Ceramics, Advanced Structural Products 1

Ceramics, Advanced Structural Products

W. Roger Cannon, Department of Ceramics, Rutgers – The State University, Piscataway, New Jersey 08854,
United States
Ernst Gugel, CFI – Ceramics for Industry GmbH & Co. KG, Roedental, Federal Republic of Germany

Gerhard Leimer, CFI – Ceramics for Industry GmbH & Co. KG, Roedental, Federal Republic of Germany

Gerhard Woetting, CFI – Ceramics for Industry GmbH & Co. KG, Roedental, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . .. 1 3.2. Zirconia . . . . . . . . . . . . . . . . . . . . 7

2. Mechanical Properties . . . . . . . . .. 2 3.3. Silicon Carbide . . . . . . . . . . . . . . . 8
2.1. Failure of Brittle Materials – Flaws . 2 3.4. Silicon Nitride . . . . . . . . . . . . . . . 9
2.2. The Small Strain to Failure . . . . . .. 3 3.5. Ceramic – Ceramic Composites . . . . 9
2.3. Effects of Microstructure . . . . . . .. 4
3.6. Other Materials . . . . . . . . . . . . . . 10
2.4. Effects of Temperature . . . . . . . . .. 4
2.5. Wear Resistance and Hardness . . .. 6 4. Manufacturing Methods . . . . . . . . . 11
3. Individual Ceramic Materials . . . .. 6 5. Uses . . . . . . . . . . . . . . . . . . . . . . 11
3.1. Alumina . . . . . . . . . . . . . . . . . .. 6 6. References . . . . . . . . . . . . . . . . . . 15

1. Introduction Further developments in chemical stoneware

The viability and lifetime of chemical engineer-
ing facilities depend on the quality of the ma-
terials from which the critical components are
made. Wear caused by abrasion and/or corro-
sion results in economic losses of many million
marks. Hence, materials which lead to a longer
lifetime of industrial structures or even to an im-
proved process, are of key importance. In this
respect, the increasing interest in ceramic mate-
rials for structural applications is not surprising,
since modern ceramic materials have reached a
high standard of quality and reliability by inten-
sive developments of materials and production
technology.
Ceramic materials are well-known to the
chemical industry; they have been used on a
large scale for many years, for example, as lin-
ings of large containers, packings, catalyst sup-
ports, filters, etc. Furthermore, in the early years
of the chemical industry, ceramics in the form of
chemical stoneware [1] made a major contribu-
tion to their success. Containers with a volume of
2000 L, columns several meters high, pipelines
and heat exchangers, and, in particular, pumps
made of the classical ceramic stoneware were
notable early forerunners of modern engineered
ceramics.
[1] led to corundum stoneware with its higher
strength, and to cordierite and Li – Al stoneware,
which show improved thermal shock resist-
ance, but unsatisfactory chemical resistance. All
these desirable properties are met by beryllium
stoneware, which did not reach application be-
cause of difficulty in processing large compo-
nents, but more especially because of its toxicity
in production.
Stoneware is made from natural raw materi-
als. Due to impurities and inhomogeneities, its
microstructure is rather coarse, contains consid-
erable glass and microcracks, and is inhomo-
geneous, resulting in only limited mechanical
properties. The decisive step from low-strength
(classical) ceramics, such as bricks, dishes, and
wall and floor tiles, to high mechanical strength
ceramics, resulted from progress in materials
science and production technology knowledge
in the course of the last few decades.
A new generation of ceramic materials is be-
ing developed with specifically controlled prop-
erties, based on fine-grained or whiskerlike pure
powders of defined composition, which have
been developed by the chemical industry and
are now available in large quantities. With these
powders, ceramics with a controlled microstruc-
ture, which are characterized by small crack and

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a06 043
2 Ceramics, Advanced Structural Products
defect sizes can be produced, provided that their
production is carefully controlled. Defects be-
come increasingly critical if the powder of the
starting material is very fine grained. Though an
extremely fine microstructure may have some
advantages, too much should not be expected of
nanotechnology, at least in the near future, as its
realization for large components with reliable
properties at acceptable costs is problematic.
The same applies to very tough ceramics.
Although considerable progress has been made
with the incorporation into ceramics of particles,
whiskers, or fibers which inhibit crack growth
and therefore lead to an increase in fracture
toughness and a certain crack tolerance, a gen-
eral elimination of the brittleness to give “duc-
tile” ceramics cannot be expected.
Regardless of these possibilities for the fu-
ture, the quality of currently available materials
is sufficiently high that even high tensile stress
applications are possible, provided the com-
ponents are properly designed. However, even
the modern, highly dense ceramics are brittle,
and the component designer needs to learn how
to design components to eliminate high tensile
stress concentrations. With increasing familiar-
ity, designers will not only look to the metallic
and polymeric materials with which they are al-
ready familiar, but also to ceramic materials for
structural design work.
Brittleness also causes a higher sensitivity to
material defects. This is reflected in the vari-
ability in strength, which can be described by
Weibull statistics (see Section 2.2). Apart from
the mean value, the statistical value for fracture
probability, expressed as the Weibull modulus,
is required for reliable design with ceramics. It
even allows data gained from small samples to
be transferred to complex components. A desir-
able low variation range is indicated by a high
Weibull modulus; a value of greater than 15 is
sufficient in most cases.
Development of modern ceramic materials is
certainly not yet finished, however. The stage
has been set for applications which could not be
imagined until a short time ago. With regard to
the future, it is not only important to increase
the strength level. The critical point is that the
properties achieved in the laboratory must be re-
alized in mass production. This requires homo-
geneous properties within components and from
part to part, which means minimizing the varia-
tion range and therefore elimination of problems
resulting from the brittleness by even tighter
control. Such control is absolutely necessary for
high-reliability applications.
2. Mechanical Properties
2.1. Failure of Brittle Materials – Flaws
The key to understanding the mechanical prop-
erties of ceramics is the Griffith theory for fail-
ure of brittle materials [3]. Unlike most met-
als and polymers, ceramics are extremely brittle
and, therefore, extremely sensitive to the pres-
ence of any sort of flaw on the surface or in
the bulk of the ceramic. Flaws of some size are
always present in a material. These may arise
during manufacture or in subsequent handling
of the material. Since polycrystalline ceramics
are usually manufactured by sintering a pow-
der compact at high temperature, the flaws may
arise from nonuniformities in the packing of the
powder or accidental inclusions in the compact.
The Griffith criterion states that if the flaw
is larger than a critical size, then the rate of re-
lease of elastic strain energy is greater than the
rate of gain of surface energy and the flaw will
grow (crack extension). The growth is catas-
trophic because as the crack grows longer, the
driving force becomes greater. The Griffith cri-
terion is a necessary but not sufficient condition
for crack growth. In addition, the stress at the
tip of the crack must be large enough to break
the ionic or covalent bonds. Orowan estimated
this stress and found that for a sharp crack the
Griffith stress was sufficient to break the bonds
[4]. The Griffith equation is


2Eγ
σf =
πC
where σ f is the fracture stress, the applied stress
at which the preexisting flaw becomes critical,
E is the elastic modulus (Young’s modulus), γ is
the effective surface energy, and C is the length
of a surface flaw or 2 C is the length of an interior
flaw. One assumption is that only the increas-
ing surface area of the crack acts to resist crack
growth. However, other features besides surface
energy resist the propagation of the crack: plas-
tic deformation near the tip of the crack, crack
 Ceramics, Advanced Structural Products
bridging, and crack deflection. Commonly these
contributions are included in γ, which is then re-
named the fracture energy, γ f .
The Griffith equation is sometimes written in
terms of the critical stress intensity factor de-
fined as
√ the mean strength of the fibers.
KC ≡Y σf C
where Y is a dimensionless constant that de-
pends on the geometry of loading and the crack
configuration. The fracture stress is then written
as follows:
1  KC
σf = 2Eγ/C = √
Y Y C
This second form of the Griffith equation is
useful because K C can be measured by vari-
ous fracture-mechanics techniques. (K IC is of-
ten used instead of K C , the subscript I indicat-
ing the mode of cracking.) Table 1 shows how
the fracture stress and the critical flaw size are
related for a promising structural ceramic such
as hot-pressed silicon carbide (SiC). The values
chosen for this example are a K C of 4 MPa m0.5
and a Young’s modulus E of 400 GPa. This table
indicates that the flaw size for the high-strength
ceramics is very small and that careful manu-
facturing techniques are necessary to avoid ac-
cidentally producing such small flaws in poly-
crystalline materials.
Table 1. Fracture strength vs. flaw size
σ f , MPa C, µm
1000 5 failure is necessary. The most widely used statis-
500 20
250 80
100 500
50 2025
Even if great care is taken to manufacture a
material so that the largest flaw is on the order of
1 µm, there is no guarantee that new flaws will
not be introduced during operation by scratching
or particle impact. As a result, most research in
developing structural ceramics is now concerned
with increasing K C . Equation (1) shows that ac-
ceptable flaw size is proportional to the square
of the K C value, e.g., doubling K C allows a flaw
size 4 times larger.
The K C value is really an indicator of
how brittle or tough the material is. Vari-
ous methods have been used to increase K C
3
to as high as 10 – 15 MPa m0.5 . These high
fracture toughnesses have been achieved with
ceramic – ceramic composites. Continuous fiber
composites, usually fabricated from woven ce-
ramic cloth, are almost completely insensitive to
flaws; however, they are strongly dependent on
2.2. The Small Strain to Failure
A second aspect of brittleness in ceramics is the
small strain to failure. Ceramics do not undergo
plastic deformation at room temperature as do
(1) metals. Plastic deformation in both metals and
ceramics results from microscopic defects called
dislocations. These dislocations move easily in
the presence of a stress field in metals, but they
do not move easily in ceramics. The stress at
which plastic deformation could take place in
ceramics is much higher than the fracture stress.
The opposite is true for metals. As a conse-
quence, the strain to failure in ceramics is usu-
ally on the order of only 0.1 %, and ceramics can
only be used when the stress is safely below the
fracture stress.
The strong sensitivity to flaws and small
strains to failure, however, may be compensated
by other outstanding properties of ceramics, e.g.,
wear resistance or corrosion resistance.
Safe design of ceramics in tensile or bend-
ing load applications requires knowledge of the
necessary safety factor. To estimate the safety
factor properly, information on the statistics of
tics are Weibull statistics. The Weibull equation
is as follows:
ln (1/ (1−Pf )) = lnV +mln (σf −σµ ) −mlnσ0
where Pf is the probability of failure of a part
subject to the stress, V is the volume of the sam-
ple under the tensile stress, σµ is the stress of
zero probability of failure, usually taken as zero,
σ 0 is a normalizing parameter of no physical sig-
nificance, and m is a constant designated as the
Weibull modulus. This equation indicates that
the probability of failure at a certain stress is re-
lated to the volume of the material under stress
(or may be related to the area under stress if fail-
ure is from surface flaws). Such a relationship
between volume and stress has been verified ex-
perimentally. The equation may be linearized by
4 Ceramics, Advanced Structural Products
plotting ln ln (1/(1 − Pf )) vs. ln σ f , allowing the
probability of failure at any given stress to be
estimated by extrapolating a straight line. This
is termed a Weibull plot (Fig. 1).
Figure 1. Failure probability vs. fracture stress, a Weibull
plot [5]
An additional important concern in design is
slow crack growth. The crack grows under stress
in the presence of atmospheric moisture. The ve-
locity v of crack growth is given by the equation
v=αK N
where K is the stress intensity factor, α is a con-
stant, and N is the velocity exponent. Such an
equation can be incorporated into Weibull statis-
tics for a more accurate treatment. This subject
is reviewed in [6].
2.3. Effects of Microstructure
Microstructure of polycrystalline materials has
an important effect on the strength of the
ceramic. Generally, strength is improved by
achieving a fine grain size. If the flaw size is
much larger than the grain size, however, grain
size has little effect. For materials having very
anisotropic thermal coefficients of expansion
and large grain size, microcracking develops
when the ceramic is cooled to room tempera-
ture after sintering. This can be detrimental to
strength. In addition, microcracking may occur
near second phases having different coefficients
of expansion than the continuous phase. Finally,
microcracking may occur if the second phase
undergoes a phase transformation involving a
large change in volume, for instance, the phase
transformation of quartz at 573 ◦ C.
Large grains and second phases are not al-
ways bad. Large grains if properly designed
may bridge cracks, so that higher stresses are
required to propagate the crack, and therefore,
toughen the ceramic and in many cases also in-
crease the fracture strength. A new class of self-
reinforced ceramics (primarily silicon nitride)
has been developed. In situ reinforced silicon
nitride mimics whisker-reinforced ceramics, ex-
cept that the whiskerlike grains are grown from
β-silicon nitride seed grains during the sintering
process. Careful control of the additives, tem-
perature, and the starting powder is necessary to
achieve high toughness and strength. A strength
of 1000 GPa and a toughness of 10 MPa · m0.5
can be achieved by careful control of the num-
ber and size of the whiskerlike grains in a fine-
grained silicon nitride matrix [7]. This innova-
tion was necessary for the commercialization of
silicon nitride roller bearings.
2.4. Effects of Temperature
The effect of temperature on the strength of
ceramics is illustrated in Figure 2. There is
a decrease in strength at high temperatures,
where some plastic deformation begins to take
place. The temperature at which this decrease
in strength begins depends on the material. In
materials with a cubic crystal symmetry, such
as MgO or UO2 , the temperature at which the
strength begins to drop is generally low, but in
Al2 O3 the strength drops off little up to 1000 ◦ C.
At high temperatures the strength depends on the
rate at which the stress is applied.
Above one-half the melting temperature,
creep (slow time-dependent deformation) be-
comes appreciable. Since many of the important
applications of ceramics are high-temperature
applications, creep is important. Creep of ce-
ramic materials has been reviewed by Cannon
and Langdon [8]. Most fine-grained polycrys-
talline ceramics under moderately low applied
stresses deform according to one of the follow-
ing two equations: the Nabarro – Herring equa-
tion [9],
10Ω σDv
ε̇ = (2)
kT d2
or the Coble equation [10],
 Ceramics, Advanced Structural Products
50Ω σwDb
ε̇ =
kT d3
where ε̇ is the creep rate, Ω is the volume of
a vacancy, σ is the applied stress, Dv is volume
self-diffusion coefficient, d is grain diameter, k is
Boltzmann’s constant, T is temperature (K), w is
the effective width of the grain boundary, and Db
is grain boundary diffusion coefficient. The two
equations indicate that the most highly creep re-
sistant materials are large-grained ceramics. The
equations also indicate that the creep resistance
is related to the diffusion coefficient. The diffu-
sion coefficient is generally very low in ceramics
having a high melting temperature, and therefore
ceramics are generally creep resistant materials
at high temperatures (> 1000 ◦ C). If the ceramic
contains a glassy grain boundary phase, then
creep rates are somewhat higher than those given
in these equations. If high creep resistance is de-
sired, the glassy phase should be eliminated or
high-temperature viscous glass should be used.
Figure 2. Typical fracture strength vs. temperature curves
Ceramics are sometimes limited as a high-
temperature material by the inability to with-
stand thermal shock, i.e., rapid drop in temper-
ature. Their lack of thermal shock resistance is
primarily due to their inability to accommodate
the strain caused by a rapidly cooling surface
adjacent to a hot interior. The low thermal con-
ductivity of ceramics contributes to this lack of
thermal shock resistance. The critical tempera-
ture drop ∆T c through which a material may be
5
shocked without exceeding the fracture stress at
the surface is given by the equation
σf (1−ν)
∆Tc =
ψE α
where α is the thermal coefficient of expansion,
ν is Poisson’s ratio, and ψ is a factor depend-
ing on thermal conductivity, size of piece, and
heat transfer coefficient. The equation contains
several materials parameters generally available,
and therefore may be used to estimate the rel-
ative thermal shock resistance of various ma-
terials. Table 2 compares the thermal shock
resistance of various advanced structural ce-
ramic materials for both rapid thermal shock
(R=σf (1−ν) /E α) and slow thermal shock
(R =σf k (1−ν) /E α), where k is the thermal
conductivity).
2.5. Wear Resistance and Hardness
Metallic parts that tend to wear out, e.g., in
engines, may be replaced by ceramic parts for
longer life. Ceramics exhibit good wear resist-
ance and erosion resistance because of their
hardness, i.e., they do not plastically deform eas-
ily. Those with the greatest resistance to plas-
tic deformation are the covalently bonded ma-
terials and the ones of greatest hardness. How-
ever, resistance to crack propagation also has
some influence on the hardness and wear re-
sistance since cracks form under concentrated
point loading. These point loadings may be due
to dust particles, grit, or other types of concen-
trated loads. Some of these cracks propagate par-
allel to the surface at first and then up toward
the surface, resulting in small chips dislodged
from the surface. After many of these chips have
been dislodged, the surface is rougher and wears
even faster. Thus, under severe load conditions
ceramics may not have better wear resistance
than much softer materials. Improving fracture
toughness can improve abrasion resistance.
3. Individual Ceramic Materials
Table 3 lists a number of ceramics that are con-
sidered advanced structural ceramics. The most
important advanced structural materials being
6 Ceramics, Advanced Structural Products
Table 2. Factors affecting the thermal shock behavior

Material Bending Modulus of Poissons ratio Coefficient of Thermal R, K R
,

strength, elasticity E, ν thermal expansion conductivity kW m−1
MPa GPa α, 273 – 1273 K, k at 773 K,
10−6 K−1 W m−1 K−1

Hot-pressed Si3 N4 850 310 0.27 3.2 17 625 11

Reaction-bonded Si3 N4 240 220 0.27 3.2 15 250 3.7
Reaction-bonded SiC 500 410 0.24 4.3 84 215 18
Hot-pressed Al2 O3 500 400 0.27 9.0 8 100 0.8

developed at this time are the oxides zirconia and talline alumina lamp hulls for high-temperature
alumina and the covalent materials silicon car- sodium vapor street lamps.
bide and silicon nitride. In addition, cordierite is
important because of its use in heat exchangers.
Table 4 lists the important mechanical properties
of several of these materials. Flexure strengths
are included though they depend strongly on the
flawsize and therefore the care in fabrication.
The range of values of K IC is included, although
these values depend strongly on the method of
testing. (For the general production methods and
economic aspects of advanced structural prod-
ucts → Ceramics, General Survey.)
Table 3. Some advanced structural ceramics and potential materials
with their chemical formulas
Generic name Chemical formula

Alumina [1344-28-1] Al2 O3

Zirconia [1314-23-4] ZrO2
Zircon [1490-68-2] ZrO2 · SiO2
Spinel [1302-67-6] MgO · Al2 O3
Mullite [55964-99-3] 3 Al2 O3 · SiO2
Cordierite [12182-53-5] 2 MgO · 2 Al2 O3 · 5 SiO2
Silicon carbide [409-21-2] SiC
Silicon nitride [12033-89-5] Si3 N4
SiAlON Si6− z Alz Oz N8− z
Boron carbide [12069-32-8] B4 C
Aluminum nitride [24304-00-5] AlN
Glass ceramics a common composition is
Al2 O3 , Li2 O, and SiO2
with TiO2 or ZrO2
nucleating agents Figure 3. Ionic self-diffusion coefficients in ceramic oxides
[11]

Several grades of sintered alumina are avail-

3.1. Alumina
Of the advanced structural materials polycrys-
talline alumina is perhaps the easiest to manufac-
ture, is relatively inexpensive, has high strength,
and is the most widely used. It is widely used
for crucibles, tubes, and rods for high tempera-
ture and for a large number of wear-resistant and
corrosion-resistant specialized items. Perhaps
the most important single products are spark
plugs and the optically translucent polycrys-
able, the grades being distinguished by the pu-
rity. The chief impurity is silica, which forms
glass at the grain boundary. This glass acts as a
sintering aid, lowering the sintering temperature
by several hundred kelvin, but as a result these
aluminas have lower strength and hardness. The
proper glass compositions, however, can im-
prove the low-temperature strength. High-purity
alumina is necessary for high-temperature creep
resistance, for otherwise the glass in the grain
boundary begins to flow, producing grain bound-
 Ceramics, Advanced Structural Products 7
Table 4. Engineering ceramic materials and their basic properties

Property Si3 N4 SiC ZrO2 Al2 O3 (+ ZrO2 ) Al2 TiO5

3
Density, g/cm 3.2 3.2 6 3–4 3
Bending strength, MPa 200 – 1000 500 500 to > 1000 300 – 600 40
Bending strength at 1400 ◦ C, MPa 200 – 600 200 – 400 100 100 – 400 50
Hardness, GN/m2 14 – 17 25 – 30 12 18 – 23
Fracture toughness K IC , MPa m0.5 3 – 10 3–5 6 – 15 3 (8) 1
Young’s modulus 200 – 300 400 200 400 (300) 20
Coefficient of thermal expansion 3 4.5 10 8 2
20 – 1200 ◦ C, (10−6 K−1 )
Thermal conductivity, W m−1 K−1 10 – 40 100 – 140 2 30 2
Thermal shock resistance high high medium low (medium) very high
Abrasion resistance very good very good good good no

ary sliding. Magnesium oxide is used as a sin-
tering aid to sinter high-purity, high-density alu-
mina.
Figure 3 is a summary of bulk diffusion coef-
ficients of various ions in ceramic oxides. Equa-
tions (2) and (3) predict that creep rates should
be proportional to the diffusion coefficients, and
a comparison of diffusion coefficients is a good
way of comparing the fundamental resistances
to creep. As shown in Figure 3, both the Al ion
and the O ion in alumina have two of the low-
est diffusion coefficients, accounting for the low
creep rate of high-purity alumina. However, the
creep resistance of alumina is exceeded by that
of silicon carbide, and thus for many very creep
resistant applications, silicon carbide is being
increasingly used.
New developments in improving the creep
resistance of alumina are noteworthy. Ohji et
al. [12] reported that alumina containing 17 %
silicon carbide nanocrystalline particulates have
a creep rate three orders of magnitude slower
and creep lifetimes ten times longer than mono-
lithic alumina polycrystals. French et al. [13]
reported alumina with only 1000 ppm of yttria
had a creep rate one to two orders of magni-
tude slower than monolithic alumina polycrys-
tals. The former development, though somewhat
difficult to manufacture, would allow alumina to
approach competitiveness with silicon carbide
for creep resistance without the oxidation prob-
lems of the latter.
3.2. Zirconia
Because of its high melting temperature
(2764 ◦ C) zirconia can be used for structural ap-
plications at higher temperatures than alumina.
It is also used widely as a refractory because
it does not react with glass. A few percent of
MgO, CaO, or Y2 O3 are added to zirconia to
stabilize the high-temperature cubic phase; oth-
erwise, zirconia undergoes a destructive phase
transformation from tetragonal to monoclinic
when cooled from the sintering temperature.
However, partially stabilized zirconia, i.e., that
containing less additive than necessary to estab-
lish 100 % cubic, was determined as early as
1947 to be more resistant to thermal shock than
the fully stabilized form [14].
The thermal shock resistance of the partially
stabilized zirconia may result from a very fine
tetragonal precipitate present even at room tem-
perature. The tetragonal precipitate is prevented
from transforming to monoclinic by the con-
straint of the matrix, since the precipitate must
necessarily expand 3 – 5 % and shear 8 % dur-
ing the transformation to monoclinic. The tough-
ening effect of the precipitate arises from the
transformation that takes place as a crack ap-
proaches the precipitate [15]. The stress field
of the crack interacts with the precipitate, al-
lowing the transformation to occur. As the crack
passes the precipitate, the transformation of the
precipitate then places a compressive stress on
the crack, thus reducing its tendency to propa-
gate further. This type of transformation, which
takes place in response to stress rather than a
change in temperature, is termed a martensitic
transformation.
If less than 4 % yttria is added to zirconia and
a fine grain structure is maintained, the material
can be made 100 % tetragonal phase. These ma-
terials, called tetragonal zirconia, are stronger
than partially stabilized zirconia. They can be
8 Ceramics, Advanced Structural Products
made even stronger by adding alumina precipi-
tates [16].
Transformation-toughened ceramics [17], as
these materials are called, are thus far limited
to low-temperature use. The strength drops off
linearly as the temperature approaches 1200 ◦ C,
where the tetragonal-to-monoclinic transforma-
tion normally occurs, as shown in Figure 4.
Thermal fatigue is also important. If the materi-
als soak at a high temperature, the microstruc-
ture changes slightly, reducing the strength. The
high-temperature loss of strength and thermal
fatigue characteristics are of concern since one
potential use is for the cylinder lining in an “adia-
batic” diesel engine. The high strength and good
insulating ability of transformation-toughened
ceramics make them a strong candidate for this
use.
Figure 4. Bending strength of several commercial partially
stabilized zirconia materials [18]
The companies and stabilizers:

NGK, Y2 O3 ; 
Nilsen, MgO;  Coors, 3 % MgO; and ◦• Feldmühle,
MgO. Filled symbols are room-temperature strength after
1000-h exposure at 1000 ◦ C
3.3. Silicon Carbide
Silicon carbide [19], like most other covalent
materials, is not easily sintered from a powdered
compact. One process for producing a dense sil-
icon carbide structure is to bond silicon carbide
grains, produced by the Acheson process, to-
gether with fired clay, glass, silicon nitride, or
by other proprietary means. These materials are
quite creep resistant and thus can be used for fur-
nace elements and for high-temperature struc-
tural use.
The first self-bonding silicon carbide was
originally known as Refel silicon carbide, but
is now generally known as reaction-sintered sil-
icon carbide. It is made by forming a compact
of silicon carbide grains with excess carbon and
then at a high temperature immersing the com-
pact into a molten silicon bath. The silicon and
carbon are then allowed to react at some high
soak temperature to form a silicon carbide reac-
tion layer around the original grains. A variation
in the process is to introduce the silicon in the va-
por phase. Another variation is to introduce the
excess carbon as a polymer binder during injec-
tion molding. Although the properties are usu-
ally considerably better than those of the glass-
bonded or clay-bonded types, they are some-
what degraded by the residual unchanged sili-
con nearly always present in reaction-sintered
silicon carbide.
In 1973 Prochazka of the General Elec-
tric Co. demonstrated that very fine grained SiC
could be pressureless sintered with only a small
amount of sintering aids, typically 0.5 % boron
and 1 % excess carbon. The sintering tempera-
ture is 1900 – 2100 ◦ C [19]. Later a similar pro-
cess was patented to sinter α-SiC.
Both reaction-sintered silicon carbide and
sintered silicon carbide have structural proper-
ties superior to those of the earlier bonded silicon
carbides. The sintered silicon carbide, generally,
is slightly superior to the reaction-sintered sili-
con carbide. Even better mechanical properties
may be achieved by hot pressing silicon carbide
to full density with boron and carbon or alumina
sintering aids. Since hot pressing is expensive,
this material is not widely produced.
3.4. Silicon Nitride
Silicon nitride [20], also a covalent material,
is likewise not sinterable from powder without
additives. Unlike silicon carbide, however, no
sintering aids have been found that allow sili-
con nitride to be sintered to full density with-
out very high pressures except for intentionally
added 5 – 15 % glass phase. The sintering ad-
ditives commonly used are Al2 O3 , Y2 O3 , MgO
and rare earth additives. These sintering addi-
tives combine with silica present on the surface
of the powder to form a glass that allows the ma-
terial to densify during the sintering operation.
A sufficient amount of glass of low viscos-
ity is necessary to achieve high densities; how-
 Ceramics, Advanced Structural Products
ever, large amounts of glass of low viscosity de-
grade the important high-temperature properties
of the material. Hence, an optimum is sought
between high density, which results in good low-
temperature strength, and additives that produce
good high-temperature strength. Ideally, the ad-
ditive after sintering would enter into solid solu-
tion with silicon nitride, but thus far only limited
success has been achieved in finding such alloys.
A compound related to silicon nitride that
has found successful commercialization is
SiAlON, an aluminum silicon oxide nitride.
The most common form has the formula
Si6−z Alz Oz N8−z , where z ranges from 0 to
4. Compounds with z near zero have good high-
temperature strength, creep resistance, and ox-
idation resistance, whereas those with z ap-
proaching 4 have good low-temperature prop-
erties, i.e., strength, toughness, and abrasion re-
sistance.
The properties of silicon nitride are strongly
dependent on the additive. Table 5 compares
properties of silicon nitride hot pressed with
MgO additive, silicon nitride sintered with
Y2 O3 additive, reaction bonded silicon nitride,
and SiAlON. Generally higher strengths are
achieved both at low and high temperatures
by hot pressing; however, this is not an eas-
ily commercialized process for mass production.
Reaction-bonded silicon nitride, made by expos-
ing a silicon powder compact to nitrogen at high
temperatures, has poor low-temperature strength
but good high-temperature strength.
In situ reinforced silicon nitrides containing
high-temperature second phases [22] have in-
creased creep resistance almost comparable to
that of sintered α-silicon carbide [23]. They
have, however, two advantages over silicon car-
bide. The thermal expansion coefficient of sili-
con nitride is lower than that of silicon carbide,
and therefore the rapid thermal shock resistance
of silicon nitride is better. Second, the strength
of silicon nitride, even at high temperature, is
quite high and generally much better than that
of silicon carbide.
3.5. Ceramic – Ceramic Composites
There has been much activity in developing var-
ious ceramic – ceramic composites [24]. These
include continuous fiber composites, whisker
9
composites, layered composites, and particulate
composites. Most of the activity has centered on
two-dimensional woven continuous fiber com-
posites made either by chemical vapor infiltra-
tion (CVI), or ceramic precursor polymer infil-
tration into woven ceramic cloth layed-up into
two-dimensional layers. The most popular fibers
are silicon carbide and more recently alumina.
The advantages are extremely good flaw insen-
sitivity, high thermal shock resistance and high
strains to failure. Figure 5 illustrates an extreme
example of the increased strength and strain to
failure gained by adding carbon fibers to glass.
Figure 5. Stress – strain data for glass and carbon fiber re-
inforced glass (CRG) tested in bending [25]
At the point where the dotted line deviates
from the solid line, the matrix, but not the fibers,
begins to crack. At higher strain the fibers begin
to crack and pull out of the matrix, but the com-
posite still supports some load until all the fibers
have fractured. As shown in the figure, the strain
can be greater than 1 % before complete failure,
a contrast to the normal 0.1 % strain before fail-
ure. This improvement in strain to failure is the
most appealing attribute of fiber composites.
Most composites do not exhibit such high
strains, but they do have strains two to ten times
higher than those of monolithic ceramics. The
second major advantage of the fiber composite is
its insensitivity to flaws. Flaws introduced dur-
ing machining or impact by high velocity grit
have little effect on the fracture strength. The
key to achieving high strength and large strains
to failure is to have strong fibers and a weak in-
terface between the fibers and the matrix. When
a crack impinges on a fiber, the matrix/fiber in-
terface debonds, allowing the crack to pass by
without fracturing the fiber. Various coatings are
applied to fibers to allow them to debond, but
the most popular are carbon and boron nitride.
10 Ceramics, Advanced Structural Products
Table 5. The effects of additives on the properties of silicon nitride [21]
Material Bending strength, four point, MPa
RT∗ 373 K 1648 K
Hot pressed (MgO additive) 690 620 330
Sintered (Y2 O3 additive) 655 585 275
Reaction bonded (2.45 g/cm3 ) 210 345 380
SiAlON (sintered) 485 485 275
∗ RT = room temperature.
Application of high temperature may burn off
the carbon and boron nitride coatings, limiting
the fiber composites to generally about 1000 ◦ C.
Much research is focused on oxide coatings,
which will readily debond but are not burned off
at high temperatures. There are already a few
applications where these materials have found
a niche, but generally their cost is prohibitive.
The fibers themselves cost from a few hundred
to thousands of dollars per kilogram.
Whisker composites are much less expensive
and easier fabricated into a variety of shapes.
Alumina/silicon carbide whisker composites are
already used widely for cutting tools. The advan-
tage again is flaw insensitivity. When silicon car-
bide whiskers are added to alumina, the tough-
ness increases from 4 MPa m0.5 to 9 MPa m0.5 .
This is not so large a flaw insensitivity as those
of continuous-fiber composites, but it is suffi-
cient to make them very useful. The largest dif-
ficulty facing whisker-reinforced ceramics are
the environmental health and safety issues dur-
ing manufacturing. These issues have discour-
aged some companies from introducing ceramic
whisker composite products.
A third technology is layered composites.
The layers are usually produced by tape casting
and stacking, similar to multilayered microelec-
tronic packages. The key to toughness is a weak
interface between the layers. These composites
are only in the research stage.
3.6. Other Materials
Several other materials listed in Table 3 have a
wide range of uses. Glass ceramic has a wide
range of compositions and uses. Cordierite has
a low coefficient of thermal expansion and is
Modulus of Coefficient Thermal
elasticity, of thermal conductivity,
GPa expansion, W m−1 K−1
10−6 K−1
317 3.0 30 – 15
276 3.2 28 – 12
165 2.8 6–3
297 3.2 22
widely used where good thermal shock resis-
tance is required: cordierite is used for substrates
in catalytic converters (see → Automobile Ex-
haust Control) and in the regenerator core of heat
exchangers. Mullite is used much like alumina
but at lower temperature. Its thermal shock resis-
tance is better than that of alumina, and mullite
of the proper composition and grain structure
can be very resistant to creep. Zircon also has an
excellent thermal shock resistance. Aluminum
nitride has a high thermal conductivity.
4. Manufacturing Methods
The ability to produce specific components in a
desired shape and size depends on the ceramic
shaping and sintering processes (see Fig. 6).
The starting powders are mixed homoge-
neously with appropriate organic additives, sol-
vents or water, and disperants, depending on the
forming technique. In the next step, this mixture
is shaped into a green body. This green body
can be machined mechanically in an intermedi-
ate step, if it is not possible to obtain the de-
sired shape by the ceramic shaping process it-
self. After pyrolysis of the temporary binders
etc. that are necessary for shaping, the sintering
step follows under temperature, time, pressure,
and atmospheric conditions that depend on the
material. During the sintering process the body
suffers a 10 – 20 % shrinkage, making exact tol-
erances difficult. For this reason and because
of the possible low-quality surface finish, costly
mechanical machining with diamond tools is of-
ten required. These machining processes have
also been considerably improved resently.
In special cases the piece that is to be sintered
is subjected to hot isostatic pressure (HIP) under
N2 or Ar gas to optimize density and strength.
 Ceramics, Advanced Structural Products 11

Figure 6. Production of engineering ceramic components

12 Ceramics, Advanced Structural Products
Fittings
This is used for the production of ball bearings Bearings
made of silicon nitride. – Friction bearings, tube protectors SiC
To avoid defects, nondestructive testing – Roller bearings Si3 N4
Heat exchangers
methods, such as ultrasonic testing, microfocus – Tubes SiC
radiography, and proof tests, are applied. Non Ventilators
– Rotors, turbines SiC, Si3 N4
destructive testing has been developed to a high Wear protection
level and proven to be reliable, for example, for – Linings Al2 O3
the quality control of silicon nitride ball bearings – Nozzles Al2 O3 , B4 C, SiC,
Si3 N4
for space flight, and can be easily integrated into – Metal forming Si3 N4 , ZrO2
mass production. Thermocouple protection tubes Al2 O3 , ZrO2 , Si3 N4 ,
SiC
Several engineering ceramic components are
already produced in bulk quantities. In many
cases the quantities are still rather small, but
an impressive variety of shapes can be fabri- Thread Guides. Ceramic thread guides have
cated. The fact that ceramics are not easily ma- been used for many decades now and are a good
chined for prototype parts has been a disad- example illustrating the reliability of ceramics.
vantage; however, solid free form fabrication Generally, Al2 O3 is the material of choice, but in
(SFF) techniques, which are CAD/CAM com- special cases also TiO2 or Si3 N4 . Due to the ap-
puter designed, can fabricat prototypes with a plication of ceramics, durability of thread guides
rapid turnaround time and are likely to be widely in textile machines has been improved consid-
used in the future [26]. erably. About 3 × 106 km of textile thread at
a speed of 6000 m/min runs through a thread
guide. The costs for the ceramic material is less
5. Uses than DM 1 per tonne of processed textile threads.

The application of engineered ceramics is Fittings. In the broad field of fittings for the
widely spread over many fields of technical pro- measurement and control technology, such as
cesses for which use is made of their unique cocks, valves, pushers, and gates for gaseous,
properties. Furthermore, the high potential ex- liquid, and powder media, ceramics also have
tends well beyond already established applica- attained an increased significance, especially,
tions. due to their outstanding wear resistance. As
Compared with other structural materials, an example aluminum oxide seal disks have
metals or polymers, ceramic materials will not become standard equipment. Furthermore, fit-
play in future such a big role with respect to tings equipped with engineering ceramics can
quantity. Their significance can be seen more in be found in mining, steel and metallurgical en-
the fact that they will be found in key applica- gineering, oil and gas industry, power stations,
tions. They are applied in essential parts that are chemical and petrochemical plant, paper and
crucial for the functionality of the whole system, pulp industry flue gas desulfurization, and in-
i.e., enabling technologies. cineration plants for refuse, chemicals, and toxic
Some applications and possibilities for ce- media [27], [28]. Although the price for fittings
ramics in chemical engineering are summarized equipped with ceramics is slightly higher, cost
in the following: reduction results from the broader cost/profit re-
duction, in the crucial improvements in function-
Fittings ality, lower servicing requirements, and greater
– Valves (cones, seats, relief nozzles) Si3 N4 (ZrO2 , SiC)
– Cocks (ball, cylinder, rotating-disks) Al2 O3 , SiC, ZrO2 , durability. For example, inductive mass flow me-
Si3 N4 ters are now made of aluminum oxide or zirco-
– Seal disks Al2 O3 , SiC
– Flow meters Al2 O3 , ZrO2 nium oxide [29].
Pumps
– Face seals SiC, Al2 O3
– Separation cans Si3 N4 , ZrO2
Mechanical Face Seals. A good example of
– Plungers Al2 O3 , ZrO2 successful substitution of metals by ceramics is
– Impellers, cases Al2 O3 , SiC the ring and its counterpart in modern face seals.
 Ceramics, Advanced Structural Products
The requirement for resistance to wear, corro-
sion, and heat under increasingly severe condi-
tions, cannot be met by other materials. Hard
metals and materials based on carbon have from
the beginning substituted for metallic seal mate-
rials; however, these are being increasingly re-
placed first by aluminum oxide and then later
by silicon carbide [30]. The main applications
for pumps are chemical and engineering tech-
nology, petrochemistry, energy generation, wa-
ter supply, and environmental technology [31].
As a result of increased production rates, costs
could be reduced to a level such that silicon car-
bide can even replace aluminum oxide in the
seals of the automotive cooling-water pumps.
Friction Bearings. A steadily increasing ap-
plication is magnetically coupled, seal-less
pumps which enable an absolutely leakage-free
and therfore emission-free and environmentally
harmless transportation of media [31].
The impeller of the pump has a bearing which
is lubricated by the pumped medium itself. Be-
cause of their high wear resistance, especially
radial and axial friction, ceramic bearings have
proved to be an excellent application. However,
in some cases insufficient running quality has
been noticed; here the application of roller bear-
ings is recommended.
Separation Can. In the magnetically driven
fluid pump described above, a separation can is
applied as a separator between the media and the
environment. Using a ceramic material, such as
zirconium oxide or silicon nitride, is advisable
here due to its corrosion resistance [30]. Because
of the required low wall thickness, production of
this component is not simple but is feasible.
Pump Cases and Wheels. The classical
materials for pumps, cast iron and cast steel,
are sometimes unsatisfactory because of corro-
sion and erosion; polymers are often unsuitable
due to insufficient thermal resistance. In such
cases, only ceramic materials can meet the re-
quirements (Tables 4 and 6) [33].
Formerly stoneware was primarily used but
increasingly has been replaced by polymers and
metals. However, where these do not work en-
tirely satisfactorily for technical or cost reasons,
it is possible to use ceramics, especially alu-
minum oxide and silicon carbide. These com-
13
plex components are a real challenge for the ce-
ramic producer.
Silcon carbide pumps are excellently well
suited for titanium dioxide production by the
sulfate process, where metal pumps usually fail
within a few months [34].
Roller Bearings. Silicon nitride has proved
to be an ideal material for roller bearings. Hy-
brid bearings with ceramic rolling elements and
metallic bearing races can be found in many
applications [35]. In chemical environments,
mainly full ceramic bearings are used [36]. Prop-
erties, such as low weight, low thermal expan-
sion, high hardness, low wear, high strength and
temperature stability, high chemical resistance,
nonmagnetism, and electrically insulating be-
havior are important advantages. These result,
for example, in higher bearing stiffness, lower
friction and therefore lower rate of heating, as
well as the possibility of operating at higher
speeds.
Finally, ceramic ball bearings can be used in
various media and still show excellent running
properties, especially in case of deficient lubri-
cation or even lack of lubrication. For high-speed
bearings centrifugal force is lower because of the
lower weight, leading to better kinematic prop-
erties. These result in a more favorable roll-off
behavior as well as a higher lifetime.
Silicon nitride roller bearings are also applied
as stiff and high-speed, high-precision spindle
bearings in machine manufacturing, aeronau-
tics, and space technology. But also in com-
mon machine manufacturing, in automotive and
technical engineering, in chemical engineering,
in instrument technology as well as in mea-
surement and control technology, silicon nitride
roller bearings have found more and more in
roads and are increasingly being considered for
wider use. Hybrid bearings in vacuum pumps,
for example, have become standard [35], as they
lead to an increased lifetime with a higher re-
liability. Furthermore, hybrid bearings are also
increasingly applied to high-speed drilling ma-
chines in dental technology, especially due to
better sterilizability. For full ceramic bearings
a wide field of application is opening up in
media-lubricated pumps for chemical environ-
ments [36]. Unlike friction bearings based on
silicon carbide, they do not have dry-running
problems during start-up.
14 Ceramics, Advanced Structural Products
Table 6. Comparison of materials used in pumps

Stress ∗

Mechanical Temperature Corrosion Abrasion erosion Tribological Cavitation

Cast iron + + – + + +/–

High-/low-alloy ++ + ++/+ – – +/–
iron/cast steel
Polymers +/– – +/– + +/– +/–
Ceramics – ++ ++/+ ++ ++ +/–

∗ ++ Very high resistance, + high resistance, – limited resistance.

Production of ceramic ball bearings, rollers, considered for the cylinder lining and the pis-
and rings is a great challenge, in view of fabri- ton caps, both for wear resistance (ceramics may
cation processes and final grinding technology. not require lubrication) and heat resistance: the
Due to the local stress concentration during use, cylinder may be allowed to get much hotter, im-
microstructures need to be very homogeneous proving the efficiency of the engine and requir-
with a grain size on the order of 10 µm, i.e., ing little or no cooling. These engines are often
without any larger grain, pores, and/or inclu- called adiabatic engines, although they are not
sions. Not long ago, this was only possible by adiabatic in the strictest sense. In a turbocharged
hot isostatic pressing at up to 1000 bar. Now a engine a ceramic rotor is a good candidate be-
suitable quality can be achieved by use of cost- cause its moment of inertia is lower than those
effective gas-pressure sintering and careful pro- of metal rotors.
cessing [37]. Mechanical finishing to required Table 7. Uses of advanced structural ceramics in engines
dimensions and surface quality require special
processes that need to be further optimized. Ex- Diesel Turbocharger Gas turbine
perience developed with metals can only be par- bearings bearings blades
tially utilized. Structural design of ceramic bear- cylinder liners heat shields heat exchangers
ings is also quite different from those made of glow plugs housing manifolds
manifolds turbocharger rotors rotor shaft
metals [38]. piston caps shrouds
piston rings stators
prechamber
High-Temperature Heat Exchangers and seals
Ventilators. For heat exchangers, silicon car- tappets
valves
bide is highly suitable because of high thermal valve seats
conductivity as well as its dimensional repro-
ducibility [39]. However, construction is quite A second type of engine for which ceramics
difficult and costly; for this reason a wider ap- have great potential is the gas turbine engine.
plication has not yet been achieved. The primary purpose of ceramics would be to
At present, the movement of gas at high tem- improve the thermodynamic efficiency by allow-
peratures is still a problem to be solved. Of great ing the engine to operate at a higher temperature.
interest is a ventilator equipped with ceramic el- The expected temperature of the turbine blades is
ements which is beginning to show promising 1200 – 1350 ◦ C. Not only are high-temperature
results [40]. strength and impact resistance important, ther-
mal shock resistance is also necessary. The can-
Uses in Engines. A list of applications for didates for these uses are silicon carbide and sil-
advanced structural ceramics is shown in Ta- icon nitride.
ble 7.
In a reciprocal engine, a number of ceramic Other Wear Resistance Applications. Im-
parts may replace their current metal equiva- portant applications for high-performance ce-
lents. Parts that must be wear resistant, such as ramics can be found in almost every field of
the rocker arm chip and the tappet face, may be chemical production, where processes can be
replaced with ceramics. Ceramics are also being disrupted by mechanical and/or chemical wear
 Ceramics, Advanced Structural Products
which leads to significant economic loss or even
impact on the environment. In addition, as pre-
viously discussed, ceramics can be introduced
for highly wear related parts, such as for the
milling and pouring of loose material or abra-
sive and corrosive slurries, liquids and gases. In
pipelines, cyclones, locks, etc., ceramic wear-
protected parts can be found, particularly alu-
minum oxide [41], [42]. Ceramics have become
the standard material, for example, for welding
nozzles which are made of aluminum oxide;
sand-blasting nozzles which are made of sili-
con carbide or the even harder boron carbide
and aluminum titanate, which are used in the
atomization of metals.
Applications also cover tools for metal work-
ing (cold and melt processing) as well as linings,
flowing, sealing, and dosing components used in
metallurgy. All these examples indicate a clear
advantage in applying ceramic materials rather
than the competing metallic materials. However,
it has to be pointed out that in all these cases ce-
ramic materials can only be applied successfully,
if designed properly to avoid high tensile stress
concentrations.
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