) 6.8 26 ⬎1014 9.5
Al2O3 (99%) 6.7 35 ⬎1014 10
AlN 4.5 140–240 ⬎1014 9
BeO 6.4 250 ⬎1014 6.5
Diamond 2 2000 ⬎1014 5.5
Silicon 2.8 150
Note: CTE and thermal conductivity are at room temperature, and the dielectric constant is at 1
MHz.
4 APPLICATIONS 431

Table 7 Dielectric Constants for Various Ceramic

Capacitor Materials
Material Dielectric Constant at RT
Tantalum oxide (Ta2O5) ⬃25
Barium titinate ⬃5,000
Barium–zirconium titinate ⬃20,000
Lead–zirconium titinate (PZT) ⬃2,000
PZT with W or Mg additives ⬃9,000
Lead magnesiun niobate (PMN) ⬃20,000
Lead zinc niobate (PZN) ⬃20,000

with both temperature and frequency. Thus, for actual design precise curves of
materials performance over a relevant range of temperatures and frequencies are
often utilized. Many ceramics utilized as capacitors are ferroelectrics, and the
dielectric constant of these materials is usually a maximum at or near the Curie
temperature.
4.5 Piezoceramics
Piezoceramics are a multi-billion dollar market.14 Piezoceramics are an enabling
material for sonar systems, medical ultrasonic imaging, micromotors and micro-
positioning devices, the timing crystals in our electronic watches, and numerous
other applications. A piezoelectric material will produce a charge (or a current)
if subjected to pressure (the direct piezoelectric effect) or, if a voltage is applied,
the material will produce a strain (the converse piezoelectric effect). Upon the
application of a stress, a polarization charge, P, per unit area is created that
equals d␴, where ␴ is the applied stress and d is the piezoelectric modulus. This
modulus, which determines piezoelectric behavior, is a third-rank tensor15 that
is thus highly dependant on directions along which the crystal is stressed. For
example, a quartz crystal stressed in the [100] direction will produce a voltage,
but one stressed in the [001] direction will not. In a polycrystalline ceramic the
random orientation of the grains in an as-fired piezoceramic will tend to mini-
mize or zero out any net piezoelectric effects. Thus, polycrystalline piezocer-
amics have to undergo a postsintering process to align the electrically charged
dipoles within the polycrystalline component. This process is known as poling
and it requires the application of a very high electric field. If the piezoceramic
is taken above a temperature, known as the Curie temperature, a phase trans-
formation occurs and piezoelectricity will disappear. The piezoelectric modulus
and the Curie temperature are thus two key materials selection parameters for
piezoceramics.
The ability of piezoceramics to almost instantaneously convert electrical cur-
rent to mechanical displacement, and vice versa, makes them highly usefull as
transducers. The efficiency of conversion between mechanical and electrical en-
ergy (or the converse) is measured by a parameter known as the coupling co-
efficient. This is a third key parameter that guides the selection of piezoelectric
materials.
Although piezoelectricity was discovered by Pierre and Jacques Curie in
1880, piezoceramics were not widely utilized until the development of poly-
432 OVERVIEW OF CERAMIC MATERIALS

crystalline barium titanate in the 1940s and lead zirconate titanates (PZT) in the
1950s. Both of these materials have high values of d and thus develop a high
voltage for a given applied stress. PZT has become widely used because in
addition to a high d value, it also has a very high coupling coefficient. Sonar,
in which ultrasonic pulses are emitted and reflected ‘‘echoes’’ are received, is
used to locate ships, fish, and map the ocean floor by navies, fishermen, and
scientists all over the globe. Medical ultrasound utilizes phased arrays of piezo-
ceramic transducers to image organs and fetuses noninvasively and without
exposure to radiation. A relatively new application that has found significant use
in the microelectronics industry is the use of piezoceramics to drive microposi-
tioning devices and micromotors. Some of these devices can control positioning
to a nanometer or less. Piezoceramic transducers combined with sophisticated
signal detection and generation electronics to create ‘‘active’’ noise and vibration
damping devices. In such devices the electronics detect and quantify a noise
spectrum and then drive the transducers to provide a spectrum 180⬚ out of phase
with the noise, thereby, effectively canceling it.
Many of the current high-performance applications of piezoceramics are
based on proprietary modifications of PZT, which contain additions of various
dopants or are solid solutions with perovskite compounds of Pb with Mg, Mn,
Nb, Sn, Mo, or Ni. Table 8, lists the range of several key piezoceramic selection
parameters for proprietary PZT compositions from one manufacturer.
4.6 Transparencies
Transparent ceramics (which include glasses, single-crystal, and polycrystalline
ceramics) have been used as optical transparencies or lenses for millennia. Glass
windows were in commercial production in first century Rome, but it was not
until the 1800s, with the need for precision optics for microscopes, telescopes,
and ophthalmic lenses, that glasses and other optical materials became the object
of serious scientific study. As noted in the introduction, progress in glass science
and technology, coupled with lasers, has led to the current broadband digital
data transmission revolution via optical fibers. Various ceramic crystals are used
as laser hosts and specialty optical lenses and windows. A significant frac-
tion of supermarket scanner windows combine the scratch resistance of sapphire
(single-crystal alumina) with its ability to transmit the red laser light that we see
at the checkout counter. While such windows are significantly more costly than
glass, their replacement rate is so low that they have increased profitability for
several supermarket chains. For the same reason the crystal in many high-end
watches are scratch-resistant manmade sapphire. Polycrystalline translucent (as
opposed to fully transparent) alumina is used as containers (envelops) for the
sodium vapor lamps that light our highways and industrial sites.

Table 8 Key Properties for PZT Based Piezoceramics

Piezoelectric Curie Temp Coupling
Material Modulus, d33 (⬚C) Coefficent, k33
A 226 ⫻ 10⫺12 m / V 320 0.67
B 635 ⫻ 10⫺12 m / V 145 0.68
C 417 ⫻ 10⫺12 m / V 330 0.73
5 INFORMATION SOURCES 433

Not all windows have to pass visible light. Radar or mid- to far-infrared
transparencies look opaque to the human eye but are perfectly functional win-
dows at their design wavelengths. The most demanding applications for such
transparencies is for the guidance domes of missiles. Materials that can be used
for missile radomes include slip-cast fused silica, various grades of pyroceram
(glass ceramics), and silicon-nitride based materials. Infrared (IR) windows and
missle domes include MgF2 and ZnSe. Requirements exist for having missile
guidance domes that can transmit in the visible, IR, and radar frequencies (multi-
mode domes). Ceramic materials that can provide such functionality include
sapphire and aluminum oxynitride spinel (AlON). In addition to optical prop-
erties missile domes must be able to take high aerothermal loading (have
sufficient strength) and be thermal shock resistant (a high-speed missile encoun-
tering a rain cloud can have an instant ⌬T of minus several hundred degrees
kelvin).
Key properties for visible and IR optical materials include the index of re-
fraction, n (which will be a function of wavelength), and absorption or loss. For
radar transparencies key parameters are dielectric constant (which can be thought
of as analogous to the index of refraction) and dielectric loss.
5 INFORMATION SOURCES
5.1 Manufacturers and Suppliers
There are hundreds of manufacturers of advanced ceramics and glasses. Locating
ones that either already have the material that is needed, and can produce it in
the configuration required, can be a daunting task. There are two resources
published annually that make this task much easier. The American Ceramic
Society publishes a directory of suppliers of materials, supplies, and services
that can help locate such information quickly. It is called Ceramic Source. This
directory can also be accessed on the worldwide web at www.ceramics.org. A
similar Buyers Guide is published by Ceramic Industry Magazine, and this can
also be viewed online at www.ceramicindustry.com. Once a likely source for
your need has been identified, a visit to the supplier’s web site can often provide
a great deal of background information and specific data, which can make further
contacts with the supplier much more meaningful and informative.
5.2 Data
Manufacturer’s literature both hardcopy and posted on the worldwide web, are
invaluable sources of data. The handbooks, textbooks, and encyclopedias listed
below are also excellent sources of data. However, before committing to a fi-
nalized design or to production, it is advisable to develop one’s own test data
in conformance with you own organization’s design practice. Such data should
be acquired from actual components made by the material, processing route, and
manufacturer that have been selected for the production item.

ASM, Ceramics and Glasses, Vol 4, Engineered Materials Handbook, ASM

International, Materials Park, OH, 1991.
J. F. Shackelsford, W. Alexander, and J. Park (eds.), Materials Science and
Engineering Handbook, 2nd ed., CRC Press, Boca Raton, FL, 1994.
434 OVERVIEW OF CERAMIC MATERIALS

C. X. Campbell and S. K. El-Rahaiby (eds.), Databook on Mechanical and

Thermophysical Properties of Whisker-Reinforced Ceramic Matrix Com-
posites, Ceramics Information Analysis Center, Purdue University, W. La-
fayette, IN, and The American Ceramic Society, Westerville, OH, 1995.
R. J. Brook (ed.), Concise Encyclopedia of Advanced Ceramic Materials,
Pergamon Press, Oxford, 1991.
5.3 Standards and Test Methods
To reliably design, procure materials, and assure reliability, it is necessary to
have common, agreed-upon, and authoritative test standards, methods, and prac-
tices. Institutions such as the American Society for Testing of Materials (ASTM),
the Japanese Institute for Standards (JIS), the German Standards Organization
(DIN), and the International Standards Organization (ISO) all provide standards
for there various constituencies. The following are a sampling of standards avail-
able from the ASTM and JIS for advanced ceramics and ceramic matrix com-
posites. One can reach these organizations at the following addresses.

American Society for Testing Materials (ASTM), 100 Barr Harbor Drive,
Conshohocken, PA 19428-2959:
● C-177-85(1993), Test Method for Steady State Heat Flux and Thermal
Transmissionby Means of the Gradient-Hot-Plate Apparatus
● C-1161-90, Test Method for Flexural Strength of Advanced Ceramics
at Ambient Temperature
● C-1211-92, Test Method for Flexural Strength of Advanced Ceramics
at Elevated Temperature
● C-1259-94, Test Method for Dynamic Young’s Modulus, Shear Mod-
ulus and Poisons Ratio for Advanced Ceramics by Impulse Excitation
of Vibration
● C-1286-94, Classification for Advanced Ceramics
● C-1292-95A, Test Method for Shear Strength of Continuous Fiber-
Reinforced Ceranic Composites (CFCCs) at Ambient Temperatures
● C-1337-96, Test Method for Creep and Creep-Rupture of CFFFs un-
der Tensile Loading at Elevated Temperature
● C-1421-99, Standard Test Method for Determination of Fracture
Toughness of Advanced Ceramics at Ambient Temperature
● C-1425-99, Test Method for Interlaminar Shear Strength of 1-D and
2D CFCCs at Elevated Temperature
● E-228-85(1989), Test Method for Linear Thermal Expansion of Solid
Materials with aVitreous Silica Dilatometer
● E-1269-94, Test Method for Determining Specific Heat Capacity by
DifferentialScanning Calorimetry
● E-1461-92, Test Method for Thermal Diffusion of Solids by the Flash
Method
The Japanese Standards Association, 1-24, Akasaka 4, Minato-ku, Tokyo 107
Japan:
6 FUTURE TRENDS 435

● Testing Methods for Elastic Modulus of High Performance Ceramics

at ElevatedTemperatures; JIS R 1605-(1989)
● Testing Methods for Tensile Strength of High Performance Ceramics
at Room and Elevated Temperatures; JIS R 1606-(1990)
● Testing Methods for Fracture Toughness of High Performance Ceram-
ics; JIS R 1607-(1990)
● Testing Methods for Compressive Strength of High Performance Ce-
ramics; JIS R 1608-(1990)
● Testing Methods for Oxidation Resistance of Non-Oxide of High Per-
formance Ceramics; JIS R 1609-(1990)
● Testing Methods for Vickers Hardness of High Performance Ceram-
ics; JIS R 1610-(1991)
● Testing Methods of Thermal Diffusivity, Specific Heat Capacity, and
ThermalConductivity for High Performance Ceramics by Laser Flash
Method; JIS R 1611-(1991)

In addition to testing standards, it is possible to obtain standard materials with

certified properties to calibrate several of these new standards against your own
tests. Such standard materials can be obtained from the National Institute of
Science and Technology (NIST). For example, a standard material to calibrate
ASTM C-1421-99 has just been made available. Materials standards are not
available for all of the above tests.
5.4 Design Handbooks
It has been widely recognized that procedural handbooks that provide method-
ology on how to design with advanced ceramics and which can provide high
quality evaluated design data are sorely needed for ceramic materials. The ce-
ramics matrix composites (CMCs) community has taken the initiative to begin
the process of creating such a handbook for its constituency. The activity is
sponsored by various U.S. governmental agencies including the Department of
Defense, the Department of Energy, The Federal Aviation Administration, and
the National Aeronautics and Space Administration and is entitled MIL-
Handbook-17. This activity brings together materials suppliers, materials testers,
designers, and end users who are engaged in developing a handbook that will
provide design tools and guidance, provide guidelines on data generation, doc-
umentation, and use, and provide an authoritative source of design quality data.
This is a work in progress and its completion is many years off, if ever. Nev-
ertheless, much guidance in design and testing of advanced CMCs has already
resulted from this activity. Progress can be followed by periodically accessing
the handbook websites at http://mil-17.udel.edu or http://www.materials-
sciences.com/MIL17/. Unfortunately, no similar activity exists for monolithic
ceramics.
6 FUTURE TRENDS
It has been estimated that in the United States advanced ceramics of the type
discussed above are an over $8-billion-dollar a year industry with a growth rate
of ⬃8% per year.16
436 OVERVIEW OF CERAMIC MATERIALS

The largest segment of this growth will come from the electronics area. Not
only will there be significant growth in the ‘‘traditional’’ roles of ceramics as
insulators, packages, substrates, and capacitors, but structural ceramics will play
a major role in the equipment used in semiconductor manufacturing. This trend
will be especially driven by the resistance of ceramics such as SiC, AlN, silicon
nitride, and alumina to the erosive and corrosive environments within high-
energy plasma chambers used in single-wafer processing operations.
The intertwined global issues of energy sufficiency and environmental pro-
tection will see commercial use of advanced ceramics in energy systems as
diverse as solid oxide fuel cells and pebble-bed modular reactors (nuclear). As
more and more industries move toward ‘‘green’’ (pollution free) manufacturing,
there will be growth in wear- and corrosion-resistant ceramics for industrial
machinery. There will also be substantial growth potential for ceramic filters and
membranes. One major environmentally driven opportunity will be particulate
traps for diesel trucks and industrial power sources. This technology is just
beginning to be commercialized, and it is certain to see rapid growth as emis-
sions requirements for diesel engines grow more stringent. Not all progress in
these areas will create increased markets for ceramics; some will reduce them.
For example, the rapid growth of energy-efficient light-emitting diode technol-
ogy for illumination will create a significant growth opportunity for producers
of single-crystal SiC substrates and GaN materials. However, this will come at
a cost to the ceramics industry of a significant decrease in glass envelopes for
incandescent bulbs and fluorescent tubes. Another area of growth will be filters
and membranes for filtration of hot or corrosive, or both, gases and liquids.
The explosive growth of fiber-optic- and microwave-based digital communi-
cations technology has produced significant opportunities and markets for ad-
vanced ceramics and glasses and will continue to do so into the foreseeable
future.
Medical applications are sure to grow, both in the area of diagnostics and
prosthetics.
At the entrance to the Pohang Steel complex in Pohang, Republic of Korea,
is a wonderful sign. It proclaims; ‘‘Resources are Limited—Creativity is Unlim-
ited.’’ This thought certainly applies to the global future of advanced ceramics.
Creatively utilized advanced ceramics will effectively expand our resources, pro-
tect our environment, and create new technological opportunities. The potential
opportunities go far beyond the few discussed in this chapter.
REFERENCES
1. P. B. Vandiver, ‘‘Reconstructing and Interpreting the Technologies of Ancient Ceramics,’’ in
Materials Issues in Art and Archaeology, Materials Res. Soc. Symposium Proceed., Vol. 123,
MRS, Pittsburgh, 1988, pp. 89–102.
2. Materials Science and Engineering for the 1990’s, National Academy Press, Washington, DC,
1989, p. 24.
3. R. N. Katz, ‘‘Piezoceramics,’’ Ceramic Industry, Aug. 20 (2000).
4. D. W. Richerson, Modern Ceramic Engineering, 2nd ed., Marcel Dekker, New York, 1992,
pp. 582–588.
5. J. S. Haggerty and Y. M. Chiang, ‘‘Reaction-Based Processing Methods for Materials and Com-
posites,’’ Ceramic Eng. Sci. Proceed., 11(7–8), 757–781 (1990).
6. See Ref. 4, Chapters 9–11.
REFERENCES 437

7. A. F. McLean and D. Hartsock, ‘‘Design with Structural Ceramics,’’ in Treatise on Materials

Science and Technology, Vol. 29, J. B. Wachtman (Ed.), Academic Press, Boston, 1989, pp. 27–
95.
8. N. N. Nemeth and J. P. Gyekenyesi, ‘‘Probabilistic Design of Ceramic Components with the
NASA / CARES Computer Program,’’ in Ceramics and Glasses: Vol. 4, Engineered Materials
Handbook, ASM International, Metals Park, OH, 1991, pp. 700–708.
9. R. N. Katz, ‘‘Application of High Performance Ceramics in Heat Engine Design,’’ Materials Sci.
Eng., 71, 227–249 (1985).
10. R. N. Katz, ‘‘Ceramic Materials for Roller Element Bearing Application,’’ in Friction and Wear
of Ceramics, Said Jahanmir (Ed.), Marcel Dekker, New York, 1994, pp. 313–328.
11. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2nd ed., Wiley,
New York, 1976, p. 822 ff.
12. D. P. H. Hasselman, ‘‘Figures-of-Merit for the Thermal Stress Resistance of High Temperature
Brittle Materials: A Review,’’ Ceramurgia International, 4(4), 147–150 (1998).
13. D. W. Richerson, The Magic of Ceramics, The American Ceramic Society, Westerville, OH,
2000, p. 141.
14. NSF Workshop Report, Fundamental Research Needs in Ceramics, Washington, DC, April, 1999,
p. 9.
15. J. F. Nye, Physical Properties of Crystals, Oxford University Press, London, 1964, pp. 110ff.
16. T. Abraham, ‘‘US Advanced Ceramics Growth Continues,’’ Ceramic Industry, Aug., pp. 23–25
(2000).