Ceramics, Ceramic – Metal Systems 1

Ceramics, Ceramic – Metal Systems

Victor A. Greenhut, Rutgers – The State University, Piscataway, New Jersey 08854, United States

Richard A. Haber, Rutgers – The State University, Piscataway, New Jersey 08854, United States

1. Introduction . . . . . . . . . . . . . . . 1 4.6. Vapor-Phase Metallizing . . . . . . . 14

2. Fundamentals of Bonding . . . . . . 2 4.7. Liquid-Phase Metallizing . . . . . . . 14
2.1. Wetting . . . . . . . . . . . . . . . . . . . 2 4.8. Electroforming . . . . . . . . . . . . . . 14
2.2. Bonding and Adherence 4.9. Graded Powder Process . . . . . . . . 14
Mechanisms . . . . . . . . . . . . . . . 3 4.10. Nonmetallic Fusion Process . . . . . 15
2.3. Stresses in Ceramic – Metal Systems 4 5. Thin Films and Coatings . . . . . . . 15
3. Glass-to-Metal Joining . . . . . . . . 5 5.1. Uses . . . . . . . . . . . . . . . . . . . . . 15
3.1. Glass-to-Metal Seals . . . . . . . . . . 6 5.2. Deposition Techniques . . . . . . . . . 16
3.2. Enamels . . . . . . . . . . . . . . . . . . 7 5.2.1. Chemical Vapor Deposition (CVD) . 16
3.2.1. The Enameling Process . . . . . . . . . 7 5.2.2. Evaporation . . . . . . . . . . . . . . . . 17
3.2.2. Theory of Adhesion . . . . . . . . . . . 10 5.2.3. Sputtering . . . . . . . . . . . . . . . . . 19
4. Ceramic-to-Metal Joining . . . . . . 12 5.2.4. Plasma Spraying . . . . . . . . . . . . . 20
4.1. Sintered Metal Powder Process 5.2.5. Sol – Gel Processing . . . . . . . . . . . 20
(SMPP) . . . . . . . . . . . . . . . . . . . 12 5.2.6. Ion Implantation . . . . . . . . . . . . . 21
4.2. Metal Powder – Glass Frit Method . 13 6. Ceramic – Metal Composites . . . . . 21
4.3. Active Metal Process . . . . . . . . . . 13 6.1. Cermets and Cemented Carbides . 22
4.4. Gas – Metal Eutectic Process . . . . . 13 6.2. Metal Matrix Composites . . . . . . . 23
4.5. Pressed Diffusion Joins . . . . . . . . 14 7. References . . . . . . . . . . . . . . . . . 25

1. Introduction els used as corrosion protection and decora-

The use of ceramics and metals in conjunction
allows for a combination of properties. Ceram-
ics, here to include glasses, typically show strong
covalent/ionic bonding with chemical inertness,
high elastic modulus (stiffness) and compressive
strength, low electrical and thermal conductiv-
ity, low friction and wear behavior, and trans-
parency to electromagnetic radiation. Metallic
bonds result in complementary properties, for
mechanical ductility is not usually exhibited
by ceramic materials. Ceramic – metal systems
have been used since prehistoric times in such
forms as enamels on metal and metallic deco-
ration on ceramics. The contributions provided
by both the ceramic and the metal make such
systems important in traditional and advanced
technologies.
The ceramic and metal may be coupled as
macroscopic pieces or engineering structures.
These find use in such components as semi-
conductor substrates, turbines, electronic equip-
ment, and lamps. Coatings of ceramic or glass
can be placed on metal or vice versa. Enam-
tion are an example. A microscopic combina-
tion of materials can be produced in the form
of a ceramic – metal composite, often termed a
cermet when the ceramic is the principal phase.
Such materials are used for carbide cutting tools,
high-temperature jet orifices, and turbine parts.
In all cases it is necessary to bring the ceramic
and metal into intimate contact and create a bond
between materials. The distinct differences bet-
ween ceramic and metal in terms of bonding and
properties make it necessary to consider the ma-
jor factors required to join the two classes of
materials and satisfy the physical, chemical, and
mechanical properties required of the system.
2. Fundamentals of Bonding
Metals and ceramics may be joined in the solid
state or with one component deposited as a liq-
uid or vapor. Intimate contact occurs between
the materials by physical means. Bonding may
occur by surface or interfacial interaction. De-
pendent on the chemical nature of the materials,

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

10.1002/14356007.a06 055
2 Ceramics, Ceramic – Metal Systems
solution and redox reactions may proceed, thus
promoting adherence. Quite commonly a liquid
phase is present during fabrication of a joint,
coating, or composite. In such a case, the wet-
ting behavior of the liquid phase on the solid is
quite important. Solution and/or redox reactions
are likely, which can affect the wetting behavior
and adherence. Wetting is usually required for
adherence between ceramic and metal.
A further factor that may affect the bond at
a ceramic-to-metal interface is stress between
the ceramic and metal. Such stresses may arise
in the presence of an applied stress because
of differences in elastic constant. As the mate-
rial cools from fabrication at elevated tempera-
ture, differences in thermal expansion can give
rise to residual stresses. Changes in tempera-
ture during use can have a similar effect. Forces
at the ceramic – metal interface can exceed the
strength of the bond between materials, prevent-
ing a macroscopic join, causing delamination of
a coating, or affecting composite properties.
2.1. Wetting
Commonly a bond between metal and ceramic
is created by either melting the metal or soften-
ing a glassy ceramic material. The success of the
bond depends on the wetting or capillary action
[1], [2]. To join two pieces of material, the liq-
uid must spread across the surface or interface.
In a composite material, a phenomenon called
sweating occurs in a nonwetting situation such
that liquid is exuded at the surface of the mate-
rial. This may cause nonuniformity or porosity,
or it may make the composite impossible to pro-
duce.
A number of methods have been developed
to determine the wetting response of the liquid
phase. These include the geometry of liquid in
a capillary or a sessile drop on a flat substrate,
the rise of liquid in a capillary, and wicking in
a porous material [2–4]. Perhaps the simplest
and most common approach is the sessile drop
method, which is shown schematically in Fig-
ure 1. A drop of liquid, shown in cross section,
is observed at elevated temperature, and the con-
tact angle θ is measured. The relationship is as
follows:
γlv cosθ=γsv −γsl
where γ lv , γ sv , and γ sl are the interfacial en-
ergies between liquid – vapor, solid – vapor, and
solid – liquid, respectively. For θ>90 ◦ , a non-
wetting situation occurs, while if the angle is
<90◦ , the liquid wets the surface. If θ = 0◦ , the
liquid spreads over the surface as a thin layer.
The surface energy can be obtained from this
experiment when equilibrium is achieved [3–6],
providing an estimate of interfacial energy and
theoretical bond strength if extrapolated to room
temperature.
Figure 1. Sessile drop configuration
The wetting angle itself is valuable in evalu-
ating the system. The contact angle may change
with small changes in the composition of the at-
mosphere, liquid, or solid phases. Temperature
and time also play an important role. In indus-
trial processes, the liquid is seldom brought to
equilibrium as it reacts with the solid oxide films,
and contaminants on the surface, as well as the
atmosphere of the furnace. While interfacial en-
ergy cannot be obtained in this case, the wet-
ting information in itself indicates the degree to
which the liquid spreads or infiltrates the solid.
Although a strict relationship cannot be drawn
between wetting and bonding, usually a good
wetting response and a degree of bonding coin-
cide. However, a reasonable bond strength may
develop in a nonwetting case, and adequate bond
strength may not develop in a wetting case. The
wetting response should, therefore, be regarded
as a necessary but not a sufficient condition for
good ceramic-to-metal bonding.
For ceramic – metal sealing, a transition from
metal oxide to metal layers may be used to
promote wetting. Such a layer may be ap-
 Ceramics, Ceramic – Metal Systems
plied as a metallizing layer in the form of a
moly1 – manganese paste (see Chap. 4). Such
a material may provide a bond to the ceramic
because of the oxide ceramic and glass phases
present while providing a low interfacial energy
with a molten metal because of a metal-rich sur-
face structure [7].
In glass – metal joining, the metal is com-
monly preoxidized [3], [5], [8]. The oxide layer
may be more compatible with the oxide bond of
the glass, thereby lowering the interfacial energy
between liquid and solid [3], [5] and possibly
promoting wetting. Glass-to-metal and ceramic-
to-metal bonding often involves a forming gas,
which may affect wetting by oxidizing or reduc-
ing the metal or ceramic, altering interfacial en-
ergies, or diffusing a particular species into solid
or liquid. These techniques suggest that some
transition between metallic and ionic/covalent
bonding enhances the wetting response.
2.2. Bonding and Adherence
Mechanisms
The mechanisms of ceramic – metal bonding
have been classed in various ways, but perhaps a
most general view is that physical, mechanical,
and chemical bonding mechanisms can occur.
These effects do not occur independently, and
all may be involved in a ceramic – metal system.
Physical bonding may be regarded as the
bonding effect that occurs when a pair of flat sur-
faces are brought within atomic-interaction dis-
tances. The work of adhesion is given by the spe-
cific energy of the metal and ceramic minus that
of the metal – ceramic interface. This work of
adhesion can yield a theoretical breaking stress
near that of the metal or ceramic [4], [9]. Nev-
ertheless, actual interfaces can fail at stresses
many orders of magnitude smaller as the result
of flaws in the bond.
Mechanical bonding relates to the interlock-
ing structure of rough surfaces, which gives rise
to either frictional effects in shear or interlocking
of microstructure, which provides mechanical
anchors in tension. When ceramic and metal are
joined, liquid metal or glass can penetrate pores
and cavities, a ductile metal solid can conform
to the ceramic surface, or a vapor phase may
deposit in surface asperities. A roughened sur-
face, which promotes mechanical bonding, also
3
increases the surface area for physical bonding.
However, a mechanically interlocked structure
could in itself lead to a bond.
Chemical bonding occurs in a transitional
oxide film between the metal and the enamel
and is responsible for adherence, the oxide film
actually bonding the enamel to the metal. Many
complex reactions take place in the transition
zone. One accepted model hypothesizes that the
adherence is the result of metal-to-metal bonds
between the atoms of the base metal and some
metallic ions in the enamel. The enamel at the
interface must be saturated with the lowest oxi-
dation state oxide of the base metal [5].
Chemical reaction can produce a transition
structure that gradually varies from metallic to
ceramic. Often such a structure is developed by
design. Metals may be preoxidized to provide
an oxide that can react with molten glass, sat-
urating the glass near the interface in the metal
species. Alternatively, the oxide may adhere to
the metal, providing a ceramic surface for the
bonding glass. A transition structure may be pro-
vided by a mixed oxide and metallic material
applied to the ceramic, such as in the sintered
powder process, which provides a ceramic-like
interface at the ceramic and a sufficiently metal-
lic one at the metal bond [1–9].
In practice, complex combinations of these
mechanisms may occur. For example, in porce-
lain enameling, a preoxidized metal surface may
undergo galvanic attack, roughening and pit-
ting the metal surface locally, changing the lo-
cal chemistry of the glass, and redepositing den-
dritic anchors of metal at the interface. Features
of physical, mechanical, and chemical contribu-
tions to bonding may all be identified, but their
relative contributions may be difficult to assess.
Chemical interaction can produce material prop-
erties rather different from those of either origi-
nal material (see also Section 3.2.2).
2.3. Stresses in Ceramic – Metal Systems
Thermally Induced Residual Stresses. The
thermal expansion of a metal is generally con-
siderably greater than those of ceramics and
glasses, as can be seen in Figure 2. An un-
constrained metal may contract significantly
more than the ceramic, but if the metal is con-
strained, the differential expansion can result in
4 Ceramics, Ceramic – Metal Systems
residual stresses in the ceramic and the metal.
These stresses add to those resulting from ap-
plied forces, thermal gradients, phase transfor-
mations, and rapid cooling. This residual stress
in itself or in combination with external stress
may cause failure of the bond.
The greater shrinkage of a metal in a flat sheet
causes net compressive stresses in the ceramic
and tensile stresses in the metal. Such a situation
is favorable because a ceramic typically shows
far greater compressive than tensile strength: a
residual stress can enhance properties such as
fracture strength and wear resistance. However,
if the stress is too great, failure may occur in the
interface or possibly in either material.
Several approaches may be used to limit
the thermally induced residual stresses. The ce-
ramic and metal can be chosen to minimize
the mismatch in thermal expansion. For ex-
ample, molybdenum and tungsten reasonably
match several ceramic and glass compositions
and can be used where their poor oxidation re-
sistance is not a limitation. For platinum and
chromium, several glasses and ceramic com-
positions show similar expansion, but expense
and useful bonding technology, respectively, can
limit application. A common alloy in glass seal-
ing, ASTM F15, is a set of iron, 28 – 29 wt %
nickel, and 17 – 18 wt % cobalt alloys. These al-
loys show expansion behavior similar to that of
borosilicate glasses, some showing an extraor-
dinary match over both low and high temper-
ature ranges. Such alloys are often referred to
by the trade name Kovar (Carpenter Technolo-
gies). These alloys also show ductility, do not
usually embrittle, and can be soldered, brazed,
and welded. Some glasses and ceramics have
been designed to match the expansions of par-
ticular alloys, e.g., lead silicate and other enamel
compositions applied to steels.
Another approach to matched expansion is
the Housekeeper seal, in which a very thin piece
of metal is used. The slight size, low yield
strength, and ductility of the metal allow it to
accommodate the induced stresses [3], [8].
Continuum mechanics can predict the magni-
tude of residual stresses that result from thermal
expansion differences [3], [8], [10] and can be
used to design a system configuration or applied
loads such that critical stresses are not exceeded.
One approach is to design a compression seal so
that the ceramic is placed in compression and
the metal is placed in tension. A compressive
seal can be used to obtain a purely mechanical
bond between solid metal and ceramic during
fabrication. One way is to use the differing ther-
mal expansions to produce a “shrink fit” dur-
ing cooling. A pair of concentric cylinders with
the metal as the outer sleeve is an example, the
greater contraction of the metal on cooling re-
sulting in a strong, tight fit. However, different
stress components can be in tension or compres-
sion for the same location in a material. Caution
must be taken not to exceed the fracture stress
for any tensile stress component in the ceramic
or the interface.
Elastic Modulus Effect. The difference in
the elastic modulus or stiffness of the ceramic
and the metal components of a system or com-
posite can result in material or interfacial failure
under applied and residual stresses. This situ-
ation is shown in Figure 3. A ceramic is typi-
cally stiffer than a metal, as shown by the greater
slope of the ceramic curve. For this example the
ceramic has been chosen to be stronger in ten-
sion than the metal. If the metal is the massive
member in the system and is loaded to a stress
σ m at the ceramic – metal interface, it will ex-
perience a strain εcm, . The deformation or strain
must be compatible across the interface, thereby
imposing a stress σ c on the ceramic or interface
because of the higher modulus of the material.
Even when the ceramic is much stronger than
the metal, the failure stress may be exceeded, as
shown by the x, which indicates failure stress.
This effect can lead to failure of a ceramic –
metal joint or coating. For composite material,
the situation may be more complex as sharing
of load may be desired for properties such as
elastic modulus. However, when a failure crack
propagates, failure at the ceramic – metal inter-
face may be desirable so that the crack is diverted
and fracture energy is expended in the process.
Such considerations may be complex, involv-
ing the properties of ceramic and metal, chemi-
cal interaction zones between materials, and mi-
crostructural and geometrical factors. Predictive
theoretical treatments for such materials are be-
ing developed.
 Ceramics, Ceramic – Metal Systems 5

Figure 2. Thermal expansion of typical ceramics (dashed curves) and metals (solid curves)

3. Glass-to-Metal Joining and in many cases these elements are not re-
moved. The formation of bubbles in the enamel
The bonding of glass and metal can be divided is considered undesirable if it weakens the bond
into two general categories, glass-to-metal seals with the base metal, results in a large bubble that
and enamels. These two areas are distinguished exposes base metal, or causes aesthetic prob-
by use, glass-to-metal seals being used primar- lems in surface roughness or color. Instead of
ily in electronic applications such as hermetic preventing bubbles from forming, a controlled
sealing of lamps and devices, isolation of elec- fine-sized bubble structure is introduced to act as
trical feed throughs, packaging, and vacuum- a getter for evolving gases, thus avoiding large,
tube technology. Enamels are used principally objectionable bubbles in the glass.
as corrosion protection and decorative coatings
on such products as domestic appliances, bath-
room fixtures, and cookware.
Enamels and glass-to-metal seals are also
distinguished by the base metal. Most enamels
are applied to low-carbon steels and cast iron,
while glass-to-metal seals are commonly used
with nonferrous metals, stainless steels, and the
iron – nickel – cobalt Kovar alloys.
A third distinguishing feature is how the car-
bon and hydrogen are treated. These species
may be either in the base metal or on the sur-
face as hydrocarbons. These elements combine
with oxygen at elevated temperature and can
form gaseous bubbles in the molten glass. In the
case of glass-to-metal sealing, the base metal is
cleaned of hydrocarbons and then decarburized
or the hydrogen baked out. In enameling, higher Figure 3. Difference in stresses for a bonded ceramic and
levels of carbon and hydrogen are permissible, metal under applied stress
6 Ceramics, Ceramic – Metal Systems
3.1. Glass-to-Metal Seals
A good glass-to-metal seal requires a glass and
metal with thermal expansions that match ade-
quately over the temperature range of fabrica-
tion and application. The base metal is gener-
ally cleaned and then decarburized and/or the
hydrogen baked out. Other products, such as ni-
tride in the case of titanium alloys, may need
to be removed. The metal generally is oxidized
to provide a tightly adherent layer of oxide that
remains adherent during forming of the glass-to-
metal join. The oxide typically is wet by the glass
and dissolves in the glass to yield a structure with
sufficient chemical bonding [5]. Glass-to-metal
sealing has been reviewed [3], [8], [11].
Metals commonly used for glass-to-
metal joining include tungsten, molybde-
num, titanium, tantalum, nickel – iron alloys,
iron – chromium alloys, iron – nickel – cobalt
alloys, platinum, copper, gold, and copper-
clad nickel or iron – nickel Dumet alloys. A
large range of borosilicate and lead silicate
glasses are commonly used in glass-to-metal
seals; borosilicate glasses are most commonly
used. Where copper and copper-clad alloys or
iron – chromium alloys such as stainless steels
are used, lead silicate glasses are more common.
The glass is usually applied as a frit, bead,
or paste. A solid fabricated glass shape may be
heated and softened to the required viscosity by
electrical, flame, or radio-frequency heating, and
then pressed into contact with the preoxidized
metal to bond. Frequently a protective or spe-
cial forming atmosphere is required to promote
wetting and bonding. Careful cooling or anneal-
ing avoids residual stress because of excessively
rapid cooling.
A typical sequence of operations is that of
the specialty Kovar alloy ASTM F15 (1983)
(Fe –29 % Ni – 17 % Co) glass-to-metal sealed
with borosilicate glass. This system is com-
mon because of the excellent thermal expan-
sion match between materials, good wetting re-
sponse, and strong bond. It is used for microelec-
tronics packages, electrical and high-frequency
feed throughs, laser cavity-to-window bonding,
and other diverse applications.
The Kovar is first degreased, chemi-
cally cleaned, and decarburized in a hydro-
gen, hydrogen/nitrogen, or dissociated am-
monia atmosphere with various water levels
at 900 – 1100 ◦ C. The temperature should be
higher than final glass-to-metal sealing temper-
ature. A typical cycle is 1100 ◦ C for 10 – 15 min
in a hydrogen/nitrogen/water vapor atmosphere,
typically 1 vol % water and as little as 10 vol%
hydrogen.
The next step is to preoxidize the metal in a
controlled fashion. While air and natural gas can
be used, the variability of components such as
water in these gases makes process control dif-
ficult. Pure oxygen gives a thick, flaky coating
that does not penetrate metal grain boundaries.
An atmosphere of nitrogen/water/hydrogen at
800 – 1050 ◦ C is used: an atmosphere of nitro-
gen/1 vol% water/0.4 vol% hydrogen at 1000 ◦ C
for 10 min produces good oxide structure with
optimum thickness and grain boundary penetra-
tion.
The final step is the glass sealing. The glass
preform or frit is assembled or applied. Firing
is performed in a nitrogen-based atmosphere,
such as that used for controlled preoxidation,
or an exothermic (natural) gas atmosphere is
employed. Sealing is done at ca. 1000 ◦ C, the
precise time and temperature depending on part
geometry, glass viscosity, and wetting response
[12].
3.2. Enamels
Enamel is a fused, vitreous, superficial coating
on metals or a decorative pattern on a glass sur-
face. Enamels are similar in properties to ce-
ramic glazes.
History. The origin of enameling metals
goes back to the Egyptians, centuries before
Christ. Enamels were used to provide elabo-
rate designs in jewelry. The materials enameled
were typically gold and silver. Later more metals
were enameled; bronze and copper jewelry in-
serts were coated with enamels. By variations in
the composition of the enamel the glassy coating
could be made to hide defects in the metal.
The application of enamels to iron and steel
made enamels available for uses other than jew-
elry. Enamels were sought to provide decorative
coatings on a wide variety of cast-iron shapes.
In the earliest operations, cast iron was heated to
redness, the enamel was dusted upon the metal
as a fine dry powder, and as the powdered glass
 Ceramics, Ceramic – Metal Systems
stuck to the hot metal it softened and adhered
to the surface. This operation required a num-
ber of successive coating steps to obtain a layer
thick enough to provide the desired effect. Many
problems were related to the firing: enamels blis-
tered, turned black, lacked the desired color, and
exhibited poor adhesion.
Advances corrected or improved these prob-
lems. Adherence was related to the surface prop-
erties of the metal. Surface pretreatments, such
as sand blasting, cleaning, and pickling, evolved.
New, cheaper sources of raw materials were
found, e.g., borax, allowing lower firing temper-
atures and producing cheaper enamels. The ap-
plication of enamels as a suspension, rather than
dry powder, was a great improvement. Greater
control of the chemistry was found to provide
newer, more stable enamels.
3.2.1. The Enameling Process
The enameling process can be simplified into
three basic steps: (1) metal preparation, (2)
ground-coat application, and (3) cover-coat ap-
plication. Figures 4 and 5 provide process flow
diagrams for three commonly enameled metals
– cold-rolled steel, low-carbon steel, and cast
(enameling) iron [13].
Metal Preparation. The metal surfaces
must be free from grease, machining oils, dirt,
oxidation products, and rust. A roughened or
suitably etched surface is desirable for most
metals. The exact metal preparation depends on
the composition of the base metal and the type
of enamel to be applied.
No pretreatment is required for gold or silver,
provided the metal surfaces are clean. For copper
and bronze the cleaning step is often followed
with a 2 – 4 % nitric acid pickle and a clean wa-
ter rinse. Aluminum and its alloys require special
surface pretreatment, including cleaning, chro-
matizing, and preoxidation.
Stainless steel and other metal substrates for
high-temperature end use are usually prepared
by sand or grit blasting. Otherwise, the metals
are processed typically. The pickling acids may
be quite reactive; i.e., HF is typically incorpo-
rated into the pickle. Cast iron and heavy-gauge
sheet steel are prepared by sand or grit blasting
and then typical chemical processing.
7
Metal preparation can be described as the fol-
lowing processes:
1) Annealing. The metal to be enameled is
heated to a temperature sufficient to remove
organic surface impurities. Such impurities
can act as a source of gases that become en-
trapped in the enamel during the firing.
2) Grit or sand blasting. This acts as part of the
cleaning process where heavier rust, scale,
and dirt are removed. More importantly,
sand blasting creates a rough surface for the
enamel to anchor mechanically.
3) Solvent cleaning. Cleaning removes mill oils
and the soaps, oils, and rust preservatives
added during forming.
4) Acid pickling. Pickling acts to remove metal
oxidation products and scale. It also acts to
create a rougher surface and increase enamel
adherence.
5) Nickel flash. The nickel deposit follows the
acid pickle and subsequent acid rinse. Its
function is to promote adherence between
ground coat and enamel and reduce the oc-
currence of defects in the ground coat result-
ing from noncontrolled metal oxidation.
6) Neutralization. This functions to increase the
pH of the metal surface.
The type of surface pretreatment is governed
not only by the metal, but also by the processing.
The three types of process systems are batchtype
immersion, continuous or automatic immersion,
and continuous spray. For example, the steps
used for sheet steel include the following:
1) Physical and chemical cleaning. Heavily ox-
idized steel is sand blasted prior to chemical
cleaning. Alkaline cleaners, typically baths
containing caustic soda at 40 – 60 ◦ C, are
used to remove organic soils.
2) Acid pickling. The removal of rust and
scale from the metal surface by pickling
is carried out in sulfuric acid (6 – 9 wt %
at 65 – 75 ◦ C) or in hydrochloric (muriatic)
acid (10 – 12 wt % acid at room temperature).
Phosphoric acid or an acid salt can also be
used. Sulfuric acid is most commonly used
because of its speed and lower cost. The sul-
furic acid should be pure, and inhibitors must
be avoided since they interfere with metal
removal and etching, resulting in faulty ad-
herence. After pickling, the metal should be
8 Ceramics, Ceramic – Metal Systems
Figure 4. Flow diagram for the enameling of cold-rolled steel or enameling iron
Figure 5. Flow diagram for the enameling of low-carbon steel
rinsed in cold running water, usually acid-
ified to pH 3 – 3.5 to prevent hydrolysis of
iron salts.
3) Nickel deposition. Time of treatment, typ-
ically 5 – 15 min, should be sufficient to
provide the desired coating of nickel. The
aqueous nickel solutions are maintained at
concentrations of 0.25 – 3 wt % nickel sul-
fate at 70 – 80 ◦ C. The pH should be bet-
ween 2.6 and 3.2. The temperature, pH, and
nickel concentration are closely monitored.
For conventional enameling, the nickel de-
posited should range from 0.27 to 1.6 g/m2 .
4) Neutralization. The final step is neutralizing
acid residuals on the metal surfaces, and also
providing rust protection and minimizing the
presence of undesirable surface chemicals.
Typically, either alkaline soda ash or borax
 Ceramics, Ceramic – Metal Systems 9

solutions equivalent to 0.02 – 0.3 wt % Na2 O surface and promoting glass – metal bonding at
are used. an earlier stage. A third may be used as a deco-
rative or colored base to hide defects prior to the
Table 1. Chemical oxide composition of ground coats for steel, parts
by weight final coat.
Ground coats are applied in the form of a
Com- I II III IV V
ponent slurry to the treated metal by spraying or dip-
ping, and are then allowed to dry. Typical firing
KNa2 O ∗
B 2 O3
17.8
16.0
18.5
15.2
21.0
11.8
18.0
14.1
19.4
13.3
temperatures range from 780 to 870 ◦ C. Table 1
Al2 O3 7.7 8.8 8.7 5.4 8.0 shows typical chemical oxide compositions of
SiO2 51.1 52.1 44.4 44.1 56.6 ground coats for steel.
CaF2 5.5 3.8 8.7 6.8
BaO 2.0
CoO 0.5 0.4 0.4 Cover Coats. Enamel cover coats are de-
Mn2 O3 0.9 1.2 0.9
NiO 0.5 0.2
signed to provide specific color and appear-
CuO 0.7 ance characteristics coupled with resistance to
CaO 1.2 atmospheric and liquid corrosion, abrasion re-
Sb2 O3 4.8 1.4
ZrO2 3.7 6.2 sistance, and thermal shock resistance, to name
a few properties. Cover coats are applied ei-
Ground coats I, II, and III are typical blue ground coats,
whereas coats IV and V are white ground coats for use with
ther as a suspension, followed by drying and
white enamel cover coats. firing, or by spreading a dry powder over the
∗ KNa2 O appears often in the enameling literature, indicating hot metal. Cover coats range in thickness from
that the proportions of K2 O and Na2 O in the oxide raw
materials do vary. The formulation K,Na2 O also appears in the 0.08 to 0.64 mm, depending on application. The
literature. firing temperatures for the cover coat are lower
than those for the ground coat to prevent exces-
Ground Coats. Porcelain enamel ground sive flow in the ground coat.
coats for sheet steel are basically alkali- The corrosion properties of the enameled
metal aluminoborosilicate glasses containing metal are most often those of the cover coat. For
adherence-promoting oxides of such metals as instance, titania-based enamels are used for acid
cobalt, nickel, and copper. These coatings serve resistance, while zirconia-based cover coats are
three purposes. The first is to provide a satisfac- used for alkali resistance. Table 2 shows typical
tory bond or adherence to the base metal by com- steel cover coats.
plex reactions with the steel during firing. The
Table 2. Chemical oxide composition of cover coats used for cast
second is to provide a protective layer or coat- iron, parts by weight
ing that minimizes surface defects caused by the Com- I II III IV V
metal or metal preparation, smoothing the sur- ponent
face for the cover coat. The last is to provide a
KNa2 O 37.1 21.8 32.0 37.6 32.4
resistant coating, in some cases decorative, ther- B2 O 3 11.8 13.4 9.1 11.8 14.9
mally resistant, or chemically resistant. While PbO 10.4 13.4 16.0
increased adherence is the primary function of Al2 O3 6.4 4.6 5.4 6.5 5.3
SiO2 39.0 2.9 24.0 44.2 14.9
the ground coat, the other functions should not CaF2 6.2 5.6 7.0 6.2 4.9
be underemphasized. For some steels satisfac- CaO 3.9 6.7 2.3 4.0 10.5
ZnO 7.5 7.9 5.0 9.2
tory adherence may be obtained without the use Sb2 O3 3.7 4.2 3.7
of ground coats; however, special surface treat- ZrO2 4.7 5.9
ments must be employed if a ground coat is not BaO 12.0 8.0
MgO 5.4
used.
Ground coats are most typically composed
of ground-glass powders or frits. In most in- 3.2.2. Theory of Adhesion
stances the base ground coat may contain a num-
ber of frits, all having specific properties that The theory of adherence can be divided into
make them useful. For example, one frit may two main branches: the mechanical theory and
provide sag resistance to the molten glass when the chemical or oxide theory [14–16]. Each is
the ground coat is heated. A second frit may fuse characterized by numerous hypotheses that have
at a lower temperature, thus sealing the metal evolved to explain adhesion. In addition, there
10 Ceramics, Ceramic – Metal Systems
is electrolytic theory and dendritic theory. How-
ever, no one theory can adequately describe ad-
hesion for all systems.
Figure 6. Schematic section of the enamel–metal interface
comparing measures of roughness
Mechanical Theory. The mechanical theory
states that adherence is due to mechanical grip-
ping of the roughened base metal. The enamel
glass is held to the metal by enclosing projec-
tions and by filling the depressions occurring on
the metal surface.
The application of porcelain enamels to cast
iron was the first commercial application of ce-
ramic coatings. Although the surface of the cast
iron was inherently rough, further roughening,
usually by sand or grit blasting, improved the
adherence. This practice suggested the mechan-
ical theory of adherence. Other metals could be
coated with ceramics if their surface was rough-
ened. Treatment included combinations of sand-
blasting, scouring, electrolytic corosion, pick-
ling, etc. This extension to other metals in-
creased acceptance of the mechanical theory.
To better understand the relationship between
the roughness of the ceramic – metal interface
and adherence, a model contrasting two mea-
sures of roughness was proposed:
1) undercuts/distance in centimeters (or anchor
points/centimeter)
2) interface ratio
Both are measured on microscopic polished sec-
tions of the ceramic – metal interface. Figure 6,
a schematic section of the enamel – metal inter-
face, shows the two measures of roughness. The
undercuts or anchor points (each marked by an
x) are counted and expressed as the number per
centimeter, in this case, number of x’s/AA . The
interface ratio is calculated by measuring the
length of the interface line with a map measure
and dividing it by the length of the line paral-
lel to the interface, in this case BB /AA . These
two measures are then correlated to adherences.
Adherence is determined by the standard test of
deforming the metal and measuring the amount
of metal exposed.
If adherence is due to the gripping action of
the rough ceramic – metal interface (mechani-
cal theory), then the best correlation should be
between adherence and anchor points per cen-
timeter. If adherence is due to chemical bond-
ing (chemical theory), the interface ratio should
give a better correlation between adherence and
roughness. For enameled cast iron:
1) Positive correlation is found between the ad-
herence of a porcelain enamel ground coat
and the roughness of the interface.
2) In general, adherence correlates better with
anchor points/centimeter than with the inter-
face ratio.
3) The method of metal preparation has a
marked effect on the relationship between
roughness and adherence, pickled iron gen-
erally producing better adherence than sand-
blasted iron for the same degree of rough-
ness.
4) Most of the roughness associated with good
adherence develops during firing.
5) Roughness of interface is a necessary but not
a sufficient condition for the development of
good adherence.
6) Factors other than roughness of interface in-
fluence adherence.
These conclusions tend to confirm the
mechanical theory of adherence. However, some
adherence phenomena cannot be explained by
the mechanical theory:
1) Excellent adherence can be obtained on ex-
tremely smooth surfaces.
2) A roughened surface exhibiting many an-
chor points does not ensure adherence signif-
icantly better than chemical adherence alone.
 Ceramics, Ceramic – Metal Systems 11

3) The measured values for the strength of the surface becomes roughened, and the glass an-
bond necessitate assignment of extremely chors itself into the depressions produced. Fi-
high values for the strength of iron because nal adhesion is basically mechanical. The elec-
the total cross section of the anchor points is trolytic theory has two main faults:
always a relatively small portion of the total
interface area. 1) Some metals that exhibit a greater potential
difference with iron than does cobalt do not
Chemical or Oxide Layer Theory. Chem- cause greater corrosion.
ical reactions include dissolution, redox, in- 2) The theory is still based on mechanical the-
terdiffusion, and precipitation, which change ory, which was previously discussed and par-
the nature of the interface and may result in tially discredited.
a transition zone between the metal and the
ceramic. The bond in metals and ceramics is
fundamentally different, and this may prevent
a strong physical bond between bare metal and
ceramic. A theory developed for glass-to-metal
bonds and verified experimentally may be ap-
plied more generally to all ceramic-to-metal
bonds. The theory states that chemical bonding
occurs across an interface when chemical equi-
librium relative to the lowest valence oxide of
the metal phase is present [5]. The glass and
the metal are saturated in the metal oxide at the
interface, and therefore the activity of the lowest
valence metal oxide is one. Then there is an ide-
alized molecular monolayer of the metal oxide
at the interface, which is part of and compatible
with both metal and glass. Bond energies should
then balance, and the electronic structure should Figure 7. Electrolytic cells between molten enamel and
be continuous across the interface. If oxide ac- cast iron
tivity is less than one, complete continuity is
not realized. Reaction of metal and glass with
chemical interdiffusion is driven by the lack of
Dendritic Theory. Dendrites are the form in
chemical equilibrium relative to the lowest va-
which the metal normally crystallizes from the
lence metal oxide. A chemical bond occurs when
melt, aqueous solutions, or any nonmetallic liq-
equilibrium in terms of chemical potentials or
uid in which compounds of the metal dissolve.
activities is reached at the interface. In glass-to-
They are branched crystals that occur periodi-
metal bonding this occurs when the glass near
cally, giving fernlike, treelike, or toothlike ap-
the interface is saturated in the metallic species.
pearance.
Electrolytic Theory. According to the elec- The dendrite theory claims that the α-iron
trolytic theory, metal oxides dissolved in enam- dendritic precipitates that occur in the boundary
els are reduced during firing to the metal- layer between enamel and base metal are respon-
lic state by the base metal. The adherence- sible for adherence. The dendrites grow from the
promoting metal in the enamel is believed to base metal into the enamel, and after cooling
form shorted galvanic cells that strongly corrode they tend to mechanically attach the enamel to
the base metal. This concept is illustrated in Fig- the base metal. This differs from the mechanism
ure 7. The current flows from the iron through of the electrolytic theory, in which the metals
the melt to the cobalt and back to the iron. These and dendrites in the interfacial zone are Co, Ni,
local cells are not exhausted during firing be- or other adherence-promoting metals.
cause anodic iron and diffusing oxygen are abun- Although a possible adherence mechanism,
dant. Iron goes continuously into solution, the dendritic theory correlates poorly with adhesion.
12 Ceramics, Ceramic – Metal Systems
4. Ceramic-to-Metal Joining
A ceramic component and a metal component
may be joined in various ways, including fasten-
ers, adhesives, and direct joining of ceramic and
metal. For durable, integral, hermetic joins capa-
ble of extended service, particularly at extreme
temperatures, the direct join is used. The suc-
cessful join usually requires a preparation step to
achieve a transition structure, good wetting, and
chemical bonding between ceramic and metal-
lic materials. The following are common joining
processes:
sintered metal powder (moly – manganese
paste)
metal powder – glass frit
active metal
gas – metal eutectic
pressed diffusion joins
vapor-phase metallizing
liquid-phase metallizing
electroforming
graded powder
nonmetallic fusion
These processes are listed in approximate order
of frequency of use.
The various joining techniques are often cat-
egorized as liquid phase, vapor phase, and solid
phase. Ceramic-to-metal joining is discussed
comprehensively in [3], [11], [17–19].
4.1. Sintered Metal Powder Process
(SMPP)
The sintered metal powder process, also referred
to as SMPP or moly – manganese paste pro-
cess, uses a paste composed of molybdenum and
manganese metals and their oxides suspended
in an organic vehicle. Compositions contain-
ing tungsten, tantalum, iron, rhenium, and tita-
nium with their oxides can also be used. Thus,
moly – manganese pastes may contain neither
molybdenum nor manganese.
A slurry of a composition such as
60 g of molybdenum powder (0.2 µm)
15 g of manganese powder (0.2 µm)
0.2 g of nitrocellulose
30 mL of butyl acetate
is applied by brushing, spraying, roller coat-
ing, transfer tape, silk screening, or dipping to
a thickness of ≈ 20 µm. For single-phase ce-
ramics such as high alumina classes without a
glassy silicate phase, the usual pastes do not
bond well. Compositions containing approxi-
mately equal amounts of the metal powders
and 13 Al2 O3 –52 MnO – 35 SiO2 or 41 Al2 O3 –
54 CaO – 5 MgO, for example, are used. (The
numbers are the weight percents.) After appli-
cation, the paste is dried in air, often under heat
lamps. It is then fired in a hydrogen atmosphere
(dew point ≈ 25 ◦ C) at 1200 – 1600 ◦ C for ca.
0.5 h. Manganese or titanium additions lower the
firing temperature by 100 – 200 ◦ C.
The process gives rise to a transition coating
with a glassy or crystalline ceramic phase that
has migrated in the metal – metal oxide powder
or that comes from the ceramic added to the paste
in the case of single-phase ceramics [1], [2], [7],
[20]. The structure of the liquid-phase sintered
product consists of a glassy phase with metal-
lic and oxide particles. This structure provides
the necessary bridging phases between ceramic
and metal. The resulting coating can be directly
brazed to metal, but more commonly it is electro-
plated or electroless plated with a 5 – 8 µm thick
nickel layer. Alternatively, copper can be plated,
or either metal can be applied as a powder and
fired to bond by diffusion in a controlled atmo-
sphere. The resulting nickel surface is suitable
for conventional brazing materials and methods.
While SMPP involves several steps, the pro-
cedures are relatively straightforward, and the
results are reliable, SMPP producing some of
the strongest ceramic – metal joins. It is the
most common method for producing ceramic-
to-metal joins and metallization in industry.
4.2. Metal Powder – Glass Frit Method
For the metallization of hybrid microelectronic
circuitry, a finely divided noble metal or alloy
(platinum, palladium, gold, silver) mixed in a
glass frit and suspended in an organic binder is
commonly used. The required pattern is usually
screen-printed on an electronic substrate mate-
rial such as alumina or on a multilayer capacitor
material such as barium titanate. These systems
permit air firing of the material. The structure of
the bridging glassy phase providing a bond bet-
 Ceramics, Ceramic – Metal Systems
ween the ceramic and a metal-rich free surface
is akin to that produced by SMPP. The metal
powder – glass frit method may be regarded as a
liquid-phase process.
The incorporation of active metal compo-
nents such as titanium, zirconium, nickel, or cop-
per can lead to formation of a mixed oxide phase
by reaction with the ceramic. These phases, like
devitrifying phases, aid in bonding and may be
fired in a reducing atmosphere [21].
Copper and nickel have been used as a less
expensive alternative to the noble metals. The
glass frit is composed of oxides that are stable
at low oxygen partial pressures (Al2 O3 , B2 O3 ,
CaO, MgO, SiO2 , ZnO). Firing is done in low
nitrogen with a low partial pressure of oxygen
(10 ppm) to achieve slight, but controlled, oxi-
dation of the metal so that it can be wet by the
glass. The glass must show sufficiently low vis-
cosity for good flow at firing temperatures [21],
[22].
4.3. Active Metal Process
The active metal techniques employ an ac-
tive constituent such as titanium, zirconium, or
hafnium in the braze metal to promote wetting
and bonding to the ceramic. The active metal
may be alloyed with a metal such as nickel or
copper to reduce its reactivity and provide a
brazing temperature as low as 800 – 1200 ◦ C.
The braze materials are used in the form of pow-
ders, shims, or wires. Brazing is typically per-
formed under vacuum or in an inert atmosphere
with careful temperature control. The hydride of
the active metal may be applied separately as a
layer on the ceramic and fired, a process resem-
bling SMPP [23].
In the liquid braze the active metal is trans-
ported to the ceramic surface where it can react
[24]. Wetting is enhanced to the point that cau-
tion must be taken to prevent braze metal from
flowing into unwanted areas. The joints formed
by this method cannot withstand elevated tem-
peratures, even in inert gas atmospheres, because
of continued reaction of the bonding phase with
the ceramic.
4.4. Gas – Metal Eutectic Process
In the gas – metal eutectic technique, a cop-
per sheet is bonded directly to a ceramic sub-
13
strate by liquid-phase reaction. A carefully con-
trolled oxygen atmosphere and temperature are
required. A eutectic copper – copper oxide melt
is formed to wet the ceramic. A reaction layer
containing AlCuO2 can form and aids in bond-
ing. Strong bonds have been reported for alu-
mina, beryllia, silica, and spinels [25], [26].
4.5. Pressed Diffusion Joins
Joining by solid-phase diffusion and reaction
can also be used to create a ceramic-to-metal
bond. Such bonds are typically termed pres-
sure diffusion, crunch, or ram joins. A low-
yieldstress metal such as copper is pressed to the
ceramic, or the ceramic is forced into a cavity in
the metal, so that there is good contact between
metal and ceramic and there is an applied or
residual force at their interface. The parts should
be as clean as possible before contact. The parts
are held, often with great external force applied
to the interface, at as high a temperature as possi-
ble above one-half the melting point of the metal
in kelvin. A variety of metals and ceramics can
be bonded by the resulting diffusion and chem-
ical reaction [27], [28].
4.6. Vapor-Phase Metallizing
A thin film of metal, which may be base, noble,
or reactive metal, is applied by various vapor-
phase deposition methods, including ion implan-
tation, evaporation, sputtering, reactive sputter-
ing, plasma methods, and chemical vapor depo-
sition (CVD). Often the initial bonding layers
are reactive metals such as Ti, Zr, and Cr to pro-
mote bonding, followed by base or noble metals
such as Cu, Ni, Au, and Pt. Because platinum
shows good ductility and its expansion matches
that of alumina, it is often directly deposited.
Final layers are usually oxidation-resistant met-
als. Layers up to several micrometers thick can
be built up in this manner, although usually the
metallization is quite thin.
These layers may be built up by more con-
ventional solder or braze methods for bonding
with a metal part. Brazing is usually done in hy-
drogen, under vacuum, or in cracked ammonia.
Strong hermetic seals can be made on various
14 Ceramics, Ceramic – Metal Systems
polyphase, single-phase, and single-crystal ce-
ramics. Furthermore, glasses and other ceramics
not tolerant of brazing can be soldered at lower
temperature.
4.7. Liquid-Phase Metallizing
An alternative metallizing method involves ther-
mal reduction of a salt solution of a precious
metal (platinum, gold, silver, or palladium). A
thin, conductive coating is obtained and may be
electroplated or soldered directly. Molten salts
have been used in conjunction with reactive met-
als (Ti, Zr, Hf, or U) to metallize ceramics [3].
4.8. Electroforming
Electroforming can be used to avoid high-
temperature brazing after a ceramic part has
been metallized by another method. The met-
allized ceramic is placed in contact with a metal
such as copper under slight pressure. The assem-
bly is then placed in an electroplating bath for
several days, and the electrodeposition of metal
in and around the gap between metal and metal-
lized ceramic creates the bond. Large, complex
parts have been joined in this way. This tech-
nique has been coupled with pressure diffusion
joining to produce an enhanced bond, but in such
a case high temperatures are not avoided.
4.9. Graded Powder Process
The graded powder process produces a join by
first pressing a powder compact of metal and
metal oxide either to the base ceramic or between
ceramic and metal. Often this process is similar
to SMPP or metal powder – glass frit methods. A
gradual change in the powder composition from
ceramic-rich to metal-rich is accomplished by
producing the preform in layers. This chang-
ing composition provided by mechanically mix-
ing powders provides a ceramic-rich layer and a
metal-rich layer for the respective materials to be
joined, with graded composition and properties
in between. The powder is sintered at elevated
temperature similar to SMPP. Bond strengths are
not especially greater than those of other meth-
ods, and the preform is expensive. Only limited
commercialization has taken place.
4.10. Nonmetallic Fusion Process
Nonmetallic fusion bonds employ a glass frit
to produce a bonding glass between ceramic
and metal components. This is a liquid-phase
method.
Ceramic glazes and glass frits can be used to
join ceramics to each other or to metals if used
in layers sufficiently thin to be incorporated into
the ceramic and metal on cooling. The incorpo-
ration of the glass in the structure may allow use
at significantly higher temperatures than the fab-
rication temperature or softening temperature of
the glass suggests.
An oxide composed of constituents such as
MnO2 , SiO2 , and Al2 O3 may be applied to
the join interface as a suspension or preform.
The assembly is heated in an inert gas atmo-
sphere for up to 15 min at 1200 – 1500 ◦ C and
then cooled relatively rapidly, 100 ◦ C/min, so
that the glass does not devitrify. The compo-
sition of the frit can be adjusted to match the
expansion, wetting, and bonding characteristics
of ceramic and metal. The bond may be heated
to temperatures substantially higher, ca. 800 ◦ C,
than SMPP joins. Success has be obtained with
high-purity alumina and sapphire. The high tem-
peratures and cooling rates can lead to defects
or interfacial failure.
5. Thin Films and Coatings
A coating may be defined as a near-surface re-
gion of a material with properties different from
those of the bulk. The fabrication of coatings
varies widely, depending on application, sub-
strate, coating materials, and economic consid-
erations. Coating techniques may be categorized
as follows: (1) those processes that produce a
layer of material in the surface region of the bulk
material that has properties differing from those
of that bulk material and (2) those processes that
modify the immediate surface of the bulk mate-
rial, causing that region to have different prop-
erties [29].
Ceramic – metal coatings can be divided into
two categories: (1) coatings containing both ce-
ramic and metal phases and (2) ceramic films
 Ceramics, Ceramic – Metal Systems 15

and coatings on metals. Ceramic – metal coat- low-friction materials. When low friction is re-
ings are a unique type of coating in that the prop- quired in addition to wear resistance, softer ma-
erties of the coating are strongly controlled by terials may be used. Calcium fluoride and com-
the microstructure of the metallic phase. These posites including calcium fluoride are among the
composite films exhibit properties unavailable most promising solid lubricants for service at ca.
from either the ceramic or metal phases alone 650 ◦ C [31].
(see Section 6.1).
Table 4. Bulk properties of some hard coat materials
Ceramic films and coatings are a special class
of ceramics in the sense of their special form Material Microhardness, Oxidation
and the special preparation techniques required. kg/mm2 temperature,
◦
C∗
However, their uses are diverse and exploit the
wide range of unique and desirable properties Al2 O3 2350
B4 C 4200 1090
that various bulk ceramics possess. In this sense, Cr3 C2 2650 1370
ceramic films and coatings should be viewed as Cr2 O3 1800
a large family of materials with quite diverse SiC 2900 1650
Si3 N4 2000 1400
compositions and properties [30]. TiC 3200 540
TiN 1950 540
WC 2050 540

5.1. Uses ∗ Temperature of appreciable detrimental oxidation. Passivating

oxide films form at lower temperatures.
Table 3 lists uses of ceramic films and coatings
and gives typical examples. The table is illus- Corrosion and oxidation resistance at high
trative rather than exhaustive, but does show the temperatures constitute a complex field of chem-
wide range of ceramic films and coatings, both ical reactions and protective mechanisms pro-
in terms of uses and in terms of compositions. vided by coatings. Often the protective mech-
anism involves the production of a dense, ad-
Table 3. Uses of ceramic films and coatings
herent, diffusion-resistant oxide film by in situ
Use Typical ceramic materials oxidation, e.g., chromia and alumina on high-
temperature superalloys and silica on silicon car-
Wear reduction Al2 O3 , B4 C, Cr3 C2 , CrB2 , CrSi2 ,
Cr3 Si2 , DLC ∗, Mo2 C, MoSi2 , SiC, bide. This requires that the base alloy or ce-
TiB2 , TiC, TiN, WC ramic has a composition that is self-passivating.
Friction reduction MoS2 , BN, BaF2 – CaF2
Corrosion reduction Cr2 O3 , Al2 O3 , Si3 N4 , SiO2
Much work has been directed toward developing
Thermal protection Ca2 Si4 , MgAl2 O4 , MgO, ZrO2 pinhole-free coatings with sufficient adherence
(stabilized with Mg or Ca) to use as corrosion protection mechanisms. An-
Electrical conductivity In2 O3 – SnO2
Semiconductors GaAs, Si other corrosion-related problem involves water
Electrical insulation SiO2 attack, especially the stress-assisted water attack
Ferroelectricity Bi4 Ti3 O12
Electromechanical AlN
involved in slow crack growth in many ceram-
Selective optical BaF2 – ZnS, CeO2 , CdS, ics. Silicon nitride films are promising barriers
transmission and CuO – Cu2 O, Ge – ZnS, SnO2 for protection of glass, including glass fibers for
reflectivity
Optical wave guides SiO2 optical communication [32].
Optical processing GaAs, InSb Thermal protection coatings, consisting of a
(electrooptic, etc.)
Sensors SiO2 , SnO2 , ZrO2
thin layer of ceramic applied over a metallic
bond coat, are used in gas turbine components,
∗ DLC = diamond-like carbon. such as combustion chambers, and are under de-
velopment for additional uses. Bond coat oxida-
Resistance to wear is generally correlated tion and stress development appear to be limiting
with hardness. Of special interest is the use of aspects of present coatings [33].
ceramics for wear resistance at elevated tem- Thin films play a central role in electronic
peratures. Table 4 gives the microhardness and and optical devices, especially as the dimensions
oxidation temperatures for some hard coat ma- of these devices are reduced. Coating applica-
terials. Although some hard-coating materials tions include thin-film resistors and photother-
have good wear resistance, they generally are not mal converts for solar energy. Indeed, modern
16 Ceramics, Ceramic – Metal Systems
electronics would not be possible without thin-
film technology [34].
5.2. Deposition Techniques
Table 5 lists coating techniques that have been
used for ceramics. Table 5 includes four sub-
categories of processes: (1) atomic deposition,
(2) particulate deposition, (3) bulk coating, and
(4) surface modified coatings. Ceramic coating
processes could also be divided into those that
directly apply the ceramic compound or a pre-
cursor and those that react metallic species with
gases to form the ceramic coating compound
[35].
With the exception of CVD-coated cutting
tools, traditional ceramic coatings were limited
to those materials that could be applied to a sur-
face as a powder and subsequently fused, such as
glazes (→ Ceramics, General Survey, Chap. 5.)
and enamels (see Section 3.2), which were either
dipped or sprayed. Studies have shown that non-
traditional ceramic materials, such as nitrides,
carbides, and oxides, could be applied to a vari-
ety of materials ranging from polymers to metals
to other ceramics. The techniques that are most
used include chemical vapor deposition, evapo-
ration, sputtering, plasma spraying, sol–gel pro-
cessing, and ion implantation [36].
5.2.1. Chemical Vapor Deposition (CVD)
Chemical vapor deposition is the reaction to
form the desired compound and the condensa-
tion of the compound or compounds from the
gas phase onto a substrate where reaction oc-
curs to produce a solid deposit. The compound
bearing the deposit material, if not already a gas,
is vaporized by either a pressure differential or
the action of a carrier gas and is transported to
the substrate. Since the vapor condenses on any
relatively cool surface that it contacts, all parts
of the deposition system must be at least as hot
as the vapor source. The reaction portion of the
system is generally much hotter than the vapor
source but considerably colder than the melting
temperature of the deposit.
Generally the deposition process is either
thermal decomposition (Fig. 8) or chemical
reduction. Both thermal decomposition and
chemical reduction most frequently involve
organometallic compounds, but halides and
other simple inorganic compounds can be used.
CVD processes are dependent on both the ther-
modynamics and kinetics of the reaction. Even
though the formation of a material is thermody-
namically feasible, its growth rate must not be
too slow. When reaction occurs on the substrate,
the stages required to obtain a deposit are
1) Formation of the gaseous phase
2) Gas transfer to the substrate
3) Adsorption
4) Decomposition of the adsorbed phase
5) Compound deposition and desorption of the
other decomposition products
6) Removal of these products
Table 6 lists ceramics that can be deposited by
CVD. The CVD process finds its greatest ap-
plication in the preparation of coatings that are
not easily applied by physical vapor deposition
(PVD) techniques.
It has become common to apply thin coatings
of carbide and oxide ceramics to cemented car-
bides and cermets to increase performance. Such
coatings are commonly applied by chemical va-
por deposition in micrometer thicknesses and
can provide abrasion resistance (Al2 O3 , TiC),
oxidation resistance (Al2 O3 ), friction reduction
(TiN), or a thermal or diffusion barrier (Al2 O3 ,
TiN, TaC). Often many different coatings are
used to obtain matched thermal expansions and
better adherence properties. In the area of ce-
mented carbide cutting tools, cutting speeds can
be increased by three times and tool lifetimes
may be two to ten times greater than those of
an uncoated tool. In the past decade such coated
tools have been introduced and now dominate
the marketplace for industrial machining of steel
[37].
The advantages of CVD are the following:
1) Various kinds of coatings possible – car-
bides, nitrides, and oxides
2) Crystal growth controlled by controlling the
reactive gas concentrations
3) High deposition rates
4) Possibility to coat complex bulky shapes
Its disadvantages include the following:
1) Rather high temperatures required to pro-
duce certain compounds
 Ceramics, Ceramic – Metal Systems 17
Table 5. Categorization of ceramic coating techniques

Atomic deposition Particulate deposition Bulk coatings Surface modification

chemical vapor environment fusion coatings diffusion chemical (liquid)

chemical vapor deposition sol–gel diffusion bonding oxidation
reduction thermal spraying hot isostatic pressing chemical (vapor)
decomposition plasma spraying wetting processes thermal
plasma enhanced low-pressure plasma spraying dipping plasma
plasma environment laser-assisted plasma spraying enameling ion implantation
sputter deposition electric arc spraying spraying sputtering
diode
triode
reactive
evaporation
direct
activated reactive
vacuum environment
vacuum evaporation
ion implantation

Figure 8. Schematic of CVD reactor

2) Low pressures restrict the types of substrate Evaporation processes for the deposition of
that can be coated refractory compounds are subdivided into two
3) Uniform heating of the substrate at times dif- types:
ficult
4) Reactor vessel design is critical to coating 1) Direct evaporation – the evaporant is the re-
complex shapes uniformly [38]. fractory compound itself.
2) Reactive evaporation – a metal or compound
in a low valence state is evaporated in the
presence of a reactive gas to form a com-
5.2.2. Evaporation pound deposit.

In the evaporation technique, the coating mate-
rial is placed in a vacuum chamber opposite the
substrate. A relatively high vacuum is used, typi-
cally 10−6 Torr (≈ 10−4 Pa), because the coating
material must be evaporated either by heating it
to some large fraction of its melting point or by
using an electron beam to locally heat it. When
it is evaporated, its atoms are ejected in straight
lines from the solid and impinge and condense
on all exposed surfaces, including the substrate
to be coated. Because there is no driving force to
accelerate the freed coating atoms, they impinge
with ca. 0.2 eV.
Direct evaporation of ceramics can occur
with or without dissociation of the compound
into fragments. However, the observed vapor
species show that very few compounds evapo-
rate without dissociation. Examples are MgF2 ,
B2 O3 , CaF2 , SiO, GeO, and SnO. In the more
general cases, ceramic materials are not trans-
formed to the vapor state with the same molec-
ular composition as the solid. Subsequently the
fragments must then recombine to reconstitute
the compound. Therefore, the stoichiometry of
the deposit depends on several factors, which
can lead to cation- or anion-deficient structures.
18 Ceramics, Ceramic – Metal Systems

Reactive evaporation broadens the range of

ceramics for coatings – the ceramic need not
form directly or recombine from a vapor. Rather,
a metal or suboxide is evaporated in the presence
of a reactive gas to produce a ceramic deposit by
reaction.
Figure 9 illustrates the evaporation process
with an electron-beam source. The entire system
is within a vacuum chamber. If reactive gas is al-
lowed to enter the vacuum chamber, evaporation
can be reactive rather than direct. However, the
reaction must be both thermodynamically and
kinetically feasible.

Table 6. Chemical vapor deposition of ceramics

Figure 9. Schematic of evaporation (reactive if reactive gas
Materials Reactive gas Temperature, ◦ C present)

Nitrides Compounds that have been synthesized by

BN BCl3 + NH3
thermal decomp. B3 N3 H3 Cl3
1000 – 2000
1000 – 2000
the reactive evaporation process include α-
HfN HfClx + N2 + H2 950 – 1300 Al2 O3 , γ-Al2 O3 , Y2 O3 , TiO2 , In2 O3 , In2 O3 –
Si3 N4 SiH4 + NH3 950 – 1050 SnO2 (ITO), SnO2 , BeO, SiO2 , TiC, ZrC, NbC,
SiCl4 + NH3 1000 – 1500
TaN TaCl5 + N2 + H2 2100 – 2300 Ta2 C, VC, W2 C, HfC, VC–TiC, TiC–Ni, Ti2 N,
TiN TiCl4 + N2 + H2 650 – 1700 TiN, MoN, Cux Mo6 S8 , and Cux S [39].
VN VCl2 + N2 + H2 1100 – 1300
ZrN ZrCl4 + N2 + H2 2000 – 2500
Oxides
Al2 O3 AlCl3 + CO2 + H2 800 – 1300 5.2.3. Sputtering
SiO2 SiH4 + O2 300 – 450
thermal decomp. Si(OC2 H5 )4 800 – 1000
Silicon SiH4 + H2 + CO2 + NH3 900 – 1000 Sputtering is a coating process that involves the
oxide transport of almost any material from a source, or
nitride
SnO2 SnCl4 + H2 O target, to a substrate of almost any other material.
TiO2 TiCl4 + O2 + hydrocarbon The ejection of the source material is accom-
(flame)
Silicides
plished by the bombardment of the surface of
V3 Si SiCl4 + VCl4 + H2 the target with gas ions accelerated by high volt-
MoSi SiCl2 + Mo (substrate) 800 – 1100 age. Particles of atomic dimensions from the tar-
Borides
AlB2 AlCl3 + BCl3 ≈1000 get are ejected as a result of momentum transfer
HfBx HfCl4 + BX3 (X = Br, Cl) 1900 – 2700 between incident ions and the target. The target-
SiBx SiCl4 + BCl3 1000 – 1300
TiB2 TiCl4 + BX3 (X = Br, Cl) 1000 – 1300
ejected particles traverse the vacuum chamber
VB2 VCl4 + BX3 (X = Br, Cl) 1900 – 2300 and are subsequently deposited on a substrate as
ZrB2 ZrCl4 + BBr3 1700 – 2500 a thin film. Sputtering can be direct or reactive.
Carbides
B4 C BCl3 + CO + H2 1200 – 1800 It can be accomplished with diode, triode, or
B2 H6 + CH4 magnetron sources. Figures 10 and 11 illustrate
thermal decomp. (CH3 )3 B ≈ 550
Cr7 C3 CrCl2 + H2 ≈1000
diode and triode assemblies.
Cr3 C2 Cr(CO)5 + H2 300 – 650 Diode sputtering uses a simple two-element
HfC HfCl4 + H2 + C6 H5 CH3 2100 – 2500 electrode configuration. The expendable target
HfCl4 + H2 + CH4 1000 – 1300
Mo2 C Mo(CO)6 350 – 475 is attached to the cathode and an anode platen
Mo + hydrocarbon 1200 – 1800 supports the substrates. The system can be mod-
SiC SiCl4 + C6 H5 CH3 1500 – 1800
MeSiCl3 + H2 ≈1000
ified to allow for reactive sputtering. Diode sput-
TiC TiC4 + H2 + CH4 980 – 1400 tering may be operated in either the d.c. or
W2 C thermal decomp. W(CO)6 300 – 500 RF (radiofrequency) excitation modes, with RF
WF6 + C6 H6 + H2 400 – 900
VC VCl2 + H2 ≈1000 being preferred for ceramics because it per-
mits lower pressures and thus generally purer
films. In addition, RF sputtering reduces charge
 Ceramics, Ceramic – Metal Systems
buildup, permitting direct sputtering of ceram-
ics.
In triode sputtering a hot electron-emitting
filament is added between the anode and cathode
and serves to control the plasma. The ion current
is significantly increased, and lower gas pres-
sures can be used. These are important advan-
tages for the sputtering rate: production through-
put is increased, while potential radiation dam-
age to sensitive electronic devices is minimized.
Figure 10. Schematic of a diode sputtering assembly [9]
Figure 11. Schematic of a triode sputtering assembly
In magnetron sputtering the cathode incorpo-
rates a magnetic field aligned perpendicular to
the electric excitation field. The magnetic field
serves to impart a cycloidal motion to the free
electrons being liberated at the cathode surface
both by the electric field and by the ionized ar-
gon. The great length of the cycloidal path taken
by the electrons in response to the presence of
the magnetic field greatly enhances the yield of
argon ionization for a given current density and
voltage. The greater flux of argon ions imping-
ing on the cathode causes rapid disintegration
of the cathode and a sputtering rate for a given
voltage and current density much higher than
that for diode or triode sputtering.
19
The driving force for sputtering is electrical
rather than thermal (as in evaporation). Because
of the high kinetic energy transferred, the sput-
tered atoms impinge on the substrate with ca.
5 eV. Because of this relatively high kinetic en-
ergy of impingement, adhesion to the substrate
is usually stronger than for evaporation.
Materials having refractive indices ranging
between 1.45 and 4.08 have been investigated
for optical applications. Indium tin oxide, zinc
oxide, and titanium and tantalum oxides have
been sputtered for window films, solar cells, and
antireflective coatings.
5.2.4. Plasma Spraying
The plasma spraying process is a technique that
combines particle melting, quenching, and con-
solidation into a single process. The arc plasma
spraying process involves injection of powder
particles into a plasma jet stream created by
heating an inert gas in an electric arc. The par-
ticles injected into the plasma jet melt rapidly
and at the same time are accelerated toward
the workpiece surface. Rapid quenching of the
molten particles occurs when the droplets im-
pact the surface. Cooling rates are typically 105 –
106 K/s, and the resulting microstructures are
fine grained but may retain a substantial amount
of porosity.
The torch itself consists of two concentric
electrodes that are cooled by water and electri-
cally isolated from each other. Inert or nonox-
idizing gases, or a mixture, are passed through
the annular space formed by these electrodes,
and a d.c. arc is initiated. With proper operat-
ing procedure, the arc is continually sustained,
forming a high-temperature plasma that issues
from the nozzle front. Figure 12 illustrates the
configuration of a typical arc plasma torch sys-
tem.
Plasma-sprayed coatings offer several advan-
tages over other coating processes:
1) High particle velocities result in higher bond
strength coupled with higher coating density.
2) The heat source is more efficient because the
plasma is in a high-energy state, providing
efficient particle heating.
3) The heating source is inert, minimizing oxi-
dation.
20 Ceramics, Ceramic – Metal Systems
4) High plasma temperatures permit the spray-
ing of materials with high melting points.
Disadvantages include the following:
1) Consistency and compositional uniformity
of a coating over a large area at times can
vary.
2) Spraying tends to produce porous coatings,
especially at high velocities, because of gas
entrapment.
3) Reactive materials cannot be sprayed in open
air; however, low-pressure plasma spraying,
LPPS, can be used in air.
4) The deposits contain oxidation products, to-
gether with some porosity because of in-
complete melting, wetting, and fusing of de-
posited particles.
Figure 12. Schematic of an arc plasma spraying assembly
In LPPS the reduction of the amount of air
present in the torch region is accomplished by
maintaining the plasma system under vacuum
with only 30 – 60 Torr (4 – 8 kPa) of inert gas.
This greatly reduces the chances of included
porosity; therefore, denser deposits and more
uniform deposits are possible.
5.2.5. Sol – Gel Processing
Sol – gel coatings are based on a process of ap-
plying sols, stable dispersions of hydrous ox-
ides or hydroxides, to a substrate material. Once
these liquid dispersions are applied to a surface,
they undergo a catalyzed transition to form a gel.
The sol – gel coating is subsequently dried to re-
move excess water and densified. The specific
properties of the films, such as pore volume and
pore-size distribution, can be controlled during
densification. Typical applications of these films
include dipping and spin coating [40].
Advantages of sol – gel-derived films include
1) Low densification temperatures
2) High degree of chemical homogeneity
3) Multicomponent films possible
Disadvantages include
1) High shrinkages due to high volume of sol-
vent present
2) Difficulty in making physically stable, thick
coatings
3) Coating and substrate densified by heating
5.2.6. Ion Implantation
In ion implantation, ions are formed by colli-
sions with electrons ejected from a heated fila-
ment and accelerated in an electric field. In the
instances where the element to be ionized is a
gaseous species, such as argon, nitrogen, oxy-
gen, or carbon dioxide, which is typical for im-
planted ceramic coatings, the gas is introduced
directly into the ionization chamber, where the
high-velocity electrons strip away other elec-
trons, creating a plasma. An electric field then
directs the plasma from the chamber to a mag-
net, which is able to select ions of the desired
mass. These ions are then focused in an elec-
tric field and accelerated to the final energy to
bombard the specimen. The penetration depth
depends on the type and energy of the ions and
material to be implanted. Figure 13 illustrates an
ion implantation system [41].
Sputtered films of carbides, nitrides, and
borides exhibited increased adhesion and micro-
hardness when bombarded with heavy inert ions,
such as Kr and Xe. The formation of nitride layer
on the surface of a Ti – Al – V alloy by bombard-
ment with nitrogen ions has been found to slow
the wear rate of the metal by a factor of ten [42].
6. Ceramic – Metal Composites
Ceramic – metal composites may be defined as
the heterogeneous combination of one or more
ceramic phases with one or more metals or
alloys. Systems with very small amounts of
 Ceramics, Ceramic – Metal Systems
metal or ceramic are usually not considered as
composite materials. Also not generally viewed
as ceramic – metal composites are materials in
which metal particles may be in a continuous
ceramic – colloidal and other metal particle col-
orants in glasses, glazes, and enamels, and thin-
film materials such as sputtered and CVD resis-
tors and microwave devices for hybrid micro-
electronics.
Figure 13. Schematic of an ion implantation system
The distribution of phases in ceramic – metal
composites is typically at a fine structural level,
commonly microscopic. The metal and ceramic
phases are usually mixed physically, often with
a binder, formed, and fired at elevated tempera-
tures. For the usual production times and temper-
ature, there is relatively little or only incomplete
solution between phases.
A nomenclature problem exists for the
ceramic – metal composite materials. Two
classes of materials have evolved: cermets and
21
metal matrix composites (MMC). Neither strict
definition nor common technological usage pro-
vides a clear distinction. Indeed, some use the
two terms interchangeably. Usually, however, a
cermet is understood to consist of continuous or
partially continuous metal phase with ceramic
particles having similar size in all dimensions.
The metal matrix composites may be distin-
guished by the high aspect ratio of the ceramic
constituent: the metal surrounds long continu-
ous or chopped fibers or elongated single-crystal
whiskers of ceramic composition.
6.1. Cermets and Cemented Carbides
Within the cermet subcategory of
ceramic – metal composites, there is a nomen-
clature difficulty. Tungsten carbide – cobalt
is termed a cemented carbide, while other
carbide – metal materials, such as titanium
carbide – nickel, chromium carbide – nickel, as
well as oxide ceramic – metal systems, such as
alumina – chromium and thoria – tungsten, are
termed cermets. This distinction is largely his-
torical. The cermets were developed during and
after World War II as materials with better hard-
ness and high-temperature properties than the
cemented carbides. However, the microstruc-
tures and properties of the cemented carbides
and the cermets, particularly the carbide cer-
mets, are closely related. The structure consists
of a continuous metal or alloy cement bond-
ing grains (particles) of carbide and/or oxide
ceramic.
Cermets and cemented carbides derive their
usefulness from the combination of compressive
strength, hardness, and thermal resistance pro-
vided by the ceramic with ductility, lubricity, and
adhesion provided by the metal. The cermets and
cemented carbides are used for their strength,
hardness, and abrasion resistance, particularly
at elevated temperatures, which may arise from
the environment or frictional heating. Uses in-
clude metal and rock cutting or grinding tools,
friction and glide devices, turbine parts, flame
nozzles, magnetron tube cathodes, seals, high-
temperature containers and pouring spouts, and
the ball for ballpoint pens.
Cermets are generally prepared by mixing
carbide and/or oxide powder with metal pow-
der in the presence of a binder. The chemistry of
22 Ceramics, Ceramic – Metal Systems

each component is often quite complex. Tung- provides fracture toughness. Hardness decreases
sten carbide typically contains purposeful addi- with increased metal binder because the cermet
tions of tantalum carbide and titanium carbide. is less resistant to deformation [43], [44]. The
Molybdenum is added to nickel to promote wet- size of the ceramic grain also affects hardness:
ting of titanium carbide. Some cermet is unidi- for a 16 wt % Co cemented carbide, the hard-
rectionally or isostatically pressed and heated to ness decreases almost linearly from 89 to 85 RA
a temperature at which the metal liquifies, coats, as the grain size decreases from 1 to 6 µm. Fine
and bonds the ceramic. Alternative preparation submicrometer grain size increases hardness and
methods may include slip casting, liquid-metal resistance to deformation. However, for a fixed
infiltration, or hot pressing of parts. The factors amount of binder metal, a decrease in the grain
that dictate the properties of the final part are the size and the corresponding increase in grain sur-
following [43–45]: face area may result in inadequate metal to wet
1) Bonding between carbide grains and matrix the grain, leading to loss of fracture strength.
2) Composition and structure of the matrix
3) Shape and size of the carbide or oxide grain
4) Dispersion of the carbide grain in the matrix
A good bond between metal binder and ce-
ramic grain is required to transfer load properly
and to provide a homogeneous microstructure
for uniform load bearing and deformation. Fur-
thermore, since a wetting angle of near zero de-
grees is usually desired to have uniform spread-
ing of binder, the degree of bonding is usually
quite high. The wetting angle is affected by the
composition of the metal binder and ceramic
grain, as well as by the firing atmosphere [43].
Phase composition, distribution, and stabil-
ity have major effects on properties. For ex-
ample, the tungsten carbide – cobalt system is
stable only over a narrow carbon content. At Figure 14. Effect of increased binder on mechanical prop-
erties of TiC – Ni – Mo cermet with an average TiC grain
16 wt % cobalt, WC and Co are the sole size of 1 µm
phases in the compositional range from 6.00 to
6.12 wt % C – an allowable composition range of
0.12 %. Graphite forms above 6.12 % C and eta
phase (η-WC1−x ) below 6.00 % (see Carbides,
Chap. 2.1.). Both phases embrittle the cemented
carbide, causing a loss of one-quarter of the op-
timum strength for compositions about 0.1 %
outside the acceptable range [44], [45].
The microstructure of a cemented carbide or
cermet has an important influence on its prop-
erties. A uniform dispersion of carbide or oxide
ceramic grains in a matrix of metal binder gives
the best mechanical properties. Rounded grains, Figure 15. Effect of mean free path on hardness for a ce-
which can result either during powder prepara- mented carbide
tion or from partial dissolution by molten metal A useful way of examining the properties of
during firing, improve the fracture strength. The cermets and cemented carbides, as well as other
relative amount of binder phase strongly affects composites, is provided by the concept of mean
the mechanical properties, as can be seen in free path, the average distance between neigh-
Figure 14. Fracture strength increases with the bor ceramic grains, i.e., the average thickness of
amount of binder because the metal ductility
 Ceramics, Ceramic – Metal Systems
the binder phase. The mean free path depends
on the size and shape of the ceramic grain and
the amount of metal available. The hardness (as
well as a variety of other mechanical proper-
ties) depends, within a narrow band, only on this
mean free path (see Fig. 15), provided there is
adequate metal binder phase to cover the grains
uniformly. For the tungsten carbide – cobalt ex-
ample shown, a mean free path of less than ca.
0.1 µm corresponds to incomplete binder and
poorer properties.
6.2. Metal Matrix Composites
The concept of reinforcing a metal with ceramic
is not new. In the 1950s the need for jet engine
components that could withstand high tempera-
tures for long periods of time began the search
for materials that had properties better than those
that could be attained by the metal alone.
The advantages that metal matrix compos-
ites offer over conventional metals include (1)
taking advantage of the anisotropic character of
the composite in the efficient design and fabri-
cation of components, (2) manufacturing an en-
gineered material with a specific set of strength
and toughness requirements, and (3) increasing
the strength, modulus, creep resistance, and ox-
idation resistance of common engineering al-
loys such as aluminum, titanium, and nickel.
In addition, a major advantage of metal ma-
trix composites arises from the reduction in the
strength : weight ratio. For instance, an alu-
minum alloy reinforced with graphite exhibits
the same strength as steel while exhibiting a
45 % increase in the strength : density ratio [46],
[47].
In comparison to other composite matrices,
the greatest potential advantages of the metal
matrix are its resistance to severe environments,
toughness, and strength at high temperatures.
The temperatures where metal matrix compos-
ites exhibit the greatest potential advantages
over rival metallic alloys and polymer matrix
composites are above 800 ◦ C (Fig. 16). In fiber-
or filament-reinforced metals the environmen-
tal stability of the matrix at elevated tempera-
tures can be emphasized because the required
mechanical strength and stiffness are obtained
from the reinforcement. The strength require-
ments of the matrix are nominal, the matrix
23
only serving to transfer load into the fiber. Up
to 540 ◦ C, several potential metal composite
systems have been identified. For higher tem-
peratures, at which oxidation presents a ma-
jor problem, stable reinforcements such as alu-
mina and silicon carbide fibers have consid-
erable potential. Below 320 ◦ C, the potential
is less clear, but the advantages of metal ma-
trix composites over polymer matrix compos-
ites include improved wear and erosion resis-
tance, greater shear, compressive and transverse
strength, increased toughness and hardness, and
greater strain prior to failure. The disadvantages
include higher density, more difficult fabrica-
tion, metal – fiber reactions, and higher cost.
Figure 16. Temperature regimes of usefulness for various
materials
Reinforcement Materials. The most appro-
priate reinforcing material depends on the re-
quirements put upon the metal matrix compos-
ite. A wide variety of materials of high elastic
modulus, high strength, low density, and high-
temperature stability are available. Table 7 lists
a number of ceramic materials along with typi-
cal mechanical properties; in addition, the prop-
erties of a few glasses and metals available as
fibers are shown for comparison. In many cases
the metal or the fabrication technique results in
composites with less than theoretical properties.
In these instances such things as process defects
and matrix – filler incompatibility affect prop-
erties. Matrix – filler compatibility can include
the following factors: (1) wetting, (2) chemical
bonding, (3) filler surface character, i.e., shape,
roughness, and porosity, (4) filler volume frac-
tion and size, i.e., particle size or fiber length and
diameter, (5) filler orientation, and (6) relative
thermal expansion and elastic modulus match.
The last can give rise to residual stresses that
can affect the mechanical properties.
24 Ceramics, Ceramic – Metal Systems
Table 7. Filament properties for a variety of reinforcing materials establish and maintain fiber alignment
Material Tensile Elastic Density, Strength : be able to vary filler loading
strength, modulus, density achieve a high-density matrix
ratio,
(ksi) ∗ GPa g/cm3 106
establish filler–matrix interfacial bond suffi-
cient to transmit applied load from matrix to
Fibers filler
Steel 600 200 7.9 2.1
Tungsten 575 407 19.3 0.83 allow a degree of matrix alloying
Molybdenum 320 331 10.2 0.88 allow for postfabrication heat treatment
S-glass 600 86 2.5 6.52 provide flexibility in filament spacing
E-glass 500 72 2.5 5.43
Silica 500 72 2.2 5.43 allow for cross and angle lay-ups in some
Boron 450 400 2.6 4.68 instances
Silicon carbide 350 379 3.4 2.84
Alumina 350 483 3.98 2.43 minimize product variability
Graphite 285 345 1.66 4.75 be amenable to scale-up
Whiskers
Alumina 2000 483 3.98 13.9
Silicon carbide 1500 483 3.2 13.0 Compatibility. Filler–matrix compatibility
includes the chemical reactions between matrix
∗ ksi, a non-SI unit, equals 6.89 MPa.
and filler during consolidation, secondary pro-
cessing, and use. Some degree of chemical in-
Fabrication Process. Numerous techniques
teraction should take place. In a successful com-
have been employed for the consolidation of ce-
posite, the metal completely wets the filler and
ramic fibers, whiskers, and particles into metal
chemically bonds to it. However, the exact de-
matrices. These techniques vary widely, from
gree of chemical interaction needed to produce
typical powder-metallurgical techniques such as
optimum properties is not yet known. If the metal
slip casting to techniques such as diffusion bond-
and filler are able to bond chemically during con-
ing and plasma spray bonding. The most widely
solidation, there is a likelihood that this chemical
used consolidation techniques are the following:
interaction continues during use, degrading the
diffusion bonding filler as a result. Knowledge of the thermody-
plasma spray bonding namics for the combination of metal and filler
electroforming is an important composite design criterion and
liquid-metal infiltration a suitable starting point for selecting stable sys-
high-energy rate forming tems.
explosive welding
hot roll bonding
hot drawing 7. References
cold rolling
cold drawing 1. J. T. Klomp: “Interfacial Reactions between
chemical vapor deposition Metals and Oxides during Sealing,” Bull. Am.
Ceram. Soc. 59 (1980) 794 – 800.
powder slip casting
2. M. E. Twentyman: “High Temperature
hot extrusion Metallizing,” J. Mater. Sci. 10 (1975)
Each technique employed to consolidate a 765 – 766.
composite requires specific methods for deal- 3. W. H. Kohl: Handbook of Materials and
Techniques for Vacuum Devices, Reinhold
ing with the anisotropic and fragile reinforc-
Publ. Co., New York 1967.
ing fillers. The ceramic fiber may be used in 4. J. R. Tinklepaugh, W. B. Crandall (eds.):
oriented or random configurations as individ- Cermets, Reinhold Publ. Co., New York 1960.
ual fiber, bundles, or weaves. Each process must 5. J. A. Pask, R. M. Fulrath: “Fundamentals of
meet to some reasonable degree each of the fol- Glass-to-Metal Bonding: VIII. Nature of
lowing objectives: Wetting and Adherence,” J. Am. Ceram. Soc.
45 (1962) 592 – 596.
avoid filament or fiber breakage 6. F. Bashforth, S. C. Adams: An Attempt to Test
consolidate composite with minimal filler Theories of Capillarity, Cambridge University
degradation Press, London 1883.
 Ceramics, Ceramic – Metal Systems
7. A. G. Pincus: “Mechanism of
Ceramic-to-Metal Adherence, Adherence of
Molybdenum to Alumina Ceramics,” Ceram.
Age 63 (1954) 16 – 20, 30 – 32.
8. J. D. Partridge: Glass-to-Metal Seals, Society
of Glass Technology, Sheffield, England, 1949.
9. D. Tabor: “Interaction between Surfaces:
Adhesion and Friction,” in Surface Physics of
Materials, vol. 11, Academic Press, New York
1975, pp. 475 –529.
10. S. S. Rekhson: “Annealing of Glass-to-Metal
and Glass-to-Ceramic Seals,” Glass Technol.
20 (1979) 27 – 35.
11. H. E. Pattee, R. E. Evans, R. E. Monroe:
Joining Ceramics and Graphite to Other
Materials, WASH SP-5052, NASA,
Washington, D.C., 1968.
12. J. J. Schmidt, J. L. Carter: “Using Nitrogen
Based Atmosphere for Glass-to-Metal
Sealing,” Met. Prog. 128 (1985) 29 – 34.
13. A. I. Andrews: Enamels: The Preparation,
Application and Properties of Vitreous
Enamels, Twin City Printing, Champaign, Ill.,
1945.
14. M. Borom, J. Pask: “Role of Adherence
Oxides in the Development of Chemical
Bonding at Glass-Metal Interfaces,” J. Am.
Ceram. Soc. 49 (1966) 1 – 6.
15. B. W. King, W. H. Duckworth: “Nature of
Adherence of Porcelain Enamels to Metals,” J.
Am. Ceram. Soc. 42 (1959) 504 – 525.
16. L. S. O’Bannon: “The Adherence of Enamels,
Glass, and Ceramic Coatings to Metals – A
Review,” Batelle Memorial Institute,
Columbus, Ohio, 1959.
17. G. R. Van Houten: “A Survey of
Ceramic-to-Metal Bonding,” Ceram. Bull. 38
(1959) 301 – 307.
18. G. P. Chu: “Some Aspects on Glass-Ceramics
to Metal Sealing,” Int. Cong. Glass, 10th,
Ceramic Soc. Japan, 1967, pp. 94 – 102.
19. C. I. Helgesson: Ceramic-to-Metal Bonding,
Boston Technical Publ., Cambridge 1968.
20. S. S. Cole, G. Sommer: “Glass Migration
Mechanism of Ceramic to Metal Seal
Adherence,” J. Am. Ceram. Soc. 44 (1961)
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