Yoshizo Inomata (Auth.), Shigeyuki Sömiya, Yoshizo Inomata (Eds.) - Silicon Carbide Ceramics-1 - Fundamental and Solid Reaction-Springer Netherlands (1991)

Silicon Carbide Ceramics-l
Fundamental and Solid Reaction

SILICON CARBIDE CERAMICS-l
FUNDAMENTAL AND
SOLID REACTION
Edited by
SHIGEYUKI SOMIYA
Professor, The Nishi Tokyo University, Japan
Professor Emeritus, Tokyo Institute of Technology, Japan
YOSHIZO INOMATA
National Institute for Research in Inorganic Materials,
Tsukuba, Japan
Ceramic Research and Development in Japan Series
ELSEVIER APPLIED SCIENCE

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Silicon carbide ceramics.
1
1. Silicon carbide
I. SOmiya, Shigeyuki II. Inomata, Yoshizo III. Series
661.88
ISBN 1-85166-560-9
ISBN 1-85166-559-5 pbk
Library of Coagress CafaIociaI-in-Publication nata
Silicon carbide ceramics-l/edited by Shigeyuki SOmiya and Yoshizo Inomata.

p. cm--(Ceramic research and development in Japan series)
Includes bibliographical references and index.
ISBN 1-85166-560-9.-ISBN 1-85166-559-5 (set)
1. Silicon carbide. 2. Ceramics. I. SOmiya, Shigeyuki.
II. Inomata, YoshizO. III. Series.
TP245.S5S364 1991
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Preface
Discovered by Edward G. Acheson about 1890, silicon carbide

is one of the oldest materials and also a new material. It occurs
naturally in meteorites, but in very small amounts and is not in a
useable state as an industrial material. For industrial require-
ments, large amounts of silicon carbide must be synthesized by
solid state reactions at high temperatures.
Silicon carbide has been used for grinding and as an abrasive
material since its discovery. During World War II, silicon carbide
was used as a heating element; however, it was difficult to obtain
high density sintered silicon carbide bodies. In 1974, S.
Prochazka reported that the addition of small amounts of boron
compounds and carbide were effective in the sintering process to
obtain high density. It was then possible to produce high density
sintered bodies by pressureless sintering methods in ordinary
atmosphere. Since this development, silicon carbide has received
great attention as one of the high temperature structural ceramic
materials. Since the 1970s, many research papers have appeared
which report studies of silicon carbide and silicon nitride for
structural ceramics.
Silicon carbide ceramics are applicable for use in the
semiconductor industry, atomic power plants, parts for engines,
parts for aerospace vehicles and so on because silicon carbide
ceramics have:
1) High chemical stability
2) High thermal conductivity
3) Strength at high temperature
4) Low thermal expansion
5) High thermal shock resistance
6) High temperature for abrasion
v
Preface
One of the characteristics of the study of silicon carbide in

Japan is that many physicists, crystallographers, chemists,
metallurgists, mechanical engineers, electronic engineers and
ceramicists study silicon carbide as both powders and as sintered
bodies. At the beginning of the 1970s, the study of silicon carbide
was not as active as the study of silicon nitride. However, silicon
carbide is better than silicon nitride for providing high tempera-
ture strength and corrosion resistance. At present, Japan
produces sintereable powders, whiskers, fibers, etc., as well as
silicon carbide.
The Japanese edition of this work is in one volume but the
English edition is in two volumes. This book, Volume 1, shows
aspects of Japanese research and development of silicon carbide,
especially fundamentals, new materials of powders, fibers and
whiskers by many authors; Volume 2 describes applications. For
individual needs, this book is designed to provide an understand-
ing of one of the facets of Japanese research and development of
silicon carbide.
It is hoped this book promotes a greater understanding of
silicon carbide R&D, as well as other mutual interests. The
editors also want to provide readers of this work with an
understanding of the past and present status of silicon nitride
research and development in Japan. After having read Volumes
1 and 2, readers should have an idea of the future of silicon
carbide research and development
Shigeyuki Somiya
Dean Professor
The Nishi Tokyo University, Japan
Professor Emeritus, Tokyo Institute of Technology, Japan
Yoshizo Inomata
Group Leader
The Third National Institute in Inorganic Materials
vi
Acknowledgement
To
Professor Emeritus Toshiyoshi Yamauchi
Professor Emeritus J. A. Pask
Dr. S. Prochazka
They encouraged us to study silicon carbide.
vii
Contents
Preface v
Acknowledgments vii
List of Contributors xi
1 Crystal Chemistry of Silieon Carbide 1

Y.lnomata
2 Properties and App6cations of Silieon Carbide

Ceramics 13
K. Yamada and M. Mohri
3 Epituial Growth of SiC Single Crystal Films 45

Y. Nakajima
4 Silieon Carbide Prepared by Chemical Vapor

Deposition 77
T. Hirai and M. Sasaki
5 Continuous Silieon Carbide Fibers 99

K. Okamura
6 Preparation and Sintering Properties of Ultrafine

Silieon Carbide Powder Obtained by Vapor Phase
Reaction 119
M. Endo and N. Urasato
Contents
7 Sintering Behavior of Ultrafine Silicon Carbide Powder 149

J. Hojo
8 Gnin Boundaries in High-Purity Silicon Carbide 169

Y. Ishida, H. Ichinose and Y. Inomata
9 Gnin Boundary and High-Temperature Strength in

~ m
H. Kurishita, H. Yoshinaga and Y. Ikuhara
10 Sintering of Silicon Carbide 213

H. Tanaka
11 Joining of SiC Ceramics 239

T.Iseki
12 Multiple Toughening in A120 3 /SiC Whisker/Zr02

Composites 265
T. Uchiyama, S. Inoue and K. Niihara
13 Sintering Aids and Thermal Conductivity of Polycry-

staIIine SiC 275
T. Sakai, N. Hirosaki and T. Aikawa
Index 289
x
List of Contributors
T. AlKAWA
Materials Research Laboratory, Central Engineering
Laboratories, Nissan Motor Company Ltd, Yokosuka 237,
Japan.
M. ENDO
Faculty of Engineering, Shinshu University, 500 Wakasato,
Nagano 380, Japan.
T. HIRAI
Institute for Materials Research (formerly the Research Institute
for Iron, Steel and Other Metals), Tohoku University, 2-1-1
Katahira, Aoba Sendai 980, Japan.
N. HIROSAKI
Materials Research Laboratory, Central Engineering
Laboratories, Nissan Motor Company Ltd, Yokosuka 237,
Japan.
l. HOlO
Faculty of Engineering, Kyushu University, 6-10-1 Hakozaki,
Higashi-ku, Fukuoka 812, Japan.
H.ICHINOSE
Institute of Industrial Science, University of Tokyo, 7
Roppongi, Minato-ku, Tokyo 106, Japan.
:xi
List of Contributors
Y.IKUHARA
Graduate School of Engineering Sciences, Kyushu University,
Kasugakoen, Kasuga, Fukuoka 816, Japan. Present address:
JFCC (Japan Fine Ceramics Center), 2-4-1, Mutsuno, Atsuta-
Ku, Nagoya,456, Japan.
Y.INOMATA
National Institute for Research in Inorganic Materials, 1-1,
Namiki, Tsukuba, Ibaraki 305, Japan.
S. INOUE
Riken Corporation, 810 Kumagaya, Kumagaya, Saitama 360,
Japan.
T.ISEKI
Department of Inorganic Material, Tokyo Institute of
Technology, Ohokayama, Meguro-ku, Tokyo 152, Japan.
Y. ISHIDA
Institute of Industrial Science, University of Tokyo, 7
Roppongi, Minato-ku, Tokyo 106, Japan.
K. KURISHITA
Department of Materials Science and Technology, Graduate
School of Engineering Sciences, Kyushu University,
Kasugakoen, Kasuga, Fukuoka 816, Japan.
M.MOHRI
Tsukuba Research Laboratory, Sumitomo Chemical Company,
Ltd, 6, Kitahara, Tsukuba, Ibaraki 300-32, Japan.
Y. NAKAJIMA
Materials Research and Analysis Center, Sharp Corporation,
2613-1, Ichinomoto-cho, Tenri, Nara 632, Japan.
K. NIIHARA
The National Defense Academy, Yokosuka 289, Japan. Present
address: ISIR Osaka University, 8-1, Mihogoaka, Ibaraki,
Osaka, 567, Japan.
List o[ Contributors
K. OKAMURA
The Oarai Branch, Institute [or Materials Research, Tohoku
University, Narita, Oarai-machi, Ibaraki 311-13, Japan.
Present address: College o[ Engineering, University o[ Osaka
Pre[ecture, 4-804 Toriume Mozu, Umemachi, Sakai, Osaka,
591 Japan.
T. SAKAI
National Institute [or Research in Inorganic Materials, Science
and Technology Agency, 1-1 Namiki, Tsukuba, Ibaraki 305,
Japan. Present address: AISIN SEIKI Tsukuba Lab., D-26,
Tsukuba Center Inc., 2-1-6, Sengen, Tsukuba, 305, Japan.
M. SASAKI
Institute [or Materials Research (formerly the Research Institute
[or Iron, Steel and Other Metals), Tohoku University, 2-1-1
Katahira, Aoba Sendai 980, Japan.
H. TANAKA
National Institute [or Research in Inorganic Materials, 1-1
Namiki, Tsukuba, Ibaraki 305, Japan.
T. UCHIYAMA
Riken Corporation, 810 Kumagaya, Kumagaya, Saitama 360,
Japan.
N.URASATO
Shin-etsu Chemical Co., Ltd, 2-6-1 Otamachi, Chiyoda,
Tokyo 100. Present address: 1589 Nishi-Machi, Yuuki,
Ibaraki, 307, Japan.
K.YAMADA
Tsukuba Research Laboratory, Sumitomo Chemical Company,
Ltd, 6 Kitahara, Tsukuba, Ibaraki 300-32, Japan.
H. YOSHINAGA
Department o[ Materials Science and Technology, Graduate
School o[ Engineering Sciences, Kyushu University,
Kasugakoen, Kasuga, Fukuoka 816, Japan.
1 Crystal Chemistry of
Silicon Carbide
YOSHIZO INOMATA
ABSTRACT
Recent data on crystal chemistry and polytypes on silicon carbide

are reviewed, and brief discussions are given on the origin of SiC
polytypes, i.e. the thermal stability of basic polytypes such as 2H,
3C, 4H, 15R and 6H, the effects of foreign atoms incorporated in
the lattice on the stability of the basic polytypes , and the stability of
long-period polytypes.
1.1 INTRODUcnON
SiC is well known as a substance having numerous polytypes.

Recently, sintered bodies have attracted attention as structural
materials, and active research has been conducted on single
crystals and thin films with the objective of applying them to EL
light-emitting elements and diodes and to environment-resistant
transistor elements. The polytypism of SiC should be closely
examined at least once regardless of the intended application.
With this in mind, crystal chemistry data for SiC are discussed
with comment by the author.
1.2 SYNTHESIS
Most silicon carbide is manufactured by the Acheson process, in

which a mixture of silica rock and coke is electrically heated and
1
Yoshizo lnomata
reacted at high temperatures. In this method, the core tempera-

ture reaches figures approaching 2600°C, causing repeated
recrystallization of the reacted and formed SiC. Coarse a-type
crystals (other polytypes, with the exception of cubic fJ-type
crystals, are customarily referred to as a-type) larger than 10 mm
can be obtained near the core.
Recently, fJ-type fine powders have come to be used in
sintering. This type of powder is synthesized by reacting a
mixture of high-purity silica powder and carbon black in the
temperature range 1500-18000C or by a vapor phase reaction. In
order to achieve a uniform mixture of silicon and carbon, a
method in which the primary raw material is prepared by the
sol-gel method and reacted at high temperature to synthesize
fJ-type fine powders of high purity and quality is currently under
examination.
High-purity single crystals can be produced by subliming and
recrystallizing a pre-synthesized high-purity SiC powder at
temperatures of approximately 25000C or by crystal growth in the
liquid phase using silicon as a solvent. A method of producing
single-crystal films for use in electronics by CVD using a silicon
substrate has also been under examination recently, 1 and the
future development of such methods, together with amorphous
films2 obtained using a similar method, is receiving attention.
As will be described below, numerous polytypes of SiC have
been discovered, but structurally it is extremely difficult to obtain
high-purity single crystals or powders, and the resulting products
tend to be a mixture of a number of polytypes or an imperfect
substance containing stacking faults, etc.
1.3 IMPURITY SOLID SOLUTIONS
Concerning high-purity SiC crystals obtained under relatively

stable growth conditions, detection of non-stoichiometry has not
been reported. Even if the non-stoichiometry existed it would
have a relative value of less than 0·1 % by current analytical
precision.
SiC industrially manufactured by the Acheson process contains
impurities such as Al and Fe introduced via the raw materials
silica and coke. Since nitrogen contained in the synthesis
atmosphere is also incorporated in the crystals, SiC obtained by
Crystal Chemistry of SiC
this method has a purity of approximately 98-99·9%. Compara-

tively high-purity varieties are referred to as green SiC to
distinguish them from black SiC, which contains numerous
impurities. Black SiC generally contains large amounts of AI,
sometimes as much as 1·5 wt%. Green SiC is obtained from
high-temperature portions during synthesis using relatively
high-purity raw materials, with nitrogen forming the main
impurity in solid solution.
The solid solution of impurities in SiC crystals is generally
substitutional, with Band N mainly replacing C and Al mainly
replacing Si. In the solid solution state, B and Al form the
acceptors and N the donor, but the coexistence of both groups
results in a higher solid solution limit than in the case of a single
element. 3 The phenomenon of wide-range solid solution ob-
served in the ternary system SiC-AIN-AI2 C04 is a good example
of this tendency.
The solid solution limit of a single element in SiC crystals is
0·2 wt% for B at 2500°CS and approximately 0·5 wt% for Al at
2000-24OO"C. 6 Crystals which contain approximately 0·1 wt%
nitrogen have been obtained by vapor phase reaction at
1550-1SOOOC. 7 There is no guarantee, however, that these data
are not being influenced by other impurities, and if careful
experiments are carried out concerning purity and equilibrium
the actual values may become lower.
Amorphous SiC is formed as SiC crystals are modified by the
incorporation of hydrogen and halogen elements in its structure.
The growth factors are similar to those for amorphous Si. 8 In this
state, the SiC crystal structure resembles the relationship
between the Si02 crystal phase and silicate glass and is broken
down. Therefore it is inappropriate to refer to it as a solid
solution. This could probably best be discussed in terms of the
association between composition and the conditions for forma-
tion of an amorphous structure. Currently known varieties of
amorphous SiC are non-equilibrium phase.
1.4 POLYTYPES
Numerous polytypes9 have been discovered for SiC. Polytypes

are distinguished from polymorphs in that they are heteroge-
neous structures formed by one-dimensional stacking differences.
3
Yoshizo lnomata
All SiC polytypes are characterized by the fact that any given
atom is always tetrahedrally bonded with heterogeneous atoms.
Nearest-neighbor bonding distance is approximately 1·89 A.
Located on the two edges of the structure group obtained by this
method are cubic P-SiC (zinc blende type) and hexagonal 2H
(wurtzite type).
The difference between these two structures corresponds to the
difference between the cubic and hexagonal close packing of an
isometric sphere. When the stacking order of the closely-packed
plane (the (111) plane in cubic crystals and the (0001) plane in
hexagonal crystals) is shown by the well-known ABC notation,
the stacking of P-SiC in the (111) direction is ... ABCABC ... ,
while that of the wurtzite variety in the direction of the c-axis
is ... ABAB ....
The Zhdanov notation offers an easy-to-understand description
of the polytypes located between these two structures. The
Ramsdell notation is another simple method. The Zhdanov
notation takes the order of the letters in the ABC notation to be
the order of rings and represents the number of unit layers as a
set of forward and backward layers (with the exception of p-type
varieties). In this notation, P-SiC is represented by (00), while the
wurtzite polytype is (11).
In the Ramsdell notation, a number indicating the unit layer
number of the closely packed hexagonal lattice plane, is followed
by a letter indicating the crystal system to which that polytype
belongs. C represents a cubic system, H a hexagonal one, R a
rhombohedral one, and T a trigonal one. According to this
notation, the p-type variety is represented by 3C, while wurtzite
is 2H. This system of notation is often used together with the
Zhdanov notation. For more detailed information on other
systems of notation and the historical background thereof, Ref. 9
should be consulted.
Table 1.1 shows basic SiC polytypes as described by the three
systems of notation introduced here. 15R, for example, is
referred to as (23)3 in the Zhdanov system. The subscript
indicates that the (23) layer is repeated three times in its unit
cell. This corresponds to the special considerations of a
rhombohedral crystal system. It is needless to say that (23)3 is
identical to (32)3.
In the case of long-period polytypes, layers may differ even
though the Ramsdell notation is the same. In such cases, it is
4
Table 1.1
Ramsdell notation ABC notation Zhdanov notation Frequently
2H AB (11)
Observed SiC
3C ABC (00) Polytypes
4H ABCB (22)
15R ABCBACABACBCACB (23)3
6H ABCACB (33)
customary to provide the Zhdanov description together with the

Ramsdell; for example, 20H (42222224), 20H (32322323).10 In
addition to these regular polytypes, SiC crystals often contain
disordered layer regions, with two or more polytypes sharing the
c-axis even within the fine crystal of what appears at first glance
to be a single crystal. This is thought to be due to the extremely
small difference in free energy levels between SiC polytypes.
1.5 STABILITY OF POLYTYPES
1.5.1 Thermal Stability of Short-period Polytypes

The following findings have been made in a SiC binary system of
relatively high purity.
(1) 2H is generally formed at temperatures below 1400°C. At
temperatures of 1500°C and above, 2H obtained by the
CVD method transforms into another polytype along with
the formation of a disordered phase but maintains its
crystal appearance. Accompanying the rise in transforma-
ti6n temperature is a change in the polytypes formed by
transformation, to 3C, 4H and 6H. Virtually no 15R is
formed in this process. 11 This transformation is
irreversible.
(2) In environments with a large degree of supersaturation, 3C
is formed in all temperature regions. For the same reason,
it is often formed in the initial stage of crystal growth. 5 ,12
At temperatures of 16()()OC and above, it changes into
a-type polytypes other than 2H, mainly through
recrystallization.
(3) 15R has a tendency to be formed together with 6H at
5
Yoshizo lnomata
temperatures above 2000°C. Compared with 6H, however,

it is unstable. 13 Formation of this polytype has not been
observed with the transformation of 2H at high tempera-
tures, and it is thought to be one of the typical long-period
polytype to be discussed below.
(4) 4H has a tendency to be formed around 2000°C.
(5) In the range 2200-2600°C, 6H is more stable than 2H, 3C,
4H and 15R.
Thus, one of the reasons why thermal stability relationships
remain unclear is the extremely small differences in free energy
of formation between the various polytypes. Other important
factors include the fact that the transformation is reconstructive,
so that with the exception of 2H, SiC polytypes exhibit virtually
no structural changes due to heating and cooling; and the fact
that stability relationships are very susceptible to influence from
the solid solution of trace impurities. 14
I.S.2 Formation and Stability of Long-period Polytypes

The formation of long-period polytypes is adequately explained
by the growth theory of Frank, in which screw dislocations act as
a medium. 15 According to this theory, a screw dislocation
orthogonal to the (0001) plane of a specific polytype other than
3C or a polytype having stacking faults, and then the layers of
the steps formed on the (0001) surface, act in succession as
memories of the layers of growth. If the host crystal of the
long-period polytype is assumed to be a disordered phase,
growth of a polytype having arbitrary layers is possible. Of the
layers in the long-period polytypes reported at present, however,
many9 are (22), (23) and (33) base/6 reflecting the stability of
short-period polytypes. Up to now, only two long-period
polytypes containing a 1 in the Zhdanov notation (such as 2H)
have been observed. 17.18 This is related to the fact that 2H is
unstable at high temperatures.
The thermal stability of long-period polytypes having layers
resembling specific short-period polytypes is therefore based on
the stability of the short-period polytype.19 Therefore,
69R{(33)332h, for example, has layers approaching those of
6H(33) and thermal stability similar to that of 6H.
6
Formation of long-period polytypes using screw dislocations as

a medium can also be observed in ZnS. In the case of ZnS, since
the heating- and cooling-induced transformation of low-
temperature 3C and high-temperature 2H around 1020"C is
reversible, the formation process of crystal polytypes which have
passed through this temperature is rather complex. The following
process is suggested: the layer unit formed at the growth
temperature becomes turbulent upon passing through the
transformation temperature, this turbulence affects the entire
crystal via the screw dislocation, and the polytype is endowed
with long periodicity. 20
With the exception of 2H, layers once formed in SiC are
extremely stable, and even in long-period polytypes structures
formed at high temperatures during crystal growth can be
considered to be frozen.
1.5.3 Impurity So6d Solutions and Polytypes

From the fact that a plurality of polytypes form in a synthesis
space thought by ordinary standards to be uniform, it is thought
that the difference in the free energy of formation for SiC
polytypes is extremely small. The gap between 3C and 6H
around 2500°C has been calculated at less than 100 cal/mol. 12
This gap is due to the fact that the total of the covalent cohesive
energy, the ionic cohesive energy (Maderlung energy), and the
lattice vibration energy differs for each polytype.
An overall view of compounds having zinc blende or wurtzite
structures shows that the larger the ionicity, the larger the stable
region of the wurtzite structure (2H) , while the smaller the
contribution of ionic cohesive energy, the larger the stable region
of the zinc blende structure (3C). This is probably related to the
fact that, given the same bond ionicity, bond length and bond
angle, the cohesion-induced energy gain becomes greater for 2H.
The phenomenon of SiC polytypes is manifested as a
competition between the very small ionicity possessed by this
compound and its vibration energy. Solid solutions of elements
which would increase the ionic cohesive energy will therefore
increase the ratio of hexagonal layers. (In the ABC notation, the
ratio of layer positions whose ring order is reversed. This ratio,
also referred to as hexagonality, is 100% for 2H, 50% for 4H,
7
Yoshizo lnomata
33% for 6H and 0% for 3C.) The well-known fact that solid
solutions of AI will stabilize 4H6,21-23 and the fact that a 2H-type
solid solution forms in the ternary system SiC-AlN-Al2CO are
also explained in this way. The amount of AI solution needed to
stabilize 4H at 2200"C is thought to be at least 0·2 wt%.6
Nitrogen is another element which easily forms a solid solution
in SiC under ordinary synthesis conditions. It has also been
reported that the solution of nitrogen stabilizes 3C,24 but some
believe that this is simply inhibition of the a-transformation of 3C
formed in the initial stages of synthesis,25,26 and the details
remain unclear. The solubility limit of boron in SiC is
0·1-0·15 wt% in the range 2450-2500°C,27 but numerous unclear
points remain in the relation between solid solutions and
polytype stability.
1.6 CRYSTALLOGRAPHIC PROPERTIES
SiC has a high covalency, with the ionicity of SiC bonds

estimated by Pauling to be approximately 12%. SiC is a
semiconductor, and it has superior hardness. Table 1.2 shows
data concerning the physical properties of high-purity SiC.
The lattice constant varies only slightly between polytypes. As
the ratio of hexagonal layers increases there is a general tendency
for the lattice spacing along the c-axis to increase and for that
along a- and b-axes to contract. Precision structural analysis of 6H
single crystals31 has shown that deviations in the layer spacing in
the direction of the c-axis occur primarily in the hexagonal layer
positions. This phenomenon is thought to relate to the small
ionicity described above.
Since SiC has a large Young's modulus, a simple structure, and
consists of light elements, high-purity crystals have a large
thermal conductivity.32 The bandgap ranges from 2·2 eV (3C) to
3·3 eV (2H). As a result, high-purity 3C forms yellow transparent
crystals, with the gap located near 3 eV. 2H, 4H, 15R, 6H, etc.,
form colorless transparent crystals. When N or AI form solid
solutions, the crystals are colored green or blue due to the
impurity level. Electron mobility is highest for 3C.
The Debye temperature for 3C as calculated from thermal
expansion coefficient is 1430°C,33 It has no melting point, and at
8
Table 1.2
1. Formula weight 40·1 Physical
2. Density g/cm3 3·21 Properties of
3. Colour 3C: Yellow, others colourless High-purity SiC
4. Decomposition temperature 2830±4QOC
5. Lattice constant (RT) A 3C aD: 4·3596
a type aD: 3·076 (2H)-3·OS1 (6H)
co: {2.520 (6H)-
2·524 (2H)} x n°
6. Knoop hardness kg/cm2 3C 1. (111): 2815 28
7. Compressibility kg/cm2 1.229-2.1 x 10- 7
8. Young's modulus 3·9-4·6 x 1(f
9. Thermal expansion 4·4-4·9 x 10- 6 (mean for 25-
coefficient °C- 1 2000"Ct
10. Specific heat cal/g °C OOC 0·17
200°C 0·22
l000"C 0·28
1400-2000"C 0·30
11. Thermal conductivity OOC 1·2
cal/cm soC 7000C 0·15
12. Bandgap eV 3C: 2·2
6H: 2·86
2H: 3·30
13. Debye temperature K 1430
14. Electron mobility cm2 IV s 3C:l000
15R:500
6H:200-300
° Number of unit layers.
b With a-type varieties, there is significant expansion in the direction of
the a-axis. In the case of 6H, expansion in the a-axis direction is
approximately 10% greater than that in the c-axis direction. 3D
2830°C and under pressurized atmosphere it decomposes into a

silicon melt and graphite. At this temperature, the solubility of
carbon in the silicon melt in eqUilibrium with the SiC is
approximately 19 at. %, while the solubility of carbon in the
silicon melt near the melting point of silicon is thought to be
approximately 5 X 10-3 at. %.34
The composition of vapor in. eqUilibrium with SiC at high
temperatures is rich in silicon, the main species of vapor being Si,
Si2C, Si2 and Si~.35 Consequently, when heated to high
temperatures in an inert open atmosphere, the carbon is
transformed into evaporation residue.
9
Yoshizo Inomata
REFERENCES
1. Suzuki, A., Furukawa, K., Higashigaki, Y., Harada, S., Nakajima,

S. & Inoguchi, T., Epitaxial growth of P-SiC single crystals by
successive two-step CVD. J. Cryst. Growth, 70 (1984),287-90.
2. Kuruangam, D., Endo, T., Guang-Pu, W., Okamoto, H. &
Hamakawa, Y., Visible-light injection-electroluminescent cr-SiC/p-
i-n diode. J. Appl. Phys., Z4 (1985), L806-L808.
3. Hong, J. D., Hon, M. H. & Davis, R. F., Self-ditIusion in alpha and
beta silicon carbide. Ceramurgia International, 5 (1979), 155-60.
4. Cutler, I. B., Miller, P. D., Rafaniello, M., Park, H. K. & Jack, K.
H., New materials in the Si-C-Al-O-N systems. Nature, 275
(1978), 434-35.
5. Shatler, PT. B., The SiC phase in the system SiC-B4C-C. Mater.
Res. Bull., 4 (1969), S213-19.
6. Mitomo, M., Inomata, Y. & Tanaka, H., The influence of
aluminium on the stability of 4H- and 6H-silicon carbide at 2200"C.
Mater. Res. Bull., 6 (1971), 759-64.
7. Knippenberg, W. F., Growth phenomena in silicon carbide. Philips
Res. Rept, 18 (1963), 161-274.
8. Hamakawa, Y., Electronic properties of amorphous semiconduc-
tors. Denshi Twin Gakkai-shi, 68 (1985), 109-19.
9. Verma, A. R. & Krishna, P., Polymorphism and Polytypism in
Crystals. John Wiley, New York, 1966.
10. Nakashima, S., Nakamura, Y. & Inoue, Z., Structural identification
of SiC polytype by Raman scattering. J. Phys. Soc. Japan, 56
(1987), 359-64.
11. Tagai, T., Sueno, S. & Sadanaga, R., Thermal transformation in
SiC crystals. Mineral. J., 6 (1971), 240-8.
12. Inomata, Y. & Matsumoto, S., On the formation of P-SiC in the
initial growth stage. J. Ceram. Soc. Japan, '79 (1971), 30-6.
13. Inomata, Y., Inoue, Z. & Kijima, K., On the formation of 15R-type
in the p-cr transformation of SiC. J. Ceram. Soc. Japan, 77 (1969),
313-18.
14. Sadanaga, R., Review for the Research on SiC. NIRIM, Japan,
1967, pp. 14-28.
15. Frank, F. C., The growth of carborundum; dislocations and
polytypism. Phil. Mag., 42 (1951), 1014-21.
16. Mitchell, R. S., A correlation between theoretical screw dislocations
and the known polytypes of silicon carbide. Z. Krist., 109 (1957),
1-28.
17. Jepps, N. W. & Page, T. F., 9R-HREM observations on new silicon
carbide polytype. J. Am. Ceram. Soc., 63 (1980),102-3.
18. Miyano, S., Sueno, S., Ohmasa, M. & Fujii, T., New SiC polytype
45Rt,. Acta Cryst., A38 (1982), 4n-82.
19. Inoue, Z. & Inomata, Y., Thermal stability of the long-period
polytype of SiC 51R, at 2500"C. J. Cryst. Growth, SO (1980),
n9-82.
10
20. Mardix, S., Kalman, Z. H. & Steinberger, I. T., Periodic slip

process and the formation of polytypes in zinc sulphide. Acta Cryst.,
A24 (1968), 464-9.
21. Lundquvist, D., On the crystal structure of silicon carbide and its
content of impurities. Acta Chem. Scand., 2 (1948), 177-91.
22. Hayashi, A., The effect of impurity and temperature on the
polytypism of silicon carbide. J. Mineral Soc. Japan, 4 (1960),
363-71.
23. Adachi, H., Silicon carbide for ceramics. Bull. Ceram. Soc. Japan, 2
(1967), 166-72.
24. Kieffer, A. R, Ettmayer, P., Gugel, E. & Schmidt, A., Phase
stability of silicon carbide in the ternary system Si-C-N. Mater.
Res. Bull., 4 (1969), S153-S165.
25. Kawamura, T., Silicon carbide crystals grown in nitrogen atmos-
phere. Mineral J., 4 (1965), 333-55.
26. Addamiano, A. & Staikoff, L. S., Stabilization of cubic silicon
carbide. J. Phys. Chem. Solids, 26 (1965), 669-70.
27. Shaffer, P. T. B., The SiC phase in the system SiC-B4 C-C. Mater.
Res. Bull., 4 (1969), S213-S219.
28. Neuberger, M., Physical and electrical property of SiC. Mater. Res.
Bull., 4 (1969), S365-370.
29. Saito, S., Review for the Research on SiC. NIRIM, Japan, 1967, pp.
68-79.
30. Inoue, Z. & Kurachi, Y., Structural change of SiC at high
temperature-an application of high temperature X-ray
diffractometer to the observation of transformation and thermal
expansion. Proceedings of lst International Symposium on Ceramic
Components for Engine, ed. S. Somiya, E. Kanai & K. Ando. D.
Reidel, 1984, pp. 519-28.
31. Gomes De Mesquita, A. H., Refinement of the crystal structure of
SiC type 6H. Acta Cryst., 23 (1967), 610-17.
32. Slack, G. A., Non metallic crystals with high thermal conductivity,
J. Phys. Chem. Solids, 34 (1973), 321-35.
33. Taylor, A. & Jones, R M., The crystal structure and thermal
expansion of cubic and hexagonal silicon carbide. Silicon Carbide,
Proc. Cont Boston, 1959. Pergamon Press, Oxford, 1960, pp.
147-54.
34. Scace, R. I. & Slack, G. A., The Si-C and Ge-C phase diagonals.
Silicon Carbide, Proc. Cont Boston, 1959. Pergamon Press,
Oxford, 1960, pp. 24-30.
35. Drowart, J. & De Maria, G., Thermodynamic study of the binary
system carbon-silicon using mass spectrometer. Silicon Carbide,
Proc. Cont Boston, 1959. Pergamon Press, Oxford, 1960, pp.
16-23.
11
2 Properties and
Applications of Silicon
Carbide Ceramics
KOICHI YAMADA &
MASAHIDE MOHRI
ABSTRACT
Silicon carbide is a promzslng candidate for high-temperature

structural materials and wear-resistant materials. We have
developed pressureless-sintered silicon carbide ceramics. The
properties, applications and related technologies of silicon carbide
ceramics are described.
2.1 INTRODUCTION
In the past, the list of ceramics used as industrial materials

consisted of alumina and other oxides. In recent years, however,
there have been strong demands for the use of ceramics as
structural materials in place of metals and ultrahard alloys and
for use .in harsh environments (high temperature, heavy loads,
high corrosion, etc.) which do not allow the use of such metals
and alloys or of oxide ceramics. Consequently, nitrides, carbides
and other covalent substances are receiving attention because of
their resistance to heat and numerous other special
characteristics.
Together with silicon nitride (Si 3N4 ), the development of
silicon carbide (SiC) ceramics during the last 10 years has
proceeded at a rapid pace. Its characteristics include hardness,
heat resistance (decomposition temperature: approximately
2400°C) and corrosion resistance, which together with its
13
Koichi Yamada, Masahide Mohri
excellent resistance to oxidation make it promising as the main

material for gas turbine engine components of the future.
SiC is said to have been accidentally discovered in 1891 by E.
G. Acheson, an assistant to T. Edison, during an experiment on
the synthesis of diamonds. Acheson thought the substance was a
compound of the carbon used in the experiment and the Ah03
(corundum) contained in the clay, leading him to name the new
substance carborundum. 1 SiC rarely occurs naturally, and it is
synthesized industrially from silica and coke. This method of
mass production was also developed by Acheson. Unlike Si3N4 ,
SiC has been mass-produced on a commercial scale for many
years, and it has seen a wide range of applications, including
abrasives, heating elements and varistors.
As will be described below, however, the low sinterability of
SiC makes it extremely difficult to obtain dense sintered
compacts, and until now it was virtually never used as a
structural material. The wide application of SiC as a structural
material became possible only after S. Prochazka of the US firm
General Electric developed a technique for pressureless
sintering.
Our company has also developed a pressureless sintering
technology for SiC,z and development of structural applications
are being enthusiastically promoted. This chapter will discuss the
pressureless sintering of SiC and manufacturing technologies for
SiC compacts and will introduce the properties of this company's
SiC together with its structural applications.
2.2 PROPERTIES OF SILICON CARBIDE1 ,3
2.2.1 Crystal Structure

SiC varieties include P-SiC, which has a zinc blende structure
which is the substitutional structure of diamond, and a-SiC,
which is represented as a combination of zinc blende structure
and its similar structure of wurtzite. a-SiC exhibits polytypism, in
which the stacking sequence changes but the layer unit remains
the same. At present, approximately 50 different polytypes are
known, and the crystal lattice constant of a-SiC is represented as
a = b = 3·078 A and c = n X 2·518 A (n > 2). In the a-SiC
14
Properties and Applications of SiC Ceramics
sintered bodies produced using the pressureless sintering method

developed by Sumitomo Chemical, hexagonal crystal systems
represented by n = 6 are frequently observed (there are three
methods of labeling this variety: SiC II, 6H and ABCACB). The
relationship between Si atoms and C atoms in SiC is such that
each Si atom is tetrahedrally bonded to four carbon atoms, and
each carbon atom is tetrahedrally bonded to four silicon atoms.
The interatomic bonds are characterized by a strong covalency,
with Pauling estimating the ionicity of the Si-C bonds at a mere
12%.
Because SiC is composed of light elements (Si, C) and has a
strong covalency, it is lightweight, has a low thermal expansion
coefficient, high thermal conductivity, high strength and high
hardness, and it is a promising fine ceramic for the replacement
of conventional metals and ionic-bonded oxide ceramics such as
alumina.
2.2.2 Impurities
Fine ceramics raw materials manufactured on an industrial scale
generally have a purity of about 98-99·5%. The materials
contain impurities such as AI, Fe, 0 and free carbon and may be
colored green or black.
2.2.3 Hardness
A new Moh's hardness of 13 is exhibited by SiC, making it the
hardest available material after diamond (15) and boron carbide
(14).
2.2.4 Heat Resistance

SiC has relatively high thermal stability, with decomposition
beginning at temperatures of 2000°C or more in air (dissociation
temperature: approx. 24OO0 C). In nitrogen, the reaction SiC + N2
proceeds at temperatures of 1450°C and higher, resulting in a
transformation to Si3 N4 •
15
2.2.5 Thermal Conductivity

SiC has a high elastic modulus, its constituent atoms are
relatively light, and its atomic weight differential is small. As a
result, the lattice vibrations easily become harmonic, giving the
material a high thermal conductivity for a ceramic.
2.2.6 Thermal Expansion Coemdent

In solids, the distance between atoms is maintained in a state of
equilibrium by the balance of potential energy between inter-
atomic tensile force and repulsive force. Because of its high
interatomic bond strength, SiC has a small thermal expansion
coefficient (4·3 X 10-6 rC).
2.2.7 Conductivity
High-purity SiC falls into the category of electrical insulators, but
ordinary varieties exhibit the electrical properties of a semicon-
ductor due to the impurities they contain. These properties are
governed by the amount and type of impurity, with Al resulting
in a p-type semiconductor and N in a n-type semiconductor.
2.2.8 Chemical Stability

SiC is an extremely stable substance, showing no corrosion even
when boiled in HCI, H 2S04 , HF, or HF + HN03. Nor is it
corroded by a concentrated liquid solution of caustic soda. It is
corroded, however, by a Na20 or by Na2C03 + KN0 3 melts. It
also reacts with chlorine at temperatures of 900°C and above and
with sulfur vapor at temperatures of l()()ooC and above. In air,
oxidation begins at temperatures of approximately 850"C,
resulting in formation of a Si02 film. The rate of oxidation is
heavily influenced by the properties of the Si02 film, but since
the Si02 film is denser than in the case of Si3N4 , oxidation
resistance is far greater.
16
2.3 SYNTHESIS AND SINTERING OF SILICON

CARBIDE
2.3.1 Synthesis of SiC
2.3.1.1 a-SiC
SiC is most frequently manufactured on an industrial scale using
the Acheson method described above. In this technique, two
solid electrodes are connected with graphite powder, a mixture
of silica and coke is packed in the surrounding area, and the
whole is electrically heated to produce SiC chiefly by the reaction
of eqn (3.1).
Si02 + 3C- SiC + 2CO (1)
The thus-prepared SiC crystal blocks are then ground, refined
and classified to produce SiC powders suitable for a variety of
applications. SiC manufactured by this method generally has a
coarse grain, with a mean particle size of 5 JUIl (JIS #3(00) at
best. In order to produce powders appropriate for sintering,
therefore, a refining process capable of producing ultrafine-grain
powders is needed.
2.3.1.2 fJ-SiC
This variety of SiC is produced chiefly as a raw material powder
for sintering, and synthesis methods using solid-phase and
vapor-phase reactions have been developed. P-SiC is also
produced by the Acheson method at low temperatures. Conse-
quently, by keeping the reaction temperature within the range
1500-1800°C it is possible to manufacture P-SiC using the same
solid-phase reaction as with the Acheson method. 4 This method
is characterized by the relatively fine grain of the resulting p-SiC.
Vapor-phase methods use the reaction of SiHl or SiCl4 with
hydrocarbons such as CH4 and C3Hs or the thermal decomposi-
tion of CH3SiCh, (CH3)4Si,6 or polycarbosilane7 to produce
p-SiC. Ultrafine-grain powders of high purity and a particle size
of less than 0·1 JUIl can be obtained.
Other solid-phase methods include the direct reaction of
silicon and carbonS and the gas evaporation method,9 in which
the raw material surface is heated and melted using an arc
17
Koichi yturlllda, Mosahick Mohri
discharge in a mixed gas (consisting of an inert gas and H2 or N2)

to form ultrafine SiC particles. Various synthesis techniques are
being investigated and developed.
2.3.2 Sintering of SiC
2.3.2.1 Hot-pressing
As SiC is fundamentally a low-sinterable material, virtually no
sintering is observed when a pure SiC powder compact is heated.
This led to the development of the hot-pressing technique, by
which the compact is sintered under high pressures.
Alliegro et al. 10 reported that AI and Fe are effective as
sintering aids in the hot-pressing of SiC, with high densification
(approximately 98% of theoretical) of both a-SiC and fJ-SiC
being made possible by the addition of approximately 1% AI.
Nadeaul l investigated ultra-high-pressure hot-pressing and
reported that high densification (approximately 98% of theoreti-
cal) is possible for both a-SiC and fJ-SiC. under a pressure of
30 kbar at 1500"C. He concluded that the densification mechan-
ism responsible was not diffusion but rather particle crushing and
slip.
Prochazka12 discovered that boron was an effective sintering
aid, and by adding 1 wt% boron to a submicron SiC powder and
sintering under 10000 psi at 1950°C was able to obtain a SiC
compact of 99% theoretical density. He concluded that solid-
phase diffusion caused the densification.
2.3.2.2 Pressureless Sintering
Based on a series of studies on hot-pressing, Prochazka &
Smith13 attempted the pressureless sintering of SiC and dis-
covered that significant densification of a submicron fJ-SiC
powder was possible with the simultaneous addition of boron and
carbon. Numerous studies were then conducted on the pressure-
less sintering of SiC. Among the techniques investigated were the
sintering of a-SIC powder by the addition of boron and carbon, 14
AI and carbon1s and Ah03.16
Research is also being conducted on the mechanisms of
pressureless sintering, but this has yet to be fully understood.
18
Following is a brief discussion of currently proposed sintering

mechanisms.
Prochazka17 explained the role of boron and carbon in
sintering as follows. In order for solid-phase sintering to proceed,
it is imperative from the condition of surface tension balance
shown in t;9n (3.2) that the equilibrium dihedral be ~60°
(Ygb/Ysv < V3).
Ygb = 2. Ysv. cos(0/2) (2)
Here, Ygb is grain boundary energy and Ysv is surface energy.
From the empirical evidence that SiC alone will not sinter,
however, it is thought that Ygb/Ysv is high for SiC and that there
is a thermodynamic limit with respect to the sintering of SiC.
From this assumption, the segregation of boron on the grain
boundaries reduces Ygb. On the other hand, the SiC powder
surface is oxidized, and Ysv is reduced. Carbon, by removing this
surface oxide film, increases Ysv. As a result, Ygb/Ysv is reduced
and densification is promoted.
With respect to the above mechanism, it was later proven by
measurement of the equilibrium dihedral that () > 90-100°.
Greskovich & Rosolowskj1s then proposed the following mecha-
nism based on the assumption that there is no thermodynamic
limit to the sintering of SiC.
Figure 2.1 shows the inhibitive effect of boron with respect to
the reduction in SiC powder specific area during heating. When
Fig. 2.1.
Influence of firing
temperature on
~
121-__----------------~ specific surface
.5 10 area of P-SiC
compact. IS
f
III 8
~
.5 6
¥ B C (wt "I.)
.~ 4 • 0·6 0·8
VI
o 0·8
2
o
Temperature (0(;)
19
carbon alone is added the inhibitive effect is limited, and the rate
of the drop in specific surface area corresponds with the surface
diffusion-governed grain growth model. At temperatures of up to
1500°C, at which sintering is thought to begin, boron inhibits
surface diffusion-induced grain growth, thereby facilitating sin-
tering at high temperatures. Carbon, on the other hand, removes
the oxide film from the SiC powder surface, facilitating the
formation of point defects and thereby assisting diffusion. It was
therefore suggested that sintering is due to either volume or grain
boundary diffusion.
Suzuki & Hase 19 reported that, like boron, carbon also inhibits
surface diffusion. By observation of a sample heated to 1900°C
they confirmed the existence of a grain boundary phase
consisting of boron-carbon (B-C) system compounds. As a
result, it was proposed that sintering proceeds by diffusion via
this grain boundary phase at temperatures of up to 1950°C, while
at higher temperatures the driving force behind sintering is the
boron-induced promotion of diffusion.
As a similar mechanism, Lange & Gupta20 have proposed that
Si-B-C system compounds promote sintering as a liquid phase.
In this way, a variety of proposals have been made concerning
SiC sintering mechanisms, but a definitive conclusion has yet to
be reached. In the case of oxides such as Ah03 and Zr02, the
focus has been placed on identification of 'sintering dynamics',
i.e. diffusion mechanisms. Agreement has yet to be reached,
however, on whether or not there is relaxation of surface energy
by the formation of 'sintering driving force', i.e. grain boundary
energy. For example, Inomata et al. 21 assumed that SiC is 100%
covalent and, based on measurements of orientation relation-
ships in a-SiC bicrystals and model calculations of lattice point
correspondence, estimated the grain boundary energy of SiC. It
was concluded that Ygb/Ysv> 1·88 for SiC. This result differs from
the assumptions of Greskovich and Suzuki et al. and suggests that
there is a need when discussing SiC sintering to consider not only
sintering dynamics but sintering driving force as well. Clarifica-
tion of the effectiveness of boron and carbon as sintering aids is
awaited from these two standpoints.
Figure 2.2 shows a comparison of diffusion coefficients22 for
SiC and Ah03.23 Since Si has a lower self-diffusion coefficient
than C, it is thought that Si diffusion determines the rate of
volume diffusion in SiC. In the temperature range 2000-2100°C,
T (K) Fig.2.2. Self-

~25002400 ditIusion
10" coefficients of Si
Cinpure
~
0
x Cin n·type and C in a-SiC
C Si in pure single crystals. 22,23
" 11 0 Si in n·type
x,-, ~13+
'"E x'x ~
o'-~
~ 0 '"
o 10-12
\.'\:
at which SiC sintering proceeds, however, this diffusion

coefficient is 10- 12_10- 14 • This is not very different from the
diffusion coefficient of oxygen, which is thought to be the seed
determining the rate of AI20 3 diffusion, at temperatures of
1400-1600°C. In the case of A12 0 3, grain boundary diffusion and
MgO-induced promotion of sintering have been reported, and
for SiC as well the promotion of diffusion by the solid solution of
boron has been suggested. It has been reported, for example,
that boron promotes crystal grain growth in SiC sintered
bodies. 24 Figure 2.3 is an SEM photomicrograph of a SiC
sintered body containing boron. As can be seen in the
photograph, extremely large crystal grain growth is occurring. As
a result, boron is thought to have some kind of influence over the
solid-state diffusion of SiC.
On the other hand, it cannot be denied that carbon, in
addition to removing the oxide film from the SiC powder surface,
also acts to promote diffusion.
Concerning sintering using Al and carbon or Ah03 as sintering
aids, proposed mechanisms include the promotion of diffusion by
an Al solid solution and liquid-phase sintering. 25
21
Fig. 2.3.
Exaggerated grain
growth in a SiC
sintered body.
2.4 MANUFACTURE OF SILICON CARBIDE

COMPACTS
In the pressureless sintering technique, a submicron SiC powder

is mixed with a sintering aid and forming aid. After forming
using one of a variety of methods, the compact is sintered in an
inert gas atmosphere at a temperature of 2000-23000C to
produce a SiC compact. This method is characterized by its
ability to mass-produce at low cost compacts with complicated
shapes, this is because a variety of forming techniques can be
used. In addition, a portion of the accumulated manufacturing
technologies for Ah03, Zr02 and other ceramics can be applied.
The manufacturing process is illustrated in Fig. 2.4. Although
Fig. 2.4. SiC cer-

amics manufac-
turing process.
the basic process resembles the conventional manufacturing

process described above, the sintering step is very different.
Specifically, the atmosphere consists of an oxygen-free inert gas,
and the sintering temperature exceeds 2000°C. It was described
above that SiC is fundamentally a low-sinterable material.
Control over atmosphere and temperature is therefore extremely
important for the manufacture of SiC compacts with high density
and superior properties. Each manufacturing step will be briefly
described below.
2.4.1 Raw Material Preparation

In this step, the submicron SiC powder is blended with a
sintering aid and forming aid. It differs depending upon the
forming method to be used. For the so-called 'dry' forming
techniques, including isostatic pressing and dry pressing, after
wet-mixing of the aids the powder is formed into 50-100 J.UIl
pellets to facilitate molding. For 'wet' techniques such as slip
casting, extrusion and injection molding, uniform dispersion of
the sintering aid, selection of the molding aid, and uniform

dispersion technologies are important. These, together with the
aid mixture, are adjusted to produce a plasticity suitable for the
molding method used.
2.4.2 Forming
2.4.2.1 Isostatic pressing

With water or oil as a pressure medium, isostatic pressing is used
to form SiC powder contained in a rubber mold. Generally this
technique is used when there are few compacts to be molded; it
is possible to form large powder compacts to a relatively uniform
density. After forming, diamond tools are used to machine the
compact into the necessary shape.
2.4.2.2 Dry Pressing

Mechanical or hydraulic pressure is used to form SiC powder
contained in a metal mold. This method is well-suited to mass
production, and it also allows the forming of relatively compli-
cated shapes. Tool steel and ultrahard alloys are used for the
metal mold. In order to achieve a uniform density, it is important
to take into consideration the flow-ability and mold release
properties of the pelletized raw material as well as the design of
the metal mold.
2.4.2.3 Slip Casting

SiC powder is ordinarily dispersed in water to form a slurry. This
slurry is then poured into a gypsum or other porous mold, and
the water is absorbed by the mold. This is one of the traditional
techniques of the ceramics industry, and it allows forming of
turbine rotors and other compacts with complicated shapes.
2.4.2.4 Extrusion
Water and an organic binder much as methylcellulose are used to
confer plasticity on the SiC powder, the mixture is fluidized using
a screw or a ram, and the compact is molded using a metal mold.
Although this method allows the formation of compacts with the
24
same cross-sectional shape to desired lengths, green density is

relatively low and large pores are easily left behind.
2.4.2.5 Injection Molding

An organic binder such as polystyrene or wax is added to the SiC
powder, the mixture is heated and kneaded, and the mixture is
injected into a metal mold. Well-suited to mass production, this
method allows molding of compacts with complicated shapes.
Major problems remain, however, including abrasion of devices
by the highly abrasive SiC powder and introduction of the
material comprising the device into the compact itself. In
addition, the need to use large quantities of organic binder
makes it especially important to prevent cracks, which easily
occur during the binder removal step before sintering.
2.4.3 SioterUmg
For SiC sintering it is possible to use a resistance heating furnace
using a graphite or high-melting-point metal heating element.
For industrial purposes, however, resistance heating furnaces
consisting of graphite heating elements and refractories, which
possess superior durability at high temperatures, are utilized.
Because the sintering temperature exceeds 2000°C, an optical
pyrometer is used to measure the temperature. In order to
manufacture SiC compacts having both high density and superior
properties, control of the sintering temperature is important.
There are some problems with the measuring precision of the
optical pyrometer, but a temperature detection sensor capable of
replacing the optical pyrometer has yet to be developed.
Gases which can be used for the sintering atmosphere include
He, Ar, N2 and other inert gases. However, because of the high
cost of He and the need to further increase sintering tempera-
tures when N2 is used, Ar is used for industrial applications.
When a-SiC is used as a raw material, a sintering temperature
of 2000-2300°C is generally used. In the case of {:J-SiC, however,
because of the phase transformation to a-SiC which occurs at
temperatures exceeding -2100°C, thereby resulting in abnormal
grain growth, it is necessary to perform sintering at temperatures
of less than 2100°C.
2.4.4 Finishing
When high dimensional precIsion and surface smoothness are

required, finishing is performed using a variety of mechanical
processing devices. Ceramics, however, suffer from poor work-
ability, and it has been reported26 that the grinding ratio (volume
removed by processing/volume consumed by grindstone), which
serves as an index of workability, for SiC is approximately ~ of
the figure for A120 3 • Consequently, processing costs are
prohibitive, and it is important to limit finishing to a minimum.
2.4.5 Inspection
Ordinarily, inspections are performed to determine dimensional
precision, sintered density, and the presence or absence of
surface and internal cracks. When necessary, strength, hardness,
structure and composition may also be determined.
The properties of a ceramic compact are determined first by
the selection of a raw material and sintering and forming aids and
the adjustment technologies therefore; second, by uniform
forming technologies; and third, by sintering technologies. By
developing technologies that are optimal to the manufacture of
SiC compacts, Sumitomo Chemical can provide SiC compacts
characterized by superior properties and stable quality, as will be
described in the following section.
2.5 PROPERTIES OF SILICON CARBIDE

COMPACTS
SiC is capable of providing the various properties required of

structural materials, namely, resistance to abrasion, corrosion
and heat. Bending strength, tensile strength and fracture
toughness (KId, while higher than the values for Al20 3 , remain
lower than those for Zr02(PSZ) and Si~4'
This chapter, in addition to describing the properties of
Sumitomo Chemical's SiC compacts, will touch on recent
development trends.
2.5.1 Mechanical Properties
2.5.1.1 Elastic Properties

Table 2.1 shows elastic properties as measured using the pulse
echo technique. Compared with Al20 3 and Si3N4, SiC possesses
high elasticity and has strong resistance to deformation.
2.5.1.2 Hardness
Table 2.1 shows micro Vickers' hardness. SiC is surpassed in
hardness only by diamond, cubic-BN and B4C, making it
well-suited to applications such as mechanical seals and bearings
which require resistance to abrasion.
2.5.1.3 Strength
Table 2.1 shows compressive strength and three-point flexural
strength as measured according to JIS-R 1601. SiC possesses
relatively high strength for a ceramic, but the value is low when
compared with Si3N4 or PSZ. This is due to a low effective
fracture energy Ye in fracture stress Or of eqn (3), which is
derived from Griffith's fracture theory.27
or=V2. E. Ye/Jr. C (3)
Here, E is elastic modulus, Ye is the effective fracture energy and
C is crack radius.
A flexural strength approaching 100 kg/mm2 has been reported
for a SiC hot-pressed compact,28 but this is thought to be due to a
small fracture origin (crack diameter). Figure 2.5 shows a
fracture origin in a SiC compact. This is a pore of approximately
30 f.l.m, and ordinarily pores and inclusions of less than 50 f.l.m will
become fracture origins. In the future, it is expected that higher
Table 2.1
Density 3'14g/cm2 Physical and
Hardness 2400kg/mm2 Mechanical
Elastic modulus of Young's 43 ()()() kg/mm2
Properties of SiC
Elastic modulus of shear 18 ()()() kg/mm2 Compacts
Poisson's ratio 0·16
Flexural strength 6Okg/mm2
Compressive strength 340kg/mm2
Fracture toughness 4·6MN/m312
27
Koich; Yamada, Masah;de Mohr;
Fig. 2.S. Fracture

origin in a SiC
sintered body.
500J,lm
strength will be achieved by reducing fracture origins through

improved manufacturing processes and increased fracture tough-
ness, which will be discussed below.
2.5.1.4 Fracture Toughness
Table 2.1 shows K 1c as measured by an indentation microfracture
method (1M). As shown in eqn (3), strength is dependent on
crack dimension and shape and does not represent the properties
of the material itself. According to fracture dynamics, fracture in
brittle materials occurs as the result of stress concentration in the
area around the crack tip.29 The degree of this stress concentra-
tion is defined as stress expansion coefficient K 1c • K 1c is shown in
eqn (4) as a critical stress expansion coefficient for the time when
the stress concentration at the crack tip begins to cause a
fracture.
(4)
28
K 1C is also dependent on effective fracture energy Ye and is not

unique to the material, but it offers a clearer representation of
the difference in strength between materials. The values of K 1C
for ShN4 and PSZ are 5-6MN/m 312 and 7-9MN/m312 , respec-
tively, both higher than the figure for SiC. The low toughness
value of SiC is a major disadvantage. Work is being conducted to
develop a variety of SiC having higher toughness, and methods
such as increasing the aspect ratio of the sintered crystallite size25
and introducing stacking faults into the crystallites30 have been
reported. At present, however, it is difficult to improve
toughness without sacrificing high-temperature properties; when
Al20 3 is added in order to increase the aspect ratio of the
sintered crystallite size, for example, high-temperature strength
drops. The development of a form of SiC offering both toughness
and resistance to heat is one of the main topics of investigation
for the future.
2.S.1.S High-temperature Strength

Figure 2.6 provides a comparison of high-temperature three-
point bending strength for SiC and ShN4 • At temperatures
exceeding 1200°C, SiC boasts higher strength than Si3 N4 • In fact,
SiC possesses better high-temperature strength than any other
material, including metals. There is a tendency for the strength
120 Fig. 2.6. High-

p-------D temperature
N'
strength of SiC.
\
E 100
E
....
Cl
~ 80
.c
o
b __________________ 6_,__ O_
C,
c: 60 SiC
~
en
40
~:::l
X
Q)
u:: 20
Atm. Ar
500 1000 1500 2000
Temperature (oC)
of SiC to increase at high temperatures, and stress relaxation at

the crack tip has been reported as a possible responsible
mechanism.
SiC possesses superior heat resistance, and it has great promise
as a high-temperature material for use in gas turbines, heat
exchangers, etc.
1.5.1.6 Thermal Shock Resistance
Figure 2.7 shows thermal shock resistance temperature as
measured by the thermal shock method (Hasselman method).
The measured value was approximately 450"C. Among high-
density ceramics, this value is second only to Si3N4 (approxim-
ately 600-9OO"C). Generally, under rapid cooling conditions such
as those used by this method, thermal shock resistance is
evaluated by the thermal shock/fracture resistance coefficient R,
shown in eqn (5).30
R= Or. (1- v)/E. a (5)
Here, Or is fracture stress, v is Poisson's ratio, E is the elastic
modulus and a is the thermal expansion coefficient.
I
Under gradual cooling, on the other hand, thermal shock
Fig.'}..7. Thermal
shock resistance 80
temperature of
SiC.
o
20
30
resistance is evaluated by the thermal shocklfracture resistance

coefficient R', shown in eqn (6).31
R' = (]f. k. (1- v)IE. a (6)
Here, k is thermal conductivity.
When room-temperature data are used, the SiC compacts of
Sumitomo Chemical have an R of 200k and an R' of 29 kw/m.
The same values for Si3N4 are 400-600k and 7-lOkw/m,
respectively, better than the values for SiC under conditions of
rapid cooling but not as good as those under gradual cooling.
The value R = 200k is lower than the measured value of 450k,
this being due to the fact that the thermal shock technique is not
for infinitely fast cooling conditions, and the influence of thermal
conductivity must be taken into consideration.
2.5.2 Thermal Properties
2.5.2.1 Thermal Conductivity

Table 2.2 shows thermal conductivity and thermal diffusivity as
measured by a laser flash method. SiC is a material possessing a
large thermal conductivity, the thermal conductivity of single-
crystal SiC being reported at 500 W1m K.32 Hot-pressed SiC
containing BeO (thermal conductivity: 270 W1m K) has been
developed as a high-thermal-conductivity IC substrate,33 but as a
structural material the value for ordinary SIC is in the range
50-120 W1m K. SiC compacts produced by Sumitomo Chemical
exhibit a high thermal conductivity of 146 W1m K, but this is
thought to be due to the lack of thermal-conduction-inhibiting
impurities on the crystal grain boundaries.
Thermal conductivity is an important property not only for
high-temperature materials requiring thermal shock resistance
but also for abrasion-resistant materials, and generally speaking a
Table 2.2
Thermal conductivity 146W/mK Thermal
Specific heat 690J/kgK Properties of
Thermal expansion coefficient 4x lO-6'rC SiC Compacts
31
high thermal conductivity is desired of materials used for

mechanical seals and bearings.
2.5.2.2 Specific Heat
Table 2.2 shows specific heat as measured by the laser flash

method.
2.5.2.3 Thermal Expansion Coefficient
Table 2.2 shows thermal expansion coefficient as measured by

differential dilatometer.
2.5.3 Corrosion Resistance
Table 2.3 shows resistance to corrosion in various liquid

solutions. SiC possesses extremly high resistance to corrosion,
and it is not corroded by either acids or alkalis. When numerous
impurities are present, however, resistance to corrosion de-
creases, making it important to manufacture SiC compacts of
high purity.
Table 2.3 Solution Weight loss Test

Corrosion (mg/dm z day) conditions
Resistance of
SiC HF:H2O 0·07 A"
34:66 vol. %
HF:~F 0·10 A
10:90 vol. % A
HF:HN0 3 0·17 Bb
86:14 vol. % B
H 2SO4 0·30 B
(cone.)
H 2S04 : H 20 0·15
50:50 wt%
NaOH:H2O 0·13
50:50 wt%
" 60°C, standing.
b 80°C, constantly stirred.
32
2.5.4 Microstructures
The properties of ceramic materials are dependent on the
characteristics of the microstructure, which in turn is influenced
by the characteristics and manufacturing process (raw material
properties, additive properties, molding conditions, sintering
conditions, etc.) of the material. Resistance to abrasion, for
example, is heavily dependent on grain dimensions and pore
dimensions and number, while corrosion and heat resistance are
affected by the composition and structure of crystal grain
boundaries. Therefore it is extremely important to select a
microstructure suited to the application and to maintain control
over the manufacturing process.
The SiC compacts produced by Sumitomo Chemical have
achieved superior properties by minimizing impurities, which Fig. 2.S. Micro-
structure of SiC
affect both corrosion and heat resistance. In addition, we have sintered bodies.
established a manufacturing process capable of producing a (a) Low-
uniform microstructure free of abnormal grain growth. Figure 2.8 temperature sin-
shows microstructures for SiC compacts which were sintered at tering, density
different temperatures. Although the difference in sintering 3·17 g/cm 3 , flexu-
ral strength
temperatures is approximately 100°C, there is little grain growth 64 kg/mm2. (b)
and no reduction in strength. Consequently, it is possible to High temperature
manufacture products having extremely stable quality. sintering, density
3·17 g/cm 3 , flexu-
ral strength
63kg/mm2.
33
2.5.5 Re6ability
When ceramics are used as structural materials, mechanical
reliability is the most important factor. As described above, the
fracture strength of low-toughness ceramic materials is heavily
dependent on the dimension and number of various defects
(pores, inclusions, coarse particles), and there is a broad
statistical distribution. It is known that in practice this distribu-
tion is that of the Weibull distribution, shown in eqn (7).
F =1- exp[ - v., (afl I aor] (7)
Here, F is fracture probability, Ve is effective volume, af is
fracture stress, ao is the normalization constant, and m is the
Weibull coefficient.
It is possible to estimate the dimensional dependence of
fracture stress using the Weibull coefficient, as shown in eqn (8).
(8)
Generally, the Weibull coefficient for ceramics is approxim-
ately 10, and for large compacts with a large effective volume the
decrease in strength is remarkable. Given these factors, the
improvement of ceramics reliability requires design-related
approaches, including the avoidance of stress concentration,
efforts to increase fracture toughness, and efforts to reduce
fracture-forming defects (i.e. an increased Weibull coefficient).
Efforts to increase the Weibull coefficient are heavily dependent
on the manufacturing process, and this, together with non-
destructive testing technologies, constitutes an important task for
those engaged in the manufacture of ceramics.
2.6 CHARACTERISTICS OF SUMITOMO

CHEMICAL'S SiC COMPACTS
Table 2.4 shows a comparison of the properties of SiC compacts

produced by various companies. Sumitomo Chemical's SiC is
characterized by balanced mechanical properties. This is due to
the careful selection of sintering aids and the optimization of raw
material preparation and the molding and sintering processes.
Sintering aids sometimes agglomerate and segregate within the
sintered body, resulting in the formation of defects. As can be
34
Manufacturer Sumilomo Chemical Table 2.4

Property A B C D Comparison of
(a-SiC) (a-SiC) (a-SiC) (/J-SIC) (/J-SIC) SiC Properties
Density 3·17 3·17 3·14 3·20 3·05

(g/cm3)
Hardness 2370 2340 2110 1710 2050
(kg/mm2)
Flexural 60 41 56 48 67
strength
(kg/mm2)
Weibull modulus 12 16 5 13 7
K)c 4·6 4·4 4·3 5·8 4·8
(MN/m 3 •2 )
Corrosion
resistance"
Acid o o o x o
Alkali o o !:::, x o
"Weight loss (mg/dm2 day): 0, 1); !:::" 1-10; x, 10( .
seen from the boron surface analysis by X-ray microanalyser in

Fig. 2.9, the sintering aid content of Sumitomo Chemical's SiC is
extremely low, and the boron is evenly dispersed. With press
molding, a typical forming technique for ceramics, it is important
to control the properties of the granulated raw material powder
Fig. 2.9. Boron

distribution in SiC
sintered bodies
(XMA). (1)
Sumitomo
Chemical SiC (2)
SiC (A, Inc.)
3S
Fig. 2.10. Cross-

sections of iso-
statically-pressed
green bodies.
0.5 t/cm 2 0 . 8 t/cm 2
1.0 t/cm 2 1.5t/cm 2
and pressure transmission, disintegration and green body strength

in particular. At Sumitomo Chemical, a granulated powder
allowing the formation of uniform, high-strength green body
even at low forming pressures has been developed and is
currently in use (Fig. 2.10). As a result, it is possible to provide a
highly reliable final product with low defect size and number
levels.
The production of sintered bodies with low defect levels is
especially important during the actual use of large products such
as bearings and liners. As described above, the manufacturing
process is designed to provide highly reliable products, but
non-destructive testing techniques such as ultrasound and X-ray
inspection have been incorporated to be absolutely sure.
36
2.7 APPLICATIONS OF SILICON CARBIDE

COMPACfS
Because of their superior resistance to heat, SiC compacts have

found wide application in various types of high-temperature
furnace components (heating elements, core tubes, refractory
brick, etc.). These applications, however, do not necessarily
require high-density sintered bodies. The development of SiC
compacts as structural materials with high density was initially
begun with the objective of application to components for gas
turbine engines. Applications of SiC compacts as structural
materials can be broadly divided into: (1) abrasion- and
corrosion-resistant components; and (2) heat-resistant com-
ponents. At present, most applications fall into the former
category. Table 2.5 offers a summary of these applications,
several of which will be introduced below.
2.7.1 Abrasion- and Corrosion-resistant Components
2.7.1.1 Mechanical Seals

Materials conventionally used for mechanical seals included
various metals, carbon, ultrahard alloys (WC), and A120 3. Since
mechanical seals must rotate at high speeds while maintaining a
seal against hot water, slurry, chemicals and oils, an extremely
wide range of properties are demanded, including resistance to
abrasion, corrosion and thermal shock, a high elastic modulus, a
low friction coefficient and a low specific gravity. SiC is
outstanding in each of these areas and, beginning as a
replacement for WC and Ah03, is seeing use in environments
which do not permit the use of conventional materials. In
addition to pressureless-sintered SiC, reaction-bonded SiC and
Si-impregnated SiC are being used in mechanical seals, but from
the standpoints of abrasion and corrosion resistance pressureless-
sintered SiC offers the best performance.
Table 2.6 shows characteristics of some of the mechanical seals
being used at a Sumitomo Chemical plant for the manufacture of
Al20 3. These seals have a much longer lifetime than those made
ofWC.
37
Table 2.S Applimtioll OPl!lYlting

Applications of
tmlJironmtmt
SiC Compacts Future
Abrasion- and Mechanical seals }

corrosion- Pump shafts and bearings
Acid/ alkali/slurry ,
resistant Nozzles
abrasion
components Liners
Valves
Bearings Abrasion, high loads
Grinding media Abrasion, shock
Paper-making components Pulp slurry/alkali,
abrasion
Heat-resistant Heat exchangers } High-temperature
components Fans
oxidation
Heating elements
Semiconductor jigs }
High temperature
High-temperature test jigs
Engine Gas turbines (inclUding}
components those for power High temperature,
generation high loads
Turbochargers
Other Components for steel }
refining and
High temperature,
manufacture
corrosion
Components for refining
of non-ferrous metals
Catalyst carrier High temperature
MHD generators High temperature,
(insulation, corrosion
electrode walls)
Fusion reactors High temperature,
(cooling walls) radiation
Table 2.6
Application to No. PVValue Slu", Temperature Lifetime (h)
Mechanical Seals (lcglt:m 2 x Conantralion rc)
mls) (g/lIiITe) SiC WC
1 21 0-01 70 24200 4000

(during operation)
2 18 0·1 93 8400 4000
3 11 380 90 21400 6000
(during operation)
Type of liquid: alkali.
38
Table 2.7
Diameter Rotating Pressure Temperature Application to
(mmtj)) speed (leg/em' ("C)
(rpm)
Pump Bearings
160 480 2·8 Room temperature

120 735 2·8 Room temperature
2.7.1.2 Pump Components

Pump shafts, bearings and sleeves are used under the same type
of environment as mechanical seals. In addition to the properties
demanded of mechanical seals, these components require high
strength because they are liable to encounter tensile stress. Many
of the components are large, and it is especially important that
the effect of dimension on strength reduction be small, i.e. that
stable quality can be maintained.
Large bearings for use in sewer pumps are currently operating
under the conditions shown in Table 2.7, and even larger
bearings are now coming into use.
2.7.1.3 Abrasion-resistant Liners
In the past, nozzles which handled slurry containing sediment
and liners for oil well pumps were made from metals because of
their mechanical reliability despite a short lifetime. With the
development of high-strength SiC, however, development is
being conducted on these applications as well. Due to the
superior abrasion resistance of SiC, good results are being
obtained in actual use.
2.7.2 Heat-resistant Components
2.7.2.1 Gas Turbines

With the objective of improving thermal efficiency, there has
been enthusiastic development of gas turbine engines and gas
turbines for power generation. Possible applications for SiC
include combustors, turbocharger rotors, vanes and blades.
Because of the extremely severe operating environment, the
stage of practical application has yet to be reached, but a wide
39
range of research is being conducted, including rotary fracture

and high-temperature tests. In the case of turbocharger rotors,
which are expected to see practical application before gas
turbines, operating tests using actual engines are already being
carried out. 34
2.7.2.2 Heat Exchangers and Ceramic Fans
In the various 'high-temperature industries', it is important from
the standpoint of thermal efficiency to be able to perform heat
exchange as well as the circulation and pressurized transport of
Fig. 2.11. SiC

products.
40
gas without reducing gas temperature. Heat exchangers have

already seen practical application, and the use of ceramic fans at
1300°C has been reported. 35
At Sumitomo Chemical development is being conducted· on
high-temperature test jigs, Al diecast components, and other
heat-resistant components with an emphasis on abrasion- and
corrosion-resistant components such as mechanical seals, pump
components, and mechanical components for paper making. In
addition, a mass production system has been established for
some of the products. Figure 2.11 shows some of these. In the
future, further product development at Sumitomo Chemical will
accompany improvements in physical properties such as tough-
ness, strength and reliability, and an expansion of the range of
potential applications for our SiC products.
2.8 SUMMARY
Based on the superior properties possessed by fine ceramics and

expectations for their future marketability (the market is
predicted to grow to 1·5 trillion yen by 1990 and 5 trillion yen by
2000), many companies are now planning advances into this field.
In the area of structural ceramics in particular, Si3N4 and SiC are
seen as promising candidates. Brushing up on conventional SiC
manufacturing technologies, Sumitomo Chemical hopes to estab-
lish ceramics manufacturing technologies offering excellent
reliability and cost performance and make contributions to the
field of structural ceramics.
We would be happy if this chapter were to assist in the
development of structural ceramics.
REFERENCES
1. K. Tanaka, Report for Research of High Purity Silicon Carbide.

National Institute for Research in Inorganic Materials, 1967, p. 4.
2. Sumitomo Aluminium Smelting Co. Ltd, US Patent 4,562,040,
1985.
3. Udagawa, S., Yanagida, H. & Sudo, G., Inorganic silicon
compounds as fine chemicals. Kodansha, Tokyo, Japan, 1982, p.
154.
41
4. Enomoto, R., Beta-silicon carbide powder 'Betarundum'. Industrial

Rare Metals, 73 (1980), 178.
5. Okabe, Y., Hojo, J. & Kato, A., 'Formation of silicon carbide
powders by the vapor phase reaction of the SiHcC14-H2 system.
J. Chem. Soc. Japan, (1980), 188.
6. Okabe, Y., Hojo, J. & Kato, A., Formation of fine silicon carbide
powders by a vapor phase method. J. Less-Common Met., 68
(1979),29.
7. Yajima, S. & Okamura, K. Science, 11 (1981), 79.
8. Hase, T. & Suzuki, H., Properties of submicron {:J-SiC prepared
from siliconization of carbon black. J. Ceram. Soc. Japan, 86
(1978), 541.
9. Ando, Y. et al., Preparation of ultrafine particles of refractory metal
carbides by a gas-evaporation method. J. Cryst. Growth, 52 (1981),
178.
10. Alliegro, R. A. et al., Pressure-sintered silicon carbide. J. Am.
Ceram. Soc., 39 (1956),386.
11. Nadeau, J. S., Very high pressure hot pressing of silicon carbide.
Am. Ceram. Soc. Bull., 52 (1973),170.
12. Prochazka, S., GE Report, SRD-72-035, 1972.
13. Prochazka, S. & Smith, P. C., Investigation of ceramics for
high-temperature turbine vanes. GE Report SRD-74-040, 1974.
14. Kennecott Corporation, US Patent 4,312,954, 1982.
15. Schwetz, K. A. & Lipp, A., Science of Ceramics, 10 (1979), 149.
16. Suzuki, K. & Sasaki, M., Pressureless sintering of silicon carbide.
Presented at Japan-U.S. Seminar on Fundamental Structural
Ceramics, 1984., ed S. Somiya & R. C. Bradt. Terra Science
Publishing Co, 1987, pp. 75-87.
17. Prochazka, S., Sintering of silicon carbide. Materials Science
Research, 9. Plenum Press, New York, 1975, p. 421.
18. Greskovich, C. & Rosolowski, J. H., Sintering of covalent solids. J.
Am. Ceram. Soc., 59 (1976), 336.
19. Suzuki, H. & Hase, T., Some experimental consideration on the
mechanism of pressureless sintering of silicon carbide., Proc. of
Internl. Symp. of Factors in Densification and Sintering of Oxide and
Non-oxide Ceramics, Gakujutsu Bunken Fukyu-kai, Tokyo, Japan,
1978, p. 345.
20. Lange, F. F. & Gupta, T. K., Discussions and notes, Sintering of
SiC with boron compounds. J. Am. Ceram. Soc., 59 (1976), 537.
21. Inomata, Y., Uemura, Y. & Inoue, S., Energy stored in a grain
boundary formed by a rotation along a hexagonal lattice plane in
SiC crystals. J. Ceram. Soc. Japan, 88 (1980), 628.
22. Houg, J. D., Davis, R. F. & Newbury, D. E., Self-diffusion of
silicon-30 in a-SiC single crystals. J. Mater. Sci., 16 (1981), 2485.
23. Asaga, K. & Hamano, K., Initial sintering kinetics of compacts of
spherical alumina particles. J. Ceram. Soc. Japan, 83 (1975), 136.
24. BOeker, W. & Hausner, H., The influence of boron and carbon
additions on the microstructure of sintered alfa silicon carbide.
Powder Metal. Int., 10 (1978), 87.
42
25. Suzuki, K., Relation between microstructure and fracture toughness

of ceramics. Bull. Ceram. Soc. Japan, 21 (1986), 590.
26. Kato, K. & Kawabata, N., Relations between properties of
diamond wheel and surface roughness on machining of ceramics. FC
Report, 4 (1986), 10.
27. Griffith, A. A., Phil. Trans. R. Soc. Lond., 221A (1920), 1631.
28. Takeda, Y. & Nakamura, K., Proceedings of the 23rd Japan
Congress of Materials Research, The Society of Materials Science,
Kyoto, Japan, 1980, p. 215.
29. Yokobori, T., Strength, fracture and fatigue of materials, 2nd
edition. Iwanami, 1974.
30. Niishata, K. & Hira, T., Super-fine microstructure and toughness of
ceramics. Bull. Ceram. Soc. Japan, 21 (1986), 598.
31. Nakayama, J. & Abe, H., Thermal properties and thermal stress
fracture of ceramics. Zhityo, 32 (1983), 685.
32. Slack, G. A., Nonmetallic crystals with high thermal conductivity. J.
Phys. Chem. Solids, 34 (1973), 321.
33. Maeda, K., Takeda, Y., Nakamura, K. & Ura, M., Grain
boundaries of SiC ceramics with high thermal conductivity and high
electrical resistivity, Bull. Ceram. Soc. Japan, 18 (1983), 217.
34. Maruyama, M., Developments for advanced ceramics in USA and
Europe. Nikkei Mechanical, 28 June (1985), 58.
35. Toriyama, A. & Takesa, K., Axial ceramics fan for high
temperature use. Turbomachinery, 13 (1985), 485.
APPENDIX
Non-destructive Testing
Non-destructive testing involves the physical inspection of the
internal shape, structure and defects of components with
complicated shapes without damaging the material. The follow-
ing methods are currently in use:
(1) Velocity, reflectance and damping frequency characteris-
tics of ultrasound waves (commercially available devices
include ultrasound CT and ultrasound microscopes).
(2) Micro-focus X-rays (X-ray CT).
(3) Neutron and electron beam radiography.
(4) Optical acoustics.
In the case of sintered bodies, items for inspection include
porosity, crystal size, density distribution, surface defects,
inclusions, cavities, cracks, and internal shape. With present
43
technologies it is possible to distinguish internal spherical defects

with size on the order of several tens of microns. Since
micro-defects have a large impact on the fracture strength of
ceramic materials, research continues on the improvement of
detectability.
K. c (Fracture Toughness)
K IC is the critical value of stress expansion coefficient K in the
I-mode (open mode) and is also referred to as the critical stress
expansion coefficient. The value can be obtained experimentally
in relation to critical stress during crack propagation. K IC is
thought to be a material constant related to energy absorption at
the time of fracture, and the larger the value the greater the
energy absorption during fracture and hence the tougher the
material. Thus it is closely related to the ease with which a
material breaks.
For certain materials, it is thought that if K IC is available it is
possible to calculate fracture stress in the open mode when
certain defects are present. For a more detailed discussion the
reader' should refer to works on linear fracture mechanics, but it
should be noted that some researchers do not consider K IC to be
a material constant.
Numerous unresolved questions remain concerning fracture
mechanisms in brittle materials, and active research continues.
44
3 Epitaxial Growth of
SiC Single Crystal
Films
YOSHIHARU NAKAJIMA
ABSTRACT
For many years, single crystal SiC has shown promise as a

candidate for high-temperature electronic devices because of its
excellent physical and chemical stability, large bandgap, and good
carrier mobility. Reflecting on these circumstances, the single
crystal growth technique has recently made great progress.
In the first half of this chapter, the various single crystal growth
methods will be described with an emphasis on epitaxial film
growth. In the second half, chemical vapor deposition (CVD) for
the heteroepitaxial growth of fJ-SiC films on Si substrates will be
discussed together with the results of characterization of the grown
films by X-ray diffraction, transmission electron microscopy,
secondary ion mass spectroscopy, and electron spin resonance
methods.
At present, epitaxially grown fJ-SiC films with a thickness of
more than several micrometres can be constantly and uniformly
prepared on Si substrates of 2-4 in. However, these films still
contain a high concentration of (111) planar defects. This problem
must be resolved if they are to be of practical use in the near
future.
3.1 INTRODUCTION
The most attractive feature of SiC (silicon carbide) is its stability

as a compound. From the standpoint of heat resistance, it is
45
Yoshiharu Nakajima
stable up to temperatures of 2800°C and above, at which it

decomposes into an excess-Si vapor phase and carbon, and also
possesses excellent chemical resistance and mechanical strength
(hardness). 1 Taking advantage of these properties, SiC has
already seen wide-ranging application in abrasives, cutting tools,
refractory bricks, coating materials, and high-temperature heat-
ing elements (so-called siliconit). Recently, attention has been
focused on the application of SiC in structural components for
ceramic engines. Another important characteristic of this mate-
rial is its properties as a semiconductor. 2 SiC has long been used
as a compound semiconductor in arresters and varistor materials,
and recently the above-described properties together with its
high-temperature electrical properties, high breakdown voltage,
saturated drift velocity, high electron mobility, and good
resistance to radiation have made it attractive as a candidate for
use in electronic devices operating in severe conditions, at high
temperatures, with high output, and in high-frequency regions. 3
Furthermore, the wide bandgap of SiC and the fact that the
conductivity of p or n types can be controlled by introducing
impurities makes it a promising candidate together with ZnSe
and ZnS for use in luminescent elements in the visible light
range. 4
While SiC possesses numerous advantageous properties and its
appearance is keenly awaited, the best reason why it has yet to
reach the stage of practical application is that the crystal growth
technologies required to obtain uniform, large-area crystals have
yet to be established. As can be seen from materials currently
used for semiconductor devices, such as silicon (Si) and gallium-
arsenide (GaAs) , these materials must possess extremely high
crystallinity, and such a high grade of SiC has yet to be achieved.
Nevertheless, progress over the last 10 years in the growth
technologies required to obtain large-area, high-quality single
crystals has been remarkable, and in reflection of this progress
various prototype devices are now being reported.5-12 This
chapter will introduce recent developments in large-area SiC
single crystal thin film fabrication technologies (for electronic
devices) with emphasis on crystal growth methods in general and
the epitaxial growth of fJ-SiC single crystal thin films onto single
crystal Si substrates in particular.
46
SiC Single Crystal Films
3.2 CRYSTAL STRUCTURE AND PROPERTIES
As shown in Fig. 3.1, SiC crystals, a typical group IV compound,

consist of a hybrid structure in which the constituent Si and C
atoms lie in 2s2p and 3s3p orbits, thus forming a so-called Sp3
hybrid orbit bond. Tetrahedrals consisting of one carbon atom
coordinated by four silicon atoms and vice versa are formed.
Carbon and silicon atoms are tetrahedrally coordinated to each
other and these tetrahedrals share the same apex to form a
three-dimensional diamond network structure. This strong coval-
ency is the source of the high strength of SiC and its stability at
high temperatures. When the Si-C bonds of SiC are considered
as one layer, differences in the regularity of the stacking of these
layers results in the presence of an extremely large number of
polytypes. I 3-16 Ordinarily, these polytypes are divided into two
groups, a-SiC and fJ-SiC, according to differences in the crystal
symmetry. The term fJ-SiC is used for crystals with a cubic zinc
blende structure, while a-SiC is used as a general term for
hexagonal and rhombohedral crystals. In order to be more
specific about the crystal structure, the various polytypes are
sometimes distinguished as 3C, 4H, 6H, 15R, 9T, etc. 16 In this
notation, C represents a cubic system, H hexagonal, and Rand T
rhombohedral and trigonal, respectively. The preceding numeral
indicates the repeat period in the stacking direction of the Si-C
Fig. 3.1. Crystal

structure of fJ-
SiC: Si and C
atoms take on a
four coordinated
tetrahedral struc-
ture and share
apexes to produce
a three-
dimensional net
structure.
8, B-SIC
47
Yoshiharu Nakajima
Fig. 3.2. Typical

polytypes ob-
served in SiC
crystals. Indicates
the stacking state
of Si-C layers. (a)
p-type; 3C
(abcabc .... )
structure; (b)
a-type;6H
(abcacba .... )
structure.
bond pair layers. In Fig. 3.2, the repeating scheme of the 6H

modification, a typical a-type structure, is compared with the 3C
«(J-type) modification.
Naturally, the physical properties of the crystal vary depending
upon the polytype modification. Table 3.1 shows typical physical
properties for 6H and 3C crystals. Among the properties
particularly important in the case of electronics materials is
bandgap. These values, at 2·2 eV for (J-SiC and 2·8 eV for 6H
SiC, are far superior to those for Si and GaAs semiconductors,
and this is the reason why SiC is so promising a candidate for use
in visible-light luminescent elements. In the case of {J-SiC, the
values for electron mobility and saturated drift velocity are both
high at 1000 cm2 /v sand 2 x 107 cm/s, respectively. (J-SiC also
has a high breakdown field of 5 x 106 V /cm. These are the
Table 3.1
Physical fJ-SiC (Je-type) a~iC (6II-type)
properties of
Crystal system Cubic Hexagonal
typical SiC
Polytype
Lattice constant a = 4·358 a = 3·082
(A) c = 15·117
crystals (3C and
6H) (from a table
Bandgap (eV) 2·20 2·86
Dielectric constant 9·72 9·66 (.L)
in Ref. 2)
(e) 10·03 (II)
Thermal conductivity 0·255 (200°C) 0·410 (20°C)
(W/em 0c)
Electron mobility 1000 460
(cm2 /V S)
Saturation electron 2·0 X 10'
velocity (em/S)
48
reasons for the research and development being conducted on

SiC as a material for high-temperature, high-output and
high-frequency electronic devices.
3.3 METHOD OF GROWING SINGLE CRYSTAL

INGOTS
As described in Section 1.3, SiC has seen wide application in

abrasives, heating elements, refractories, and FRM (Fiber
Reinforced Metals) and FRP (Fiber Reinforced Plastics), both of
which use whisker fibers, because of its superior characteristics.
Nevertheless, the development of applications utilizing the
electrical properties of SiC has been limited, the major reason
being that technologies for the growth of high-quality single
crystals with good reproducibility have yet to be established.
Extremely high temperatures are required for the synthesis of
SiC crystals, and in order to produce crystals with few defects it
is necessary to find conditions allowing thorough control over the
almost limitless number of polytypes 14 present. Here, the method
of growing substrate SiC crystals used in the epitaxial growth of
thin film single crystals will be briefly described as a reference for
the following section. The Acheson method has long been used
to prepare SiC for use in abrasives and refractories. In this
technique, coke is added to Si02 (silica), and carbon rods are
electrically heated to induce crystallization. Crystals produced
using this method contain numerous impurities, and control of
the polytypes is difficult, making it unsuitable for the production
of high-purity electronic device crystals.
The Lely method 17 was developed with the objective of
obtaining crystals of higher purity. In this technique, which uses
sublimation and recrystallization, powder SiC crystals are placed
between a double cylindrical graphite crucible to which a
temperature differential has been applied. The powder is then
heated in argon gas to sublimate the raw material in the
high-temperature portion of the crucible and recrystallize it in
the low-temperature portion. Although quantity is limited, this
technique can produce high-purity a-type crystals, and the
possibility of applying it to the preparation of electronic materials
such as rectifiers and light-emitting elements, which use pn
junctions created by impurity doping, has been studied. Because
49
Yoshiharu Nakajima
this method requires well-controlled growth technologies at

temperatures of 2500°C and above, however, it is incapable of
providing well-controlled polytypes and large crystals from the
standpoint of polynucleation. Only recently an improved Lely
method18 ,19 using seed crystals to control polytypes was de-
veloped, and it became possible to obtain relatively large
(diameter 15-20 mm, length 20-25 mm) 6H single crystals. Use
of a larger crucible for growing should make it possible to
fabricate even larger ingots.
3.4 EPITAXIAL GROWTH OF SINGLE CRYSTAL

THIN FILMS
While work continues on the production of high-quality large

crystals by bulk single crystal growth, the focus of research
concerning electronic crystals is shifting to epitaxial growth
methods. In these methods, the desired crystal is grown on a
substrate crystal while maintaining relative crystallographic
orientation. When crystals of the same type but of higher quality
are grown on the substrate, the process is called homoepitaxial
growth; when a crystallographically different type of crystal is
grown the technique is referred to as heteroepitaxial growth.
Because epitaxial growth methods allow the control of polytypes
and impurities, they are widely used, particularly with Si, GaAS
and GaAlAs. A variety of epitaxial growth methods have also
been proposed in the growth of SiC single crystal thin films.
These methods include liquid phase epitaxy (LPE),20,6 sputtering
(SP),21 chemical vapor deposition (CVD),21-26 and molecular
beam epitaxy (MBE).27,28
This section will briefly introduce the epitaxial techniques, and
the following section will contain a slightly more detailed
description of epitaxial growth on Si of fJ-SiC single crystal thin
films, in which good progress has recently been made, and an
evaluation of crystals grown thereby.
3.4.1 «-SiC Growth by Liquid Phase Epitaxy (LPE)

Of the epitaxial growth methods to be described in this section,
LPE is the only one to use a Si melt. Consequently, the
50
Fig. 3.3.
GRAPHI TE
! Schematic struc-
HOl DER ture of a liquid
0 phase epitaxy in-
strument using
0 the dipping
0 method (Suzuki et
al. 6).
0
0
0
0
COOliNG!
t t
ARGON ~
WATER GAS
temperature during crystal growth is at or greater than the Si

melting point of 1420°C, and the type of crystal which can be
obtained is limited to a-type (mostly 6H). Basically, LPE
immerses the SiC seed crystal (substrate) in the melt to grow a
thin layer on the surface of the substrate. Numerous reports have
been given concerning the technical aspects of this method, but
perhaps the most successful of these attempts is the dipping
method 6 developed by Suzuki et al. As shown by the schematic
diagram of Fig. 3.3, the SiC substrate crystal is secured to the tip
of a graphite rod and immersed in a Si melt (1650-1800°C)
contained in a high-purity graphite crucible. After epitaxial
growth but before solidification of the molten Si, the substrate is
removed from the crucible, thereby preventing crack
generation 20 because of the difference in thermal expansion
coefficients. This technique is characterized by its ability to
produce p-type crystals, through the addition of an impurity such
as Al or B to the melt, or n-type crystals, by the use of a mixed
gas atmosphere containing N 2 • Prototypes of blue light-emitting
elements have also been reported. 6
3.4.2 SiC Thin Film Growth by Sputtering

Together with GD (Glow Discharge; also referred to as
low-temperature plasma CVD), sputtering is a very common
51
Yoshiharu Nakajima
method of fabricating amorphous SiC thin films. Relatively little

research, however, has been conducted on the growth of single
crystal thin films, and most of the available material deals with
covering materials (polycrystal films) whose objective is in-
creased film hardness. Sputtering is characterized by the fact that
thin films can be prepared regardless of the melting point of the
target material, and by the fact that selective growth using
shutters or masks is possible because the deposition has
orientation. Growth of thick films and precise control over
composition, however, are difficult with this method. Concerning
the fabrication of SiC thin films, the sputtering technique itself is
not unique, so discussion will be left to other sources. Here,
related results will be briefly discussed. There are two main
methods of SiC sputtering deposition: r.f. sputtering, which uses
a SiC sintered body as the target; and reactive sputtering, which
uses Si crystals as the target and a hydrocarbon reactive gas such
as CzH2 as a carbon source. Films obtained by sputtering are
generally polycrystal thin films, and crystallinity can be improved
by high-temperature heating of the deposition substrate or by
high-temperature heat treatment after deposition. It has also
been reported29 that it is possible to deposit P-SiC single crystals
on a-type substrate crystals using high-temperature heat treat-
ment. Nishin0 21 has reported that in epitaxial growth on a Si
(111) sudace using r.f. sputtering (target material: P-SiC; rf
potential: 2·0 kV; r.f. power: 4 W/cm2 ; sputter gas: argon;
pressure 5 x 10-2 torr; Si substrate temperature: 1200"C and
above) there was epitaxial growth of P-SiC single crystals having
(111) orientation. Films obtained by sputtering often have poor
crystallinity. Reports on the use of films prepared using this
method as 'buffer layers' during growth of P-SiC thin film single
crystals on Si, a topic to be described in the following section,
have also been reported. 22
3.4.3 SiC Thin FUm Growth by Molecular Beam

Epitaxy (MBE)27,28
Both chemical vapor deposition (CVD) and sublimation-
recrystallization require temperatures of 1300°C and above for
single crystal growth. The need for such high temperatures acts
as a major restriction on the development of devices. MBE is
52
now being studied as a means of reducing growth temperatures

and improving crystallinity. Commonly used in the fabrication of
super-lattice materials, MBE involves depositing on a substrate
placed in an ultra-high vacuum (-1010 torr) molecules of a raw
material that have been accelerated using a Knudsen cell (K-cell)
or an electron beam evaporator. An ion beam may also be used.
Basically, the reaction proceeds in a state of non-thermal
eqUilibrium and crystal growth occurs at lower temperatures than
with other methods. (Fundamentally, crystal growth is a
phenomenon occurring in a state of non-equilibrium.)
Results of the growth of SiC on Si and 6H SiC substrates using
MBE have been reported; fJ-SiC growth begins at a substrate
temperature of approximately 800°C, with heteroepitaxial growth
of fJ-SiC single crystals occurring at 1150°C. Growth of SiC by
this method was begun only relatively recently, and there are few
reports of high-quality, large-sudace-area single crystal thin films
having been obtained. Further developments are awaited.
3.4.4 6H SiC Thin Film Growth by CVD

Vapor-phase growth of cubic fJ-SiC onto Si substrates will be
described in detail in the following section. Here, the growth of
a-SiC will be discussed. Figure 3.4 offers a schematic overview of
Vent 000 Fig. 3.4. Typical

diagram of vapor
phase epitaxy
usingCVD.
o 000
RF coil
1. Si substrate
2. 5usceptor
3. pedestal
4. H2 diffusion
purifier
MFC
S3
Yoshiharu Nakajima
the equipment used in chemical vapor deposition (CVD). In this

technique, after diluting a raw material gas containing Si and C
elements such as Si~-C3H8' SiCL.-C3H 8, or SiH2CI2-C3H8 with
a carrier gas such as H2 or Ar, the gas is passed to the reaction
tube to grow SiC crystals on a substrate which is placed on a
graphite susceptor heated and maintained at a prescribed
temperature using high-frequency induction heating.
Homoepitaxial growth of 6H SiC uses 6H SiC grown on the
substrate by the previously-described Acheson technique. Al-
though the substrate temperature during growth is maintained at
1500-19OO"C, with high-temperature (-1900°C) CVD growth a
sublimation reaction often occurs together with the deposition,
resulting in an extremely slow deposition rate. The growth of 6H
crystals onto 6H allows epitaxial growth of high-quality crystals
at higher temperatures. Control over the semiconductor type (p
or n) requires introduction of an impurity into the reaction gas:
B2~ or Al(CH3MTMA) gas for a p-type semiconductor; and N2
or NH3 gas for an n-type semiconductor.
One of the reasons for using the CVD method is the
improvement in productivity brought about by the growth of
crystals with large surface area. Current 6H SiC growth,
however, requires the use of 6H SiC grown by another method as
a substrate crystal, and there is an insufficient supply of 6H SiC
for large substrates. At present, work in this area has not
experienced much success.
3.S HETEROEPITAXIAL GROWTH OF fJ-SiC ON

Si SUBSTRATES BY CVD
fJ-SiC having a larger surface area and higher quality is desired

because of its attractiveness as a material for high-temperature,
high-output and high-frequency device elements. This section
will introduce heteroepitaxial growth onto Si substrates, at
present the most promising method for production of such a
material.
3.S.1 P-SiC Crystal Growth

fJ-SiC (3C) can be grown at relatively low temperatures
compared with other polytypes, but only fine crystals can be
54
Fig. 3.5. fJ-SiC

SHARP crystal grown by
CVD on a 2-in Si
substrate: shows
mirror surface
and single crystal
thin film states.
(The left half of
the wafer on the
right is fJ-SiC
crystals after re-
moval of the sub-
strate Si.)
2 inches w fer
obtained with methods such as the Acheson and Lely techniques,

which were developed for the growth of bulk crystals. In order to
grow crystals with large surface areas heteroepitaxial techniques
are used intensively. Fortunately, f:J-SiC grows at temperatures
below the melting point of Si. As a result, heteroepitaxial growth
on Si, which allows the production of substrate crystals with large
surface areas (4-6 in wafer) at relatively low cost, has been
studied enthusiastically, and good results have been obtained. In
addition to Si, sapphire and spinel are being investigated as
possible substrate crystals, but these are susceptible to the
formation of twinned crystals and/or polycrystals, and growth of
a high-quality single crystal with a smooth surface and large area
has yet to be observed. Technologies for heteroepitaxial growth
of f:J-SiC on Si have progressed to the point where single crystal
thin films of rather good quality and having large surface areas of
2-4 in and mirror surfaces can be obtained. Figure 3.5 shows an
example of a f:J-SiC single crystal thin film with a mirror surface
on a 2-in wafer.
The problem encountered during heteroepitaxial growth is
how to prevent the introduction of defects caused by the different
lattice constants of the substrate and the grown crystals. With
growth onto Si, the lattice constant of the Si crystals used as a
substrate is 5430 A, while the value for the f:J-SiC crystals which
constitute the growth phase is 4358 A. There is thus a gap, or
lattice mismatch, of approximately 20%, and the problem of how
55
Yoshiharu Nakajima
to alleviate this extremely large difference is critical. Numerous

attempts have been made to resolve this problem, including the
introduction of an amorphous or super-lattice thin layer on the
interface. At present, however, one widely used method is that
of carbonization,23 developed at the University of Kyoto. In the
initial stage of growth, the Si substrate surface is exposed to a
hydrocarbon gas alone and carbonized to facilitate later growth.
In the two-temperature continuous CVD technique,24,25 de-
veloped at the Central Research Laboratories of the Sharp
Corporation, growth is conducted through a thin film grown by
CVD at a lower temperature. Both of these techniques attempt
to alleviate the lattice mismatch between the substrate Si and
the growth-phase SiC through introduction of a 'buffer layer', 30
which consists of a carbonized layer in the former method and a
low-temperature growth layer in the latter.
Figure 3.4 is a schematic diagram of the structure of a device
commonly used for crystal growth by CVD. The growth system
consists of various gas inlet portions, a reaction tube, and an
exhaust portion. Gases used include etching gas (mainly HCI) for
cleaning of the substrate surface, reaction gas for crystal growth
(C3HS' ~H2' CC4, and Si~, SiH2Ch, SiCI4 , etc.), and dilution
and carrier gases. The reaction tube is made of quartz glass, has
either a horizontal or vertical structure, and is water-cooled. A
substrate placed in this tube is heated to the prescribed
temperature by using high-frequency induction (r.f. heater), a
graphite susceptor whose surface is coated with polycrystalline
SiC and which is, installed on a quartz table (placed at a
gradient).
In order to obtain high-quality crystals, numerous parameters
must be set to optimal values. Among these are the orientation
of the substrate crystals, the quality of the susceptor, the angle of
the substrate surface with respect to the inlet gas (i.e. the
gradient of the quartz table), the concentration of reaction gas,
flow rate, gas composition (Si/C ratio), initial growth tempera-
ture and layer thickness (buffer layer), and gas pressure
(atmospheric or reduced) during reaction.
Actual techniques have varied slightly for each researcher, but
typical growth procedures for carbonization and two-temperature
continuous CVD methods will be described below (see the
temperature programs during growth shown in Figs 3.6(a) and
3.6(b).
56
1360 Fig. 3.6.

Reaction tem-
.
G
w
00
I
I
1
I
perature program
forCVD. (a)
a: 1
I Carbonization
::> 1
~ : 800 I CVD (from Ref.
a:
w 1 I
1
5); (b) successive
n- I
::. o I SIH 4 two-step CVD.
.
0 1
W
~
1 1 •
I.
IHCq CsH.
S~'I
H, H,:I Hz HII Hz Hz Hz
0
I I
0
0 I I :
(a) TIME
ISuccessive Two SteQ cvol
2nd Step
CYO
.
(Single Crystal Growth)
0.5- 6 hs
... .
-1350 C
1st Step
CYO
10oo-lloo·C
A few
min
,
(b) GROWTH TIME
The substrate crystals have been de-greased and washed in

advance using an organic solvent, and the surface oxide film has
been removed with hydrofluoric acid (HF). After placing the Si
substrate in the reaction tube, HCI gas which has been diluted
with H2 is used to perform surface etching at llOO-1200°C for
approximately 5 min. With the carbonization method, the
temperature is raised to 1360°C under a flow of ~Hs gas for
approximately 2 min to form a carbonization buffer layer on the
Si substrate surface. The Si~ and C3Hs growth gases and the H2
carrier gas are then simultaneously introduced into the reaction
57
Yoshiharu Nakajima
tube, and growth is continued at 1350DC. With the successive

two-step continuous CVD technique, after surface etching with
HCI gas either SiR. or SiH2Ch and C3HS growth gases are
introduced, and a primary buffer layer is grown for 2-5 min at
lower temperatures of 1050-1100DC. Next, as the temperature
rises to the single crystal growth temperature (1350DC), growth is
continued to form a secondary continuous buffer layer. The main
film is grown on top of this secondary layer. The thickness of the
buffer layer is approximately 200 A in the case of carbonization
and about 100 A and 400 A, respectively, for the primary and
continuous buffer layers of. the successive two-step CVD
technique. Under reflection high energy electron diffraction
(RHEED), the crystallinity of this buffer layer is either single
crystal or twinned crystal, indicating that crystals of rather high
quality have already been formed at this stage.
The grown crystals generally show n-type conductivity in an
undoped state. In order to obtain p-type crystals, just as with
a-SiC, B2~ gas or AI(CH3)3 (TMA, tri-methyl aluminum) can
be added as impurities during growth. N2 and NH3 are used as
high-concentration n-type impurities. Although in many cases
growth proceeds at atmospheric pressure, work has been done on
growth at reduced pressures (1·5-100torr),31,32 and improve-
ments in the uniformity of film thickness within the substrate
sudace have been achieved.
3.5.2 Epitaxy and Evaluation of Crystallinity

Evaluation of the crystallinity of the obtained crystals is a critical
problem, and it is necessary to tackle this together with
evaluation of electrical properties. This section will discuss
sample evaluations of fJ-SiC crystals grown epitaxially, with
special emphasis on results obtained by the author.
3.5.2.1 Surface Morphology
Crystallinity of the grown crystals is generally well reflected in
surface morphology. In cases of poor crystallinity, the surface
becomes nebulous and is not a mirror surface. In such cases,
observation is easy with a Normalski differential interference
microscope or a scanning electron microscope (SEM), and the
crystals are usually either an aggregate of facet crystals or
58
Fig. 3.7. SEM

micrograph of fJ-
SiC thin film
grownonaSi
substrate: the ob-
served portion is
the nebulous por-
tion, and the sur-
face was gold-
coated for obser-
vation. Note that
the crystals ex-
hibit facet texture
with (111)
orientation.
irregular shaped fine crystals (see Fig. 3.7) or dendritic crystals.

Upon observation by RHEED, these are clearly indicated as
twinned patterns or as the ring patterns which characterize
polycrystals. Figures 3.8(a) and 3.8(b) show comparisons of
RHEED patterns for when the twinned crystal includes polycrys-
tals and for the case of single crystals only. When there is good
surface smoothness and high crystallinity a mirror surface is
formed. In such cases it is virtually impossible to observe surface
morphology using a differential interference microscope or
scanning electron microscope, and the RHEED pattern shows
streak-like reflections in a direction perpendicular to the surface
of the sample (Fig. 3.8(b». Chemical etching of the surface with
hot KO" solution makes possible structure observation, and the
antiphase structure can sometimes be observed. 33
3.5.2.2 Orientation Relationship with the Si Substrate
As described above, a 20% lattice mismatch exists between the
substrate Si and the formed SiC. Figure 3.9 is a schematic
representation of the atomic arrangement of Si and the (100)
plane of SiC. In order to clarify these epitaxial relationships,
single crystal X-ray diffraction was used to examine in detail the
crystal orientation relationship with the substrate. These results
59
Yoshiharu Nakajima
Fig.3.S. RHEED (a)

pattern for P-SiC
growth surface.
(a) Polycrystals,
including twinned
crystals; (b) single
crystal.
(b)
will be shown below. In previous studies it was reported, based

primarily on the results of RHEED studies, that during the
growth of fJ-SiC on the Si (111) plane the orientation relationship
with the substrate was maintained, and that during growth onto
the Si (100) plane epitaxy occurred in a state in which the
relationship was rotated 45° around the [100] axis in the (100)
plane, resulting in a reduction of the apparent lattice mismatch to
13%.
The crystals used in the experiment were fJ-SiC grown to a
thickness of several f.A.m using successive two-step CVD for the Si
(111) substrate and carbonization for the Si (100) substrate.
Samples cut out for single crystal X-ray diffraction analysis were
60
Fig. 3.9.
Comparison of
atomic
arrangement and
crystal lattices for
the (100) plane in
(a) SiC and (b) Si.
(a)
attached to the substrate to allow simultaneous measurement of

the relationship between the substrate and the grown crystals.
An Mo tube was used as an X-ray source, and the diffraction
patterns were obtained with a single crystal precession camera.
The advantage of using this type of camera is that, unlike with
other single-crystal cameras, the recorded diffraction pattern
61
Yoshiharu Nakajima
Fig.3.10. X-ray
precession
diffraction pattern
and lattice re- (A)
lationship for {J-
SiC single crystals
grown by carb-
onization on Si
.
(100). (a) and (b)
-
correspond to
zero-layer re-
ciprocallattice
planes observed
by the precession
axes of a3 and 111
respectively. a*
, 2
~~~ __ ~~
111
______ o· .
(reciprocal lattice pattern) does not distort, and the crystal-

lographic orientation relationship of the two crystals can be
directly compared. Hence it is particularly effective in cases of
epitaxial growth. Results obtained using this method are shown
in Figs 3.10 and 3.11. In conclusion, it was clear that epitaxy was
completely maintained between the fJ-SiC and the substrate for
both carbonization and successive two-step CVD regardless of
whether the planar orientation of the substrate was (111) or
(100).
In order to reduce the number of defects (see next section)
occurring near the interface with the substrate, crystals were
grown on a substrate surface whose orientation had been tilted
Fig. 3.11. X-ray

precession
diffraction pattern
and lattice re-
(A) lationship for fJ-
SiC single crystals
grown by succes-
sive two-step
CVD on Si (111).
(a) and (b) cor-
respond to zero-
layer reciprocal
lattice planes with
the a3 and 111
axes, respectively,
as precession
axes.
( B)
111
o
from the (100) or (111) plane, and in this case as well a basic
crystallographic orientation relationship was maintained.
3.5.2.3 Observation of Defect Structures by Transmission
Electron Microscope
Transmission electron microscopy (TEM) is the method best-
suited to observation of micro-defect structures, including those
on the atomic order. As a result, there are numerous reports of
the use of this method for defect observation in epitaxially-grown
layers. 34 ,35 Here, the results observed by the present worker's
TEM studies will be introduced in some detail to assist the reader
63
Yoshiharu Nakajima
in understanding the state of currently obtained crystals and to

serve as reference for work on the reduction of defects.
Even in single crystals, analysis by X-ray streaks diffraction
patterns can be observed when there is an extremely high defect
density (mainly stacking faults). In cases of very small defects or
low defect densities, however, TEM contrast analysis and lattice
image observation are more effective. Samples used for this TEM
observation were high-quality crystals with mirror surfaces
epitaxially grown onto Si (111) and (100) planes by the
above-described carbonization and successive two-step CVD
methods. Observation was performed for the (100) and (111)
growth planes as well as the cross-sectional direction (from the
direction of the [110] axis). TEM requires samples thin enough to
transmit electron beams. For planar observation the Si substrate
was dissolved in HF solution and placed directly onto the
electron microscope mesh, and an ion thinner was used to create
a thin film by Ar+ beam etching. For cross-sectional observation,
the substrate crystal was sealed in resin, sliced with a diamond
cutter, mechanically polished, and finally polished to a thickness
allowing TEM observation using an ion thinner. Typical
observation results are shown in Figs 3.12-3.15.
Figures 3.12 and 3.13 are planar TEM bright field images for
{J-SiC epitaxially grown on the (100) and (111) planes, respec-
tively. In the figures, the linear patterns which intersect at angles
of 90° or 60° correspond to planar crystal defects, with numerous
defects being generated along the (111) plane in the {J-SiC
growth layer. The difference in defect arrangements between the
(100) and (111) plane projections is due to the different
projection directions of the equivalent plane for the (111) zone
in the cubic {J-SiC. Thus, although they appear differently, the
defects are actually of the same variety. Figure 3.14 shows the
results of defect observation from the cross-sectional direction.
As can be clearly seen in the figure, numerous defects (referred
to as interface dislocations) generated as the result of lattice
mismatch) are generated from the Si interface, and the ones
shown by planar TEM are those which could not be eliminated
during crystal growth and those which were newly generated
during growth. Due to the tendency for many of the defects
generated on the interface to merge during the growth process,
the number of defects decreases as film thickness increases.
However, there are numerous surface defects which are not
64
Fig. 3.U. Planar

TEM image of
f3-SiC thin film
grown on Si (100).
Fig. 3.13. Planar

TEMimageof
f3-SiC thin film
grown on Si (111).
6S
Yoshiharu Nakajima
Fig. 3.14. Cross-

sectional TEM
image of t}-SiC
thin film grown on
Si (100).
Numerous planar
defects have
occurred on the
interface with Si.
1 pm Si 100 sub
completely eliminated and which penetrate the growth surface

from the interface.
Judging from the similarity between the defect structures
observed by TEM and the facet structures shown in the scanning
electron microscope images of Fig. 3.7, these surface defects are
thought to be a type of growth defect occurring when adjacent
crystal bodies come into contact during the formation of
numerous SiC crystal nuclei on the Si substrate and during the
following increase in particle size, and the phases of the two
crystals do not meet on the contact surface. As a result, the
strain of the contact portion is not completely eliminated. fJ-SiC
single crystal thin films ordinarily obtained by heteroepitaxial
growth on Si contain 107-1OS defects/cm 3 •
Next, high resolution TEM (HRTEM), which has been
intensively used in many fields recently and allows resolution at
the atomic level, was used to observe the interface between the
substrate and the growth layer. The results are shown in Figs
66
Fig. 3.15. Cross-

sectional high re-
solution TEM
image of Si-SiC
interfaces (see
main text). (a)
Growth on the
(100) plane; (b)
growth on the
(111) plane.
(a)
(b)
67
Yoshiharu Nakajima
Fig. 3.16. Crystal

structures of SiC
and Si projected
from a direction
corresponding to
Fig. 3.15.
(a) (b)
3.15(a) and 3.15(b). The multi-beam lattice image method, which
uses the numerous diffraction waves .passing through the
objective aperture of the electron microscope to form an image,
was used, and the observation was a [110] projection. Crystal
structures of Si and SiC as seen from the same direction are
compared in Figs 3.16(a) and 3.16(b). With the multi-beam
lattice image, portions having a high charge density (this often
corresponds to the projection to the position where numerous
atoms are piled up) are usually dark, while portions of low
density become bright. The arrangement of black and white spots
in the HRTEM images shown here corresponds to the periodic
arrangement of atoms in the crystal structures of Si and p-SiC. A
comparison of Figs 3.15(a) and 3.15(b) shows that different
growth conditions can result in very different interface states.
Specifically, while for growth on the (100) plane the interface is
virtually smooth at the atomic level, in the case of growth onto
the (111) plane the result is an irregular shape in which the
interface has penetrated the Si substrate. A comprehensive study
of the numerous available 'crystal observation results, however,
suggests that the shape of this interface is not necessarily
important, with penetration of SiC crystals into the substrate
silicon crystals having been observed during growth on the (100)
plane as well, and it is thought that complex changes are
exhibited in relation to the presence of defects, etc. Analysis of
chemical composition by Auger electron spectroscopy (AES) has
been reported to show a gradual change in composition from the
interface.2 It is very possible that the interface microstructure
68
changes depending on conditions during formation of the buffer

layer, and a firmer grasp of both buffer layer properties and the
elementary process of epitaxial growth is needed.
Next, defects observed in the growth layer will be discussed.
The defect structure indicated by Fault A in Fig. 3.15(a)
corresponds to the planar defect along the (111) plane seen in the
low-magnification bright-field images of Figs 3.12-3.14. It is
often the case that defects in the (111) plane sandwich the defect
interface such that the bodies on both sides are not coherent, but
these can also be assumed as differences in polytype stacking (i.e.
stacking faults), often seen in (l'-type SiC, occurring on the order
of a few atomic layers. Some of these stacking faults are the
remains of the previously-described growth defects, while others
were newly formed due to the lattice mismatch with the
substrate. Speaking in simplified terms, in order to alleviate a
20% lattice mismatch it is necessary to introduce defects (linear
defects) at the ratio of one lattice to every five f3-SiC lattices.
There are also numerous portions where lattice discontinuities
are observed on the interface with the Si substrate at almost
precisely this ratio. In growth on the (111) plane numerous
stacking faults parallel to the growth surface as indicated by Fault
B in Fig. 3.15(b) can also be observed. Here, stacking faults are
regularly introduced from every few layers to every few tens of
layers, as seen in the growth of regular (l'-type polytypes also
present in places. (Super-lattice reflections corresponding to
larger lattices are observed in transmission electron diffraction
patterns taken from such portions.)
It was noted above that it is possible to control SiC
conductivity type (p or n) by impurity doping. Figure 3.17 shows
defects generated on the pn junction interface. As is clear from
the figure, virtually no defects can be observed in p-type SiC,
while after crossing the interface and passing into n-type SiC
(111), planar defects occur with high frequency. The source of
these defects has yet to be fully understood, but it is thought to
be related to the concentration of impurity atoms on the
interface during impurity doping or temporary intermission of
growth during doping. Thus minor differences in growth
conditions play an important role in the generation of defects,
and this in turn affects the properties of the resulting crystal. In
order to obtain crystals of higher quality, precise evaluation of
grown crystals and careful control of conditions are required.
69
Yoshiharu Nakajima
Fig.3.17. Cross-
sectional high re-
solution TEM
imageofapn
junction inter-
face. The gener-
ation of numerous
crystal defects can
be observed along
the p . n interface.
30 nm
3.5.2.4 Residual Impurities in the Crystals

In electronics materials, the impurity atoms contained in the
grown crystals are extremely important in the sense that they can
greatly affect the properties of the material. Epitaxially-grown
undoped P-SiC crystals exhibit n-type electrical conductivity and
have a relatively high electron density (Ne = 1015_
10 16 electrons/cm3 ). The reason for this is thought to be the
presence of electrically active defects or the introduction of
impurities, and specification is important. This can be achieved
by methods such as the measurement of photoluminescence, but
here results obtained from secondary ion mass spectroscopy
(SIMS) and electron spin resonance (ESR) will be shown with an
emphasis on residual impurities.
With SIMS, primary ions accelerated in a high vacuum are
made to collide with the object of analysis, the ionized secondary
ions of the particles which fly off from the surface of the sample
are trapped by electrical and magnetic fields, and mass analysis is
performed. This technique is characterized by extremely high
sensitivity. ot was used as a primary ion for this measurement.
Analysis was performed over a broad mass range, but nitrogen
(N) was the only impurity detected. In analysis of N contained in
Si by SIMS, ordinarily 42SiN+ ions are detected (here, the
70
dN: Sic (N2 O.OOSCCM. non dope) Fig. 3.18. Mass

** Single ion detector ** Gain: 1
Rate: 32 sec
analysis spectra
by secondary ion
mass spectroscopy
,28 Si 2+(mfz =13·988464) (SIMS) of un-
doped P-SiC crys-
tals. There is an
observed peak for
14N+ , which is
contained as an
impurity.
,14N+(mfZ=14'0030740)
Amfz=001461
13·7 13·8 13·9

m/z
detection limit is approximately 1016 atoms/cm3 ), but during

analysis of SiC, 42SiN+ ions become obstructing ions. Separation
of the two requires a mass resolution, m/z, of at least 6700, and
measurement is not easy. In the current work, 14N+ was
measured directly. The mass resolution needed in this case was
approximately 900. Figure 3.18 shows one of the measurement
spectra obtained. Electron concentration in the undoped crystal
(carrier concentration, as determined from the temperature
dependency of mobility) varied depending on differences in site
atomic ratio and other synthesis conditions, but given the
correlation between the trend for increased electron concentra-
tion and the N impurity concentration as measured by SIMS
analysis, it is thought that the n-type conductivity of the undoped
P-SiC crystals and the high electron concentration are closely
related to the concentration of N introduced during growth. This
conclusion is supported by the results of ESR measurements
shown below.
Figure 3.19 shows ESR spectra obtained by varying the
temperature in the low-temperature region.36 This sample had an
electron concentration of 1·3 X 1016 /cm\ and a split into three
distinct lines can be observed around 30 K, Indicating the
presence of 14N (/ = 1).
71
Yoshiharu Nakajima
Fig. 3.19. T'50K

Electron spin re-
sonance (ESR) 39K
spectra for un-
doped tJ-SiC crys-
tals. A split peak
indicating the
presence of im- 34K
purity N can be
observed.
3.2K
G = 3200
I
3250
,
3.6 SUMMARY
This chapter has discussed SiC single crystal thin films with an
emphasis on CVD growth of J3-SiC crystals and the evaluation of
crystallinity. There is a wide range of possible applications for
such thin-film materials starting with electronic devices.
Needless to say, evaluation of a material must be performed
with the intended use in mind. Consequently, evaluation of SiC
as an electronics material should be based on an accurate
evaluation of the electrical properties of the crystals. Concerning
evaluation of the electrical properties of SiC single crystal thin
films, recently there have been numerous reports on pn junction,
MOS and Schottky characteristics as well as various prototype
devices such as LEDs and FETs, and there has been much
discussion in these. However, improvements in the crystallinity
of synthesized crystal materials form the basis for improved
properties and reliability. Evaluation, in tum, forms the
foundation for such improvements, and it cannot be avoided. In
the fast-progressing world of science and technology, fabrication
technologies for SiC single crystal thin films are making
particularly rapid strides. Reflecting these, further increases in
the tempo of work on utilization and applications can be
expected.
Finally, the author would like to express his appreciation to Dr
72
Akita Suzuki, and Mr Katsunori Furukawa Central Research

Labratories of Sharp Corporation together with the Materials
Research and Analysis Center, Drs Yoshiro Akagi, Hirosuke
Matsunaga, and Hideo Asahaina for their contributions and
assistance.
REFERENCES
1. Summary of new substance and new materials. Edited and published
by Nikkan Kohgyo Shinbun-Sha, (1986) pp. 134-5
2. Matsunami, H., Application of SiC to the semiconductor technology
and its recent trend. Semiconductor World, 11 (1986), 40-8.
3. Furukawa, K., Uemoto, A., Fujii, Y., Shigeta, M., Suzuki, A. &
Nakajima, S., Field effect transistors of CVD-grown p-SiC. Sharp
Technical Journal. 38 (1987), 18-21.
4. Yoshida, S., Sakuma, E., Endo, K., Misawa, S., Miyazawa, T. &
Gonda, S., SiC high-temperature optoelectronic devices. Bull.
Electrotech. Lab., 48(5,6) (1984), 404-19.
5. Matsunami, H., Silicon carbide films. In Thin Films from Free
Atoms and Particles, ed K. J. Klabunde. Academic Press, New
York, 1985, pp. 301-24.
6. Suzuki, A., Ikeda, M., Nagao, N., Matsunami, H. & Tanaka, T.,
Liquid-phase epitaxial growth of 6 H-SiC by the dipping technique
for preparation of blue-light-emitting diodes. J. Appl. Phys., 47(10)
(1976), 4546-50.
7. Yoshida, S., Sasaki, K., Sakuma, E., Misawa, S. & Gonda, S.,
Schottky barrier diodes on 3C-SiC. Appl. Phys. Lett., 4(;(8) (1985),
766-8. .
8. Shibahara, K., Nishino, S. & Matsunami, H., Metal-oxide-
semiconductor characteristics of chemical vapor deposited cubic-
SiC. Jpn J. Appl. Phys., 23(11) (1984), L862-L864.
9. Suzuki, A., Ashida, H., Furui, N., Mameno, K. & Matsunami, H.,
Thermal oxidation of SiC and electrical properties of AI-Si02 -SiC
MOS structure. Jpn J. Appl. Phys., 21(4) (1982), 579-85.
10. Suzuki, A., Uemoto, A., Shigeta, M., Furukawa, K. & Nakajima,
S., High-temperature characteristics of CVD-grown p-SiC p-n
junction diodes. Extended Abstracts of 18th International Con-
ference on Solid State Devices and Materials, Tokyo, 1986, pp.
101-4.
11. Furukawa, K., Uemoto, A., Shigeta, M., Suzuki, A. & Nakajima,
S., 3C-SiC p-n junction diodes. Appl. Phys. Lett., 48(22) (1986),
1536-7.
12. Suzuki, A., Uemoto, A., Shigeta, M., Furukawa, K. & Nakajima,
S., Temperature dependence of electrical properties of non-doped
and nitrogen-doped beta-SiC single crystals grown by chemical
vapor deposition. Appl. Phys. Lett., 49(8) (1986), 450-2.
13. Jepps, N. W. & Page, T. F., Polytypic transformations in silicon
73
Yoshiharu Nakajima
carbide. In Poly type Structures, ed. P. Krishina. Pergamon Press,

Oxford, 1983, pp. 259-307.
14. Inoue, Z., A simplified method of generating layer sequences for
SiC polytypes. J. Mater. Sci., 17 (1982), 3189-96.
15. Inoue, Z., Inomata, Y., Tanaka, H. & Komatsu, H., A simplified
method of generating layer sequences for SiC polytypes Part 2.
Application to the determination of new polytypes 20 H(a) and
20 H(b). J. Mater. Sci., 17 (1982), 3197-203.
16. Inoue, Z., Sueno, S., Tagai, T. & Inomata, Y., A new polytype of
silicon carbide 9 T. J. Cryst. Growth, 8 (1971), 179-82.
17. Lely, J. A., Darstellung von Einkristallen von Siliciumcarbid und
Beherrschung von Art und Menge der eingebauten Verunreinigun-
gen. Ber. Deut. Keram. Ges., 32 (1955), 229-50.
18. Lilov, S. K., Tairov, Y. M. & Tsvetkov, V. F., Study of silicon
carbide epitaxial growth kinetics in the SiC-C system. J. Cryst.
Growth, 4(J (1979), 269-73.
19. Tairoy, Y. M. & Tsvetkov, V. F., General principles of growing
large size single crystals of various silicon carbide polytypes. J.
Cryst. Growth, 52 (1981) 146-50.
20. Brander, R. W. & Sutton, R. P., Solution grown SiC p-n junction.
J. Phys. D2 (1969),309-18.
21. Nishino, S., A study on CVD growth of SiC single crystal and its
applications. Doctor thesis (Kyoto University), 1981.
22. Nishino, S., Hazuki, Y., Matsunami, H. & Tanaka, T., Chemical
vapor deposition of single crystalline tJ-SiC films on silicon substrate
with sputtered SiC intermediate layer. J. Electrochem Soc., 127(12)
(1980), 2674-80.
23. Nishino, S., Powell, J. A. & Will, H. A., Production of large-area
single crystal wafers of cubic SiC for semiconductor devices. Appl.
Phys. Lett., 42(5) (1983), 460-2.
24. Furukawa, K., Higashigaki, Y., Harada, S., Suzuki, A., Nakajima,
S. & Inoguchi, T., Epitaxial growth of tJ-SiC single crystals by
successive two step CVD. Sharp Technical Journal, 27 (1983),
27-31.
25. Suzuki, A., Furukawa, K., Higashigaki, Y., Harada, S., Nakajima,
S. & Inoguchi, T., Epitaxial growth of tJ-SiC single crystals by
successive two-step CVD. J. Cryst. Growth, 70 (1984), 287-90.
26. Furukawa, K., Uemoto, A., Fujii, Y., Shigeta, M., Suzuki, A. &
Nakajima, S., Selective growth and Schottky diode characteristics of
tJ-SiC single crystal-films on Si (111) substrates by chemical vapor
deposition. Extended Abstracts of the 19th Conference on Solid
State Devices and Materials, Tokyo, 1987, pp. 231-4.
27. Miyazawa, T., Yoshida, S., Misawa, S. & Gonda, S., Molecular and
ion beam epitaxy of 3C-SiC. Appl. Phys. Lett., 45(4) (1984),
380-2.
28. Kaneda, S., Sakamoto, Y., Nishi, C., Kanaya, M. & Hannai, S.,
The growth of single crystal of 3C-SiC on the Si substrate by the
MBE method using multi electron beam heating. Jpn J. Appl.
Phys., 25(9) (1986), 1307-11.
74
29. Berman, I., Marshall, R. C. & Ryan, C. E., Annealing of sputtered

p-SiC. In Silicon Carbide-1973, 1974, pp. 42-50.
30. Addamiano, A. & Sprague, J. A, Buffer-layer technique for the
growth of single crystal SiC on Si. Appl. Phys. Lett., 44(5) (1984),
525-6.
31. Fujiwara, Y., Sakuma, E., Misawa, S., Endo, K. & Yoshida, S.,
Epitaxial growth of 3C-SiC on Si by low-pressure chemical vapor
deposition. Appl. Phys. Lett., 49(7) (1986), 388-90.
32. Furumura, Y., Doki, M., Mieno, F. & Maeda, M., Characteristics
of P-SiC films grown from a SiHCh-CHr H 2 System. Trans. Inst.
Electronics Comm. Engrs, Japan J., 69(6) (1986), 705-14.
33. Shibahara, K., Saito, T., Nishino, S. & Matsunami, H., Inversion-
type N-channel MOSFET using antiphase-domain free cubic-SiC
grown on Si (100): Extended Abstracts of the 18th International
Conference on Solid State Devices and Materials, Tokyo, 1986, pp.
717-18.
34. Akagi, Y., Morita, T. & Nakajima, Y., Recent trends of
characterization for electronic materials. Sharp Technical Journal,
36 (1986), 7-16.
35. Carter, C. H., Jr, Davis, R. F. & Nutt, S. R., Transmission electron
microscopy of process-induced defects in P-SiC thin films. J. Mater.
Res., 1(6) (1987),811-19.
36. Akagi, Y., Furukawa, K., Uemoto, A, Suzuki, A, Nakajima, Y.
& Nakajima, S., ESR study on residual carrier in CVD grown cubic
SiC. Abstract. Ann. Meeting of Physical Society of Japan, 1987, p.
160.
75
4 Silicon Carbide
Prepared by Chemical
Vapor Deposition
TOSHIO HIRAI &
MAKOTO SASAKI
ABSTRACT
The high-temperature properties of silicon carbide prepared by

chemical vapor deposition (CVD) are superior to those of
normally sintered and hot-pressed SiC. The structure, characteris-
tics and uses of CVD SiC are reviewed. CVD in-situ composites
and CVD functionally gradient materials are also described.
4.1 INTRODUCTION
Silicon carbide (SiC) has attracted attention as a high-

temperature semiconductor and as a high-temperature structural
material because of its superior resistance to heat, oxidation,
corrosion and thermal shock. Together with ShN4 , it is one of the
representative fine ceramics. 1--4
Because of its strong covalency, SiC is difficult to sinter. In
order to obtain a dense SiC compact, therefore, research is being
conducted on various molding technologies. 5,6
With pressure-less sintering (NS), 0·4-1·0% Band 0-0·9% Care
added as sintering aids to a submicron P-SiC powder, with
sintering at 2293-2373 K providing a sintered body with relative
density of at least 95%.7 With this method it is relatively easy to
produce compacts with complicated shapes, but there are
restrictions on the sintering conditions required to produce dense
compacts, and the strength of the sintered compacts decreases at
high temperatures.
77
Toshio Hirai, Makoto Sasaki
With reaction sintering (RS) , a mixed powder of a-SiC and

C is heated to 1673 K in Si vapor to form an SiC compact by
the direct reaction of C and Si. 8 With this method, however, it is
difficult to obtain dense, high-strength compacts.
With recrystallizaion (RC), fine and coarse SiC powders are
mixed, a green body is formed, and by recrystallizing this green
body at 2373-2773 K an SiC compact possessing 18% pores is
produced. 9 As for reaction sintering, however, it is difficult to
produce compacts having high density and strength by this
method.
With hot-pressing (HP) , 1% AI might be added to an SiC
powder and the resulting mixture hot-pressed at 2273 K under
36 MPa,1O or B4C might be added and the resulting powder
hot-pressed at 2223 K under 69 MPa. l l With this method it is
possible to obtain dense, high-strength SiC compacts, but in
general it is limited to simple shapes.
The sintering methods described above generally require
temperatures of 2000 K and above, and voids and sintering aids
are often contained in the sintered body. With the CVD method,
on the other hand, a gas containing Si and C is used as the raw
material, and a solid is synthesized directly from the vapor
without passing through a sintering process. As a result, SiC
compacts possessing theoretical density can be obtained at far
lower temperatures than are required for sintering and without
the addition of sintering aids. CVD SiC thus possesses properties
superior to those of sintered SiC, and in recent years the
application of this material in a variety of areas has been studied.
This chapter will offer an overview of CVD SiC synthesis
conditions as well as the structure, properties and applications of
CVD SiC. In addition, future developments in CVD SiC will be
discussed.
4.2 CVD SiC SYNTHESIS
4.2.1 Synthesis Device

The equipment used for synthesizing SiC using the CVD method
is described in detail in the references,12 so only a brief
description will be provided here. The basic elements comprising
a CVD device include a gas inlet system, a reactor furnace, an
78
SiC Prepared by Chemical Vapor Deposition
Table 4.1
Ga Specific Boiling Vapor pressure Source Gases
gravity point (O"C, kgf/cm z) Used in Synthesis
(air =1) ("C)
ofCVDSiC
SiC!. 5·86 57·6 0·106
SiHCI3 4·68 31·8 0·296
SiH2Q 2 3·52 8·4 0·829
SiR. 1-11 -111·9 24·2
Si2~ 2·26 -14·5 1·86
Sif4 3·63 -95·5 103·5
Si2F 6 6·00 -19·1 2·5
SiHF3 2·97 -95·0 19·78
SiH2F2 2·35 -77·8 25·3
SiH3F 1·73 -98·0 53·2
CR. 0·56 -161·5
~H2 0·91 -75·0 3·47
C!. 77 0·046
CF4 3·05 -128 3·87
~H8 1·55 -42·1 4·89
exhaust system, a waste gas treatment system, a heating system,

a temperature measurement system and a control system.
The gas inlet system controls source gas and carrier gas flow
rates and blend ratios. In the case of liquid raw materials such as
CH3SiCl3 and CC~, vapor pressure is adjusted with a
temperature-controlled reservoir, and the liquid is sent using a
carrier gas. Table 4.1 shows typical source gases.
As shown in Fig. 4.1, there are two types of reactor furnace:
(a) Cold-wall systems (b) Hot-wall systems Fig. 4.1.

Classification and
Substrate Heater schematic dia-
L...-_ _ ~ Electrode I ~l Substrate
grams of reactor
furnaces.
EXha:-B>S-OUrce gas (a) Cold-wall
I=:::::><::::: I systems; (b)
hot-wall systems.
t _'<on. OO~~
~
o0
0000,
0 ~~
Substrate II ru r-
1:: ~
00000
Substrate
79
Toshio Hirai, Makolo Sasaki
the hot-wall variety, which heats the base material indirectly, and
the cold-wall variety, which heats the base material directly such
that the reactor walls do not heat up. The cold-wall setup is
preferable when mutually reactive gases are used or as a
small-scale experimental device. In the case of SiC, however, no
mutual reactivity is present between the raw material gases used,
so hot-wall systems are most often used. The hot-wall system is
well-suited to coating a substrate with a complicated shape, and
it is excellent for mass production. One disadvantage, however,
is the attachment of precipitates onto the outer walls. Whatever
the type of system, however, the flow of gas has a large impact
on SiC formation, so it is important to carefully design the
furnace structure (in the region of the substrate) according to the
purpose for which it will be used. Reactor furnaces available
include horizontal, vertical, and bell jar varieties.
The exhaust system is required for removal of residual gases
from the reactor furnace, control of the gas flow, and pressure
reduction of the reaction furnace. The exhaust pumps used for
CVD often have superior corrosion resistance and include
oil-circulating pumps, water-sealed pumps, and dry pumps.
The waste gas treatment system treats gases formed by the
reaction, unreacted gases, and the carrier gas. In recent
semiconductor manufacturing plants exhaust pollution has be-
come a major problem, and thorough treatment of the waste gas
requires a far greater capital investment than the CVD
equipment itself.
Heating methods include direct electrical heating, bigh-
frequency induction heating and laser heating. Thermocouples,
optical pyrometers and radiation thermometers can be used to
measure the temperature of the substrate, and the one to use
must be selected according to the gas pressure inside the reaction
furnace.
4.2.2 Synthesis Conditions

The synthesis of SiC using CVD may involve the use of a raw
material containing both Si and C in a single molecule or the Si
and C may be supplied from separate substances. Table 4.2 gives
the commonly used source gases and synthesis temperatures. 12
80
Synthesis temperature 110 2 K Table 4.2

Source gas Ref.
12 14 16 18 20 22 Source Gases and
CH3SiCl3/H2 (13) Synthesis Temp-
Si and C
CH3SiCl3/H2 (14) erature of CVD
are supplied
(CH3)2SiCl2/H2 --- (15) SiC12
from the
(CH3)3SiCl/H2 -- (15)
.
same
(CH 3 )4 Si/H 2, He (16)
compound
(17)
.
CH~iHCl2/H2
Si and C SICl4,C~/H2 (18)
.
are supplied
SiCl 4 ,C3 Hal H2 (19)
from (20)
SiCl 4 ,CeHw/H 2
different (21)
SiCl4,C7Ha/H2
compounds SiCl4,CCl4/H2 - (22)
Figure 4.219 shows an example of synthesis conditions

(100 kPa) for the SiC4-C3Hs system (SiCI4 flow rate: 2·9 x
10-6 m3 S-1; H2 flow rate: 1·2 x 10-5 m3S-1). The higher the
temperature and the larger the ~Hs gas flow rate, the easier C
forms with SiC. As a result, synthesis conditions must be
carefully established in order to produce high-quality CVD SiC.
The authors used a cold-wall reaction furnace with SiCl4 and
C3HS as raw material gases and succeeded in synthesizing CVD
SiC at a maximum synthesis rate of Q·39J.Ulls- 1 (1'4mmh- 1)
under temperatures of 1573-2073 K and pressures of 4-
l00kPa. 19
2100...-----------------,
Fig. 4.2. CVD
:!: 2000 SiC synthesis
~
conditions. 19
.;:l 1900
~
Co 1800
~
III 1700
'iii
QI
~ 1600
6i'
1500
2 4 6 8 10 12 14 16
81
4.3 STRUCTURE AND PROPERTIES OF CVD SiC
4.3.1 Structure
As shown in Fig. 4.3, there are two types of surface structures in
CVD SiC: the facet structure (a) in which the crystal surface of
each particle is apparent; and the pebble structure (b) which
consists of hemispherical projections and recessions. The former
type has good crystallinity and is generally obtained under low
Fig. 4.3.
Morphology of
CVDSiC. (a)
Facet morphol-
ogy; (b) pebble
morphology .
(a)
(b)
82
Fig.4.4. TEM
photomicrograph
of CVD SiC grain
boundary. 24
pressure. 23 Although it is held to be favorable for use in

semiconductor substrates, however, it suffers from low deposi-
tion rate.
The most remarkable difference between compacts of CVD
SiC and sintered SiC can be seen on the grain boundaries. As
shown in Fig. 4.4, there are absolutely no foreign substances
present on the grain boundaries in CVD SiC. 24 This is thought to
be the source of its high-temperature strength, to be described
later.
CVD SiC obtained under ordinary conditions is of the f3
crystalline type, and it generally has (111) and (110)
orientations. 23 Figure 4.5 shows the temperature dependence of
Fig. 4.5.
<110> Temperature
t
<110> dependence of
[0001]
~ t CVD SiC crystal
I
[0001] <111 > ~ growth. 23
t t -"~o"
~ <1~0> ~,~
.ffi.
~~O'
I' .....
~ 3C t:' 6H
1700 1800 1900 2000 2100 2200
Temperature/K
83
CVD SiC crystal growth. 23 At temperatures of less than 1873 K,

(111) fJ-SiC is formed, while at temperatures of 1873-2073 K
(110) fJ-SiC is formed. At temperatures exceeding 2073 K a-SiC
is formed.
CVD SiC has a density of approximately 3·2 x 103 kg m- 3 ,
which corresponds with the theoretical value.
4.3.2 Properties
The properties of CVD SiC are shown in Table 4.3. 12 ,18,23,25-27
Hardness is strongly influenced by growth orientation, with (111)
varieties having higher hardness than the (110) type. This
phenomenon is related to the slip system. 28
Figure 4.6 shows strength as measured by three-point bend
test. 26,27 CVD SiC thin films have a maximum bending strength
of approximately 1300 MPa, and no reductions are seen in this
strength even at temperatures exceeding 1000 K. 27- 3O The
difference in bending strength between CVD SiC thin films and
bulk is thought to be related to internal stress and deformation
mechanisms within the film.
Table 4.3
Properties of Property Catalog Reference Ref·
CVDSiC values" values
Thermal conductivity / 67-71 58-70 (18)
J. m- I • S-I • K- 1
Thermal expansion 4·4-4·9 4·9b (23)
coefficient/10-6 K- 1
Specific 1-14
resistance/l0- 2 Q . m
Hardness GPa 27-34 (HK) 31(HV) (25)
Three-point bending 200-690 800 (25)
strength MPa
Tensile strength MPa 590
Young's modulus GPa 320 275-465 (26), (27)
Fracture strength MPa 650 (25)
Fracture toughness 3·8 (25)
MN. m- 312
"Toyo Carbon, Mitsui Engineering & Shipbuilding, Toshiba Ceramics,

Nippon Carbon.
b Mean value for 293-1273 K.
84
1200 Fig. 4.6.

- - CVD SiC thin film Comparison of
bending strength
1000 ------- CVD SiC bulk
by SiC synthesis
- - - HP SiC method. 26,27
~ 800 - - - - RS SiC
:I
.c
....
C>
c:
600
....~
Vl
400
20~0=0::--4:-:00=-=--:6~0:-::0--::8:=0=0-;;10t:0:-::0:-:1::::2':::"00:::-:1:740:::0~16::';:0:-::0---;::!1800
Temperature/K
As shown in Fig. 4.7, the highest fracture strength and fracture

toughness values can be obtained with a particle size of 1-3 J.l.m. 29
Control over the microstructure makes possible further improve-
ments in strength and toughness.
The crystallites of a CVD SiC ceramic synthesized at 1773 K in
the system SiC~-~H8-H2 contain numerous observable stacking
faults. Figure 4.8 is a TEM photomicrograph showing the mutual
interaction of stacking faults and cracks in the CVD SiC
crystallite. The introduction of stacking faults into the CVD SiC
crystallite brings a change in the direction of the crack's progress,
Fig. 4.7. CVD

4.5 ~
SiC particle size
700 'l'
~ E versus mechanical
Z properties.28
~
:5Ol 600 4.0 ~
!:!
c "''''''''----..... , l<:
....CII~ ,/ "" ", , ui
CIl
I...
500 , ,, 3.5 .c
Ol
IDc
....u
~
I
I
I
\ ...
~
0
"'
I...
lJ..
400
I
I
\
\
\ 3.0
~
...u
~
\
300
\
\l "'
I...
lJ..
2.5
200~0~~---~~--~1~0---~10~0~
Mean particle size 111m
8S
Fig. 4.8.
Interaction of
stacking faults
and cracks in
CVDSiC. 32
Fig. 4.9.
Temperature D SiC single crystal
dependence of -o-} CVD SiC
thermal conduc- ----- HP SiC
tivity in SiC. 34 g>(3S) -~-! RS SiC
RC SiC
(32) (36) _ ..- NS SiC
102
~.
\ ..... (44)
:::::.: . . . _
(41)
(39)
-- ....... ~ ';"'--./ (27)
- -- -:- .. ~".~.""'-o.... (1S)
~""""''''''-~:-~-~:;::::~~~L
>(46~ -\..:-;:- ._ . ~ .-
... ---·_·r ·-
:.:. . .::~::;{)
.................. ./37) (35) -(47)
~~.~.~...... ::~~..
(40) ~, . 0f0
......-.~ .\
10' (45) .....- ......- (43)
J .....-.""'
. -.
--
)1S) (4S) .. _ .. -
.> c" .. .J- .. --
.,.". .."......-_ .. ..
200 400 600 SOO 1000 1200 1400 1600

Temperature I K
86
1.4 Fig. 4.10.

Temperature
dependence of
specific heat in
1.2 SiC. 34
':.:
l~
-
...,
./II...
III
r.
1.0
¥ 0.8 - CVD SiC

'u ----- HP SiC
8-
III _.- HP SiC (20wt% free C)
0.6 ~(49) o RC SiC
400 600 800 1000 1200 1400 1600

Temperature / K
i.e. it results in crack deflection, thereby causing an increase in

fracture toughness (KId from 3·1 to 6.8 MN m- 312 • 31 ,32
At high temperatures CVD SiC possesses much greater
resistance to oxidation than sintered SiC. 33 SiC is next to only
diamond and c-BN in terms of thermal conductivity, and as
shown in Fig. 4.9 the thermal conductivity of SiC tends to
decrease as the temperature rises. 34 CVD SiC containing 3% free
carbon has a thermal conductivity one order of magnitude lower
than pure CVD SiC. 18
As shown in Fig. 4.10, the specific heat of SiC increases with
temperature from 0·63-0·67 J g-1 K- 1 at room temperature to
1·30-1·34 J g-1 K- 1 at 1573 K. In addition, the presence of free
carbon in the SiC increases the specific heat. 50
4.4 APPLICATIONS OF CVD SiC
4.4.1 Heat- and Corrosion-resistant Coatings

SiC is used as a coating on a variety of shapes in order to
improve resistance to heat and corrosion. It can be used on the
inner surfaces of cylindrical base materials for use as heat-
resistant nozzles or corrosion-resistant tubes, and it can be used
87
Fig. 4.11. CVD·SiC

Susceptor for
semiconductor
manufacture.
~' ....... ,
'. : . : .. '. ;. '. '.
I
/
. "". ....
,'
.... '
' '.
Graphite
on the outer surfaces of graphite or ultrahard alloys for use as

susceptors, tubes and glass molds. Figure 4.11 is an example of
such a susceptor. In order to prevent contamination from the
graphite, which is used as a heating susceptor during deposition
on an Si wafer, the graphite is coated with SiC to a thickness of
from several tens to approximately 100 J.UIl. In this case, the SiC
must be a high-purity variety containing no free carbon or Si. In
addition to graphite, a variety of ceramics can be coated with SiC
for heat and corrosion resistance. When washing a susceptor
coated with SiC, care must be taken to prevent damage to the
SiC surface from an acidic cleaning agent (chemical damage) or
ultrasound cleaning (physical damage).
4.4.2 Fiber-reinforced Composite Materials

Using void-containing ceramics as a base material, the technique
in which a bulk is synthesized by filling these voids with CVD
and densifying is specifically referred to as CVI (Chemical Vapor
Infiltration or Chemical Vapor Impregnation).52 Since the vapor
must penetrate and deposit in the voids, deposition rate is
sacrificed and the process is conducted at low temperatures under
low pressure.
A method of fabricating composite materials is known in which
tungsten or carbon fibers are coated with SiC by CVD, the fibers
are aligned, and the CVI technique described above is used to
impregnate and deposit the SiC. The bending strength of
composites produced by this method is at least 1000 MPa, much
higher than for other SiC materials. The direction lying at right
angle to the fibers, however, poses some problems. As shown in
Fig. 4.12, a composite containing 30 vol. % SiC has markedly
improved resistance to oxidation. 52 This technique has been
applied to the prevention of oxidation in refractories, nuclear
fuel materials, and the C-C composites used in the aerospace
industry.
88
Fig.4.U.
Oxidation resis-
4 - - - Sepcarb 40 base tance of CVI SiC
material
------Sepcarb 10 base
in air2 (Sepcarb
material 40: C-C compos-
ite with a pore
diameter of
100 !1IIl; Sepcarb
C-C composite before 10: C-C compos-
CVI SiC filling ite with a pore
(porosity: 30 vol '1.)
diameter of
several !1IIl).
C-C composite afte

CVI SiC filling
,77 3 'f.. I
1773K _ - - - ...
- - - - -'373K
----------
o 0.5 1.0
Time I hr
4.4.3 Gas Turbine Materials

In order to utilize thermal energy effectively, the operating
temperatures of such components as heat exchangers and gas
turbines must be as high as possible, making necessary the
development of new high-temperature structural materials.
Among metals, metal-metal compounds, and ceramics special
hopes have been placed in Si3N4 and SiC as high-temperature gas
turbine materials. 53
Such materials greatly fulfil conditions including strength,
corrosion resistance (i.e. resistance to oxidation), and resistance
to creep. From this standpoint, therefore, a great deal of
attention is being focused on CVD SiC. 54
In order to fabricate a CVD SiC turbine rotor, a graphite rotor
mold is first prepared and coated with tungsten using CVD.
Unnecessary graphite is removed by oxidation, and after coating
the mold with SiC using CVD the tungsten is removed by acid
treatment. 55 Tests showed the CVD SiC rotor capable of
operation for 1000 h at 1873 K and 206 MPa. 27
89
Bulk CVD SiC is promlsmg because its strength does not

decrease as much at high temperatures as that of sintered SiC,
and the high-speed synthesis of CVD SiC has become the subject
of much research.
4.4.4 Mirrors
Mirrors for high-output IR lasers must satisfy conditions such as
a lack of absorption, large thermal conductivity, light weight and
low cost. In the past, Cu and Cu-AI alloys were used in mirrors.
Because of the poor shape stability of these materials, however,
a technique of coating sintered SiC with CVD SiC, grinding and
polishing, then coating with Cu by sputtering has been under
investigation. 57 Because sintered SiC contains residual pores, a
true mirror surface is impossible to obtain. Although the mirror
characteristics can be improved with hot-pressed SiC, large
pieces cannot be produced. As a result, attention is being drawn
to CVD SiC.
For mirrors in the vacuum ultraviolet spectrum utilizing high
reflectance and low scattering, Al is usually coated with MgF2.
Because of the large electrical conductivity of CVD SiC,
however, the use of uncoated CVD SiC is being studied. In this
case, a CVD SiC film with thickness of several hundred IJ.m is
Fig. 4.13.
Reflectance ver-
sus photon energy
in CVD SiC and
AuS6 (angle of Au
incidence: BOO). ,
-',,
ell
u ..
,
,
C
III I
ti 0.5
ell
;:: \CVD.SiC
ell I
Q: I
,
I
,,
I
I
~ ,., .
... , -\
~ J\_. .,.,-'" \.. .-_ . . -.. . .,. .
1/
'I
o 50 100 150 200

Photon energy leV
90
polished to a mirror surface with surface smoothness of 3-16 A.

As shown in Fig. 4.13, CVD SiC is characterized by the fact that,
with an incident angle of 800 , it ceases to reflect at energies of
100eVor greater. This makes it attractive as a high-energy cutoff
mirror as well. S7
4.4.5 Semiconductors
SiC electronic elements are being reconsidered for use as
environment-resistant elements, and active research is being
conducted. SiC possesses more than a 100 crystal polytypes, with
representative crystal structures including 3C, 2H, 4H, 6H and
15R. The bandgap at 300 K is 2·20 eV for 3C, 3·2 eV for 2H, and
2·89 eV for 6H, making it an indirect semiconductor. S8 One
application of SiC as an optical element, taking advantage of its
broad bandgap, is its use in blue light-emitting elements. For this
application 6H SiC, with a bandgap of 2·8 eV, is well-suited.
Methods of fabricating a pn junction using a 6H SiC substrate
include diffusion, S9 liquid-phase epitaxy ,tj() and doping during the
crystal growth process. 61 ,62 Since the diffusion method requires
diffusion temperatures of 2373-2673 K, however, epitaxial for-
mation of a pn junction at temperatures of 1923-2073 K is
advantageous. Because cubic and hexagonal SiC may, depending
upon the conditions, coexist on the 6H SiC substrate,63 it is
possible to achieve epitaxial growth on a 6H SiC substrate by
increasing the temperature and reducing the concentration of the
source gas.64
4.4.6 Fine Powders

In recent years ceramics in the SiC system have attracted
attention as high-temperature, heat-resistant materials and as
high-thermal-conductivity ceramics. Among the methods used by
industry of synthesizing raw material powders for these ceramics
is the crushing of bulk SiC which has been fabricated by the
direct silicification of C or the reduction of silicon oxides. 6S These
methods, however, require a crushing step, which suffers from
several drawbacks such as the difficulty of manufacturing fine
powders or powders with controlled particle size and the
introduction of impurities.
91
On the other hand, SiC powders fabricated by CVD are

receiving attention as raw materials for ceramics. Research is
being conducted on the synthesis of SiC powders by direct
thermal decomposition, which uses a mixed gas such as
CH3SiCh, Si~, SiC4, or C~, plasma CVD, and photo-
excitation CVD and on the sinterability of the resulting
powders. 66 When a mixed gas of H2 and Ar is used as a carrier,
C-rich SiC powder can be obtained. 67 With a low deposition
temperature, Si codeposits. 23
Recently, attention has been focused on composite powders
(the so-called 'nanocomposites,)68 such as SiC-B, using CVD or
arc plasma CVD to disperse B in the SiC particles,69 SiC-C,
prepared by the arc plasma method,1° and amorphous Si-C-N,
prepared by thermal CVD. 71 Samples prepared by sintering an
SiC-B composite powder containing 1·0 wt% B at 2423 K
exhibited a mean three-point bending strength of 640 MPa at
room temperature and 680 MPa at 1773 K.70 The Si-C-N
composite powder shows a complex crystallization process,72 and
a sample prepared by hot-pressing an already crystallized powder
showed a mean three-point bending strength of 780-880 MPa at
room temperature. 71
4.5 FUTURE DEVELOPMENTS
Recently, a great deal of interest has been shown in so-called

in-situ composite materials using CVD SiC as a matrix and in
functionally gradient materials, whose composition changes
continuously from SiC to C.
4.5.1 CVD of SiC-matrix in-situ Composites

Although SiC synthesized by the CVD method possesses
numerous merits, it suffers from insufficient thermal shock
resistance, one of the properties unique to SiC, and low fracture
toughness. As one means of overcoming these problems, there is
a method in which another gas is introduced during ceramic
synthesis by CVD to perform the material formation process
simultaneously with compounding. 68 Composites produced using
this technique are referred to as CVD in-situ composites, and
due to the fact that their dispersion phase is at several nm
Fig. 4.14.
Friction pro-
perties of CVD
6 w CVD SiC-C SiC-C composite
ceramic. 74
o CVD SiC
e
.E 4
° NS SiC
iii
c
o
"';;
u
f 2 Seizure Seizure
c;'q. \_..-q. w_'i -'___i .

_ _ c_c-~~o_o-o-o
w
010 20 30
Surface pressure IMPa
extremely small they are also called nanocomposites. The

appearance of new properties in these materials is expected. 73
The authors have synthesized bulk composite ceramics in the
SiC-C,14 Si-C-Ti,15 and Si-C-B76 systems. CVD SiC-C
consists of soft C grains dispersed in high-hardness CVD SiC and
is promising as an abrasion-resistant material. 74 Figure 4.14
shows the friction characteristics of CVD SiC-C. Abrasion tests
were performed under the following conditions: friction rate
8 m s-1, lubricant supply volume 3·3 x 10-8 m3 S-I, initial pres-
sure 2 MPa. As shown in the Fig. 4.14,74 seizure occurred at 21 MPa
for the sintered SiC and 27 MPa for the CVD SiC, while no
seizure was observed for the CVD SiC-C within the scope of the
experiment. From these results it can be seen that CVD SiC-C
has better abrasion resistance than CVD or sintered SiC.
Fracture toughness K IC for a CVD SiC-TiC composite ceramic
as measured by the indentation method was at least 10 MN m -312 ,
with compounding bringing significantly higher toughness than the
values for SiC (4) or TiC (3).75
4.5.2 SiC/C Functionally Gradient Materials

In conventional composite materials, a uniform dispersion phase
and properties, or so-called 'uniform functionality', has been
93
pursued. In functionally gradient materials, the morphology,

texture, structure and other 'elements' of the dispersion phase
are continuously controlled and are non-uniform. With such
materials it is possible to invest a single material with two or
more desired functions. 77
One example of such a material is thermal stress relaxation
materials. These materials require not only oxidation resistance,
high strength and corrosion resistance but also workability and a
large thermal conductivity. Typical materials capable of fulfilling
these conditions are SiC for the former group of properties and C
for the latter group. When a SiC sintered body and a graphite
plate are joined (although this is extremely difficult in practice),
stress develops on the SiC-C interface, and cracks are formed in
the region of the joining surface. In order to join the SiC and C
phases while minimizing the generation of stress, a technique is
being investigated in which CVD is used to gradually and
continuously shift the composition from SiC to C. 77 ,78
By using SiCl4 and C3H8 as raw material gases, keeping the
flow rate of ~H8 gas constant, and varying the amount of SiC4
introduced together with synthesis time, it is possible to produce
an SiC/C functionally gradient ceramic at 1773 K. Figure 4.15 is a
Fig. 4.15. Cross-

sectional SEM
photomicrograph
ofCVDSiCC
functionally gra-
dient material
(the lower portion
is SiC and the
upper portion C;
the ratio of SiC to
C continuously
chan.ges there
between).
94
cross-sectional SEM photomicrograph of an SiC/C functionally

gradient material formed on a graphite substrate. Dense CVD
SiC with a thickness of 2 x 10- 4 m (200 J.Lm) was formed on the
graphite substrate and a CVD SiC/C phase of thickness
1·9 x 10- 3 m (1·9 mm) and containing voids was then formed on
top of the first film. In this region, the ratio of SiC to C changes
continuously, and by adjusting the orientation of SiC it is
possible to control the number of voids. Finally, a CVD C film of
thickness 1·3 x 10- 4 m (130 J.Lm) is formed on top of the other
two films.79
Research has begun on functionally gradient materials which is
promoted as a national project, with the objective of developing
thermal-stress-relaxing thermal-barrier materials, a technology
necessary to space vehicle development efforts. Future develop-
ments are awaited.
4.6 SUMMARY
Characteristics of CVD, an effective method for obtaining

powder compacts, were outlined with an emphasis on the
structure, properties and applications of CVD SiC.
The synthesis of materials by CVD has come to be used by
many corporations. In most cases, this involves the relatively
easy-to-synthesize CVD SiC. With a few exceptions, however,
applications for CVD SiC remain in the development stage.
Materials development must constantly respond to the changing
demands of the age. In this sense, CVD SiC materials such as
in-situ composites and functionally gradient materials, estab-
lished based on a concept of materials design, are likely to attract
even greater attention in the future.
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42. Washburn, M. E. & Bart, R. K., Am. Ceram. Soc. Bull., 44 (1965),
555.
43. Norton, F. H., J. Am. Ceram. Soc., 10 (1927), 30.
44. Forrerst, C. W., Kennedy, P. & Shennan, J. V., In Special Ceramics
5, ed P. Popper. The British Ceramic Research Association,
London, 1972, p. 99.
45. Lezhenin, F. F. & Gnesin, G. G., Porosh. Metall., No.2 (1967),36.
46. Price, R. J., J. Nucl. Mater., 46 (1973), 268.
47. Zeigarnik, V. A., Peletskii, V. E. & Gnesin, G. G., Porosh.
Metall., No.9 (1969), 40.
48. Wilkes, G. B., J. Am. Ceram. Soc., 17 (1934), 173.
49. Torti, M. L., Alliegro, R. A., Richerson, D. W., Washburn, M.
E. & Weaver, G. Q., Proc. Brit. Ceram. Soc., No. 22 (1973),
129.
50. Walker, B. E. Jr., Ewing, C. T. & Miller, R. R., J. Chem. Engng
Data, 7 (1962), 595.
51. Kelly, K. K., J. Am. Ceram. Soc., 63 (1941), 1137.
52. Christin, F., Naslain, R. & Bernard, C., Proc. 7th Int. Conf. on
Chemical Vapor Deposition, ed. T. O. Sedgwick. The Electrochem-
ical Society, New Jersey, 1979, p. 499.
53. Godfrey, D. J., Proc. Brit. Ceram. Soc., 22 (1973), 1.
54. Gulden, T. D., J. Am. Ceram. Soc., 52 (1969), 585.
55. Alliegro, R. A., In Ceramics for High-Performance Applications,
ed. J. J. Burke, A. E. Gorum & R. N. Katz. Brook Hill Publishing
Co., MA, 1974, p. 253.
56. Rehn, V. & Choyke, W. J., Nucl. Instrum. Methods, 177 (1980),
173.
57. Choyke, W. J., Farich, R. F. & Hoffman, R. A., Appl. Opt., 15

(1976), 2006.
58. Matsunami, H., Oyo Buturi, 48 (1979), 565.
59. Kroko, L. J. & Milnes, A. G., Solid-State Electron., 9 (1966),1125.
60. Brander, R. W. & Sutton, R. P., Brit. J. Appl. Phys., 2 (1969), 309.
61. Giffiths, L. B. & Mlavsky, A. I., J. Electrochem. Soc., 111 (1964),
S05.
62. Gramberg, G. & Koniger, M., Solid-State Electron. 15 (1972), 285.
63. Jennings, V. J., Sommer, A. & Chang, H. C., J. Electrochem. Soc.,
113 (1966), 728.
64. ChampbeU, R. B. & Chu, T. L., J. Electrochem. Soc., 113 (1966),
825.
65. Kijima, K., J. Mater. Sci. Soc. Japn, 19 (1982), 12.
66. Okabe, Y., Hojo, J. & Kato, A., J. Less-Common Met., 68 (1979),
29.
67. Ford, L. H., Hibbert, N. S. & Martin, D. G., InJ. Nucl. Mater., 45
(1972/3), 139.
68. (a) Hirai, T., Textbook of Primer of New Inorganic Materials. The
Japan Society of Powder and Powder Metallurgy, 1981, p. 63; (b)
Hirai, T., Sasaki, M. & Niino, M., J. Soc. Mater. Sci. Japn, 36
(1987), 1205.
69. (a) Kondo, J. & Saiki, G., Proc. 24th Symp. Basic Sci. Ceram., The
Ceramic Society of Japan, Tokyo, Japan, 1986, p. 83; (b) Chen, L.,
Goto, T. & Hirai, T., Abstract Int. Symp. on Sci. and Tech.
Sintering, Elsevier Science Publishers, New York, 1987, p. 428.
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1986, p. 13.
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Shitara, T., Hakkai, K., Hirai, T. & Niihara, K., J. Ceram. Soc.
Japn. 95 (1987), 81.
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Inst. Met., 1987, p. 551.
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Ceramics, ed. R. E. Tressler, G. L. Messing, C. G. Pantano & R.
E. Newnham. Plenum Press, New York, 1986, p. 165.
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Proc. 95th Meeting of Japan Inst. Met., 1984, p. 149.
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p.192.
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Relaxation and Function Emergence by Fine Composites. Mitsubishi
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Ceram. Soc. in Tohoku-Hokkaido Branch, 1987, p. 39.
98
5 Continuous Silicon
Carbide Fibers
KIYOHITO OKAMURA
ABSTRACT
SiC fibers were prepared from polycarbosilane which was synthes-

ized by three methods. The molecular structure of each polycar-
bosilane was presented using three structural elements determined
by IR and NMR spectral measurements. The polycarbosilane-SiC
fiber pyrolytic process was estimated from TG-DTA, gas
evolution analysis and X -ray diffraction measurement, and the
relationship between tensile strength and the pyrolytic process was
discussed.
5.1 INTRODUCTION
Since SiC fibers were first synthesized from organosilicon

polymer polycarbosilanes,1,2 there has been active research
on the preparation of ceramic materials using organic metal
polymers. SiC, SiC-B4C, Si3N4, and Si-Ti-C-O have been
synthesized from polysilastyrene,3 polysiloxane,4 polysilazane,s,6
and polytitanocarbosilane,7 respectively. The method of prepar-
ing ceramic materials from organometallic polymers is called the
precursor method. This technique is characterized by the ease
with which organometallic polymers can be made into fibers or
thin films and the fact that shape can be maintained during
baking. As a result, it is easy to obtain ceramic fibers and thin
films consisting of SiC and Si3N4, which are fundamentally
non-sinterable, and high-melting-point compounds such as
Ah03' SiC fibers have been prepared from polycarbosilane and
currently produced by Nippon Carbon Co., Ltd under the trade
Kiyohito Okamura
name Nicalon, and Si-Ti-C-O fibers prepared from polytitano-

carbosilane and produced by UBE Industries, Ltd under the
trade name Tyranno. These SiC system fibers possess high
strength and elasticity, are resistant to heat and oxidation, and
are thin and pliant with a diameter of 10-15!UD. In addition to
the precursor method, silicon carbide fibers (CVD-SiC) can also
be manufactured by chemical vapor deposition (CVD), in which
CH3SiHCh and Hz gas are used to precipitate SiC on the core of
a heated tungsten filament (diameter: 12·4 !J.m)8 or in which
CH3SiCl3 and Hz gas are used to precipitate SiC on the core of a
heated carbon fiber (diameter: 30 !UD).9 CVD-SiC fibers are
currently being manufactured and sold by Textron Specialty
Materials (TSM) (formerly AVCO Specialty Materials). CVD-
SiC fibers have a diameter of 14O!UD, making them thicker than
those produced by the precursor method, and they cannot be
woven into two- or three-dimensional 'fabrics'. However, they
offer superior tensile strength and Young's modulus. The most
promising application of these fibers is not as refractory materials
but rather as reinforcing fibers for plastics, metals and ceramic
composites. At present, both types of fibers are being used,
taking advantage of their respective properties. For example, an
SiC composite which has been reinforced with a two-dimensional
fabric of pliant Nicalon fibers possesses both high strength and
superior toughness. 10
This chapter will investigate the properties and molecular
structure of polycarbosilanes obtained under different synthesis
conditions and discuss the properties of SiC fibers synthesized
from these polycarbosilanes using the precursor method.
5.2 PREPARATION METHOD OF SiC FIBERS
5.2.1 Preparation of Precursor Polycarbosilane

Polycarbosilane, which is skeletoned by Si and C, the precursors
of SiC fibers, is prepared by a variety of methods, and numerous
types are available. These have been summarized in the
references. 11 Typical methods include using the thermal decom-
position of monosilane or polysilane, or reacting sodium-
containing vinyl silane or disilane with K or Na. At present, the
polymer which serves as the optimal precursor for SiC fibers is
100
Continuous SiC Fibers
CH3 Fig. 5.1.

I Preparation of
Cl-Si-Cl
I polycarbosilanes.
CH3
Oi methyld ichlorosilane
l+Na
CH 3
I
~Sitn
I
CH3
Polydimethylsilane
i I
Si-O-B
C6H5
I
C6H5
(PBOPSO)
t
....0
.... 0 n
N2 gas
flow
I I I I I I I I
-fSi-C+n- ~Si-C+'; -+Si-C+" ~Si-C+n
I I I I I I I I
(PC-TMS) (PC- B) (PC-N) (PC-A)
polycarbosilane prepared using the thermal decomposition and

condensation of polydimethylsilane, which in turn is made from
dimethyldichlorosilane. Polycarbosilanes prepared by a variety of
methods in the present laboratory are shown in Fig. 5.1. First,
the method of synthesizing polydimethylsilane will be discussed.
Na (410 g) was melted in a xylene solvent under a nitrogen
atmosphere and then dispersed at 100°C. In this state, 1 liter of
dimethyldichlorosilane was dripped for 45 min and the de-
chlorination performed for approximately 10 h to produce
approximately 420 g of polydimethylsilane (Mn, n=
approximately 30). The polydimethylsilane was thermally de-
composed and condensed in an autoclave at 450°C, 460°C, and
470°C for approximately 14 h to produce PC-A 450, PC-A 460
and PC-A 470 polycarbosilanes, respectively.
In addition, polydimethylsilane was thermally decomposed and
condensed at 470°C for 120 h under flowing nitrogen and
101
~
i -.<.
'g.
S·
r~
Table 5.1
Synthesis of Polycarbosilanes
PC Reaction Reaction Distillation Yield M. Elemental analysis (%)

time temperature temperature (%) (cm 3 g-1)
(6) ("C)
" Si C H 0" B
Pressure
("Clto")
PC-A450 14 450 150/1 66·3 730 1·71
14 450 280/1 50·8 1250
PC-A460 14 460 280/1 56·0 1450 47·13 36·99 7·00 0·84( <0·93)
PC-A470 14 470 105/1 66·4 860 1·94
14 470 200/1 59·7 1210 2·14
14 470 280/1 58·8 1680 2·46 48·18 39·92 6·85 0·81( <0·88)
PC-B3.2 10 350 280/1 50·0 1740 44·50 35·80 8·00 4·83( <1· 72) 0·02
PC-B5.5 10 350 320/760 64·8 1310 44·90 39·20 7·44 3·56«1·73) 0·06
PC-TMS 27 760 200/1 6·5 620
29 760 200/1 5·1 820 1·73
'.SS}
14 770 200/1 10·0 740 44·80 39·90 6·79 1·21(0)
16 770 200/1 6·5 930 1·76
21 775 200/1 9·3 830
a Calculated values in parentheses.
thermally decomposed and condensed at 350°C for 10 h with the

addition of 3·2% and 5·5% of polyborodiphenylsiloxane
(PBDPSO) to produce, respectively, polycarbosilane, PC-N 470,
PC-B 3·2, and PC-B 5·5. For reference, tetramethylsilane (TMS)
was circulated for 14 to 29 h in a quartz tube heated to
760-775°C by the method of Fritz & Mate to produce
polycarbosilane and PC-TMS.u The conditions for synthesis of
these polycarbosilanes are shown in Table 5.1. 12
5.2.2 Synthesis of SiC Fibers

SiC fibers were formed by melt-spinning polycarbosilane at
approximately 300°C, unfusing with thermal oxidation (110-
200°C), and baking at 1000-1500°C under a flow of inert gas.
This method is illustrated in Fig. 5.2. Melt spinning was
performed by the monohole spinning method. PC-B system
polycarbosilane fibers can produce relatively small fiber dia-
meters, and unfusing was possible at low temperatures. 12
5.2.3 Method of Measurement

In order to identify the properties and molecular structure of
polycarbosilane, number average molecular weight (Mn) was
t I'
Si-
I
I+.
C
I n
polycarbosilane
Fig.S.l.
Synthesis method
of SiC fiber.
1
I
spun fiber
,L.
curing in air
unfusing
fiber
I
J. heat treatment
SiC fiber
(Nicalon)
103
Kiyohito Okamura
determined by vapor pressure osmometry, molecular weight

distribution by high-speed gel permeation chromatography
(GPC), and bonding states (chiefly of the Si atoms) by infrared
absorption spectra and lH_, 13C, and 29Si-NMR spectra. During
the thermal decomposition of polycarbosilane to SiC, weight loss
was measured by TGA-DTA, and thermal decomposition gas by
vacuum measurements and gas chromatography. The crystal
structure and grain structure of the thermal decomposition
products were identified by X-ray diffraction and electron
microscope observation respectively. Tension tests were per-
formed on the resulting SiC fibers to obtain tensile strength and
Young's modulus.
5.3 RESULTS AND DISCUSSION
5.3.1 Properties and Molecular Structure of

Polycarbosilanes
5.3.1.1 Molecular Weight and Intrinsic Viscosity
For PC-A 450, PC-A 460, and PC-A 470, kin shown in Table
5.1 increases with reaction temperature. Judging from the elution
curves obtained by GPC for the polycarbosilanes shown in Fig.
5.3, PC-A 470 approaches a monodisperse polymer. PC-A 470,
PC-B 3·2, PC-B 5·5, and PC-TMS are effective as precursors for
SiC fibers. Next, the relationship of kin to intrinsic viscosity was
determined, and this is shown in Fig. 5.4. Ordinarily, the
Fig. 5.3. Elution

curves of
polycarbosilanes.
- - PC-A470
_ . - PC-B3.2
---- PC-B5.5
.......•.•• PC-TMS
8 10 12 14 16 18 20 22
Etl min
104
• Fig. 5.4. A loga-

0.5
PC-A450 rithmic plot of the
0 PC-A470 intrinsic viscosity
A PC-TMS in benzene solu-
0.4 tion at 25°C
against the num-
ber average mole-
'01 cular weight.
....
-5c- 0.3 0
A
~
01
~
0.2
2.B 3.0 3.2 3.4

log Mn
following Sakurada-Houwink formula is established between

polymer compound molecular weight (M) and intrinsic viscosity
(n).13 That is, [n] = KM a , where K and a are constants
determined by polymer type, solvent and temperature. In the
case of ordinary polymers, 0·5 < a < 1·0. a> 0·5 assures spin-
nability and the presence of linear polymers, while a < 0·5 results
in a molecular structure that develops three-dimensionally.
In the case of rigid spherical particles a = 0, while for
bar-shaped particles a = 2. Thus the shape of the molecular
structure can be discussed using the value of a. In the case of
hydrolysed silicon tetraethoxide, Si(O~H5)4' for example, the
products of hydrolysis have an a ranging from 0·23 to 0·75
depending on the extent of hydrolysis, suggesting that branches
and bridges are formed as hydrolysis progresses. 14 The value of a
for polycarbosilane as obtained from the straight line of Fig. 5.4
(Mn was used for molecular weight M) was 0·47, indicating that it
consisted of chain structures and three-dimensional structures
and also contained planar structures.
5.3.1.2 Infrared Absorption Spectra
The infrared absorption spectra for PC-A 470, PC-B 3·2, PC-B
5·5 and PC-TMS are shown in Fig. 5.5 together with that for
105
Kiyohito Okamura
Fig. 50S. IR
spectra of
polycarbosilanes.
4000 3000 800 400

Y(cm-1)
polydimethylsilane (PDMS). Reference 15 was used to assist in

identification of the spectra. At 2970, 2910 cm- 1 (C-H stretch-
ing), 141Ocm- 1 (C-H deformation of Si-CH3), and 1260cm- 1
(Si-CH3 deformation), they had the same absorption spectra as
polycarbosilane, and near 820 em-I (Si-CH3 deformation and
Si-C stretching) there was a broad, large absorption peale The
peaks characteristic of polycarbosilane were observed at
2100cm- 1 (Si-H stretching), 1355 cm- 1 (-CH2-CH2 deforma-
tion in Si-CH2-Si), and 1020-1040 cm -1 ( -CH2- wagging
vibration of Si-CH2-Si). In the case of PC-B 3·2 and PC-B 5·5,
smail peaks were observed at 3050 cm- 1 (C-H stretching of
Si-CJIs) , 1430 em-I (C=C stretching of SiC-C6Hs) 1120 cm- 1,
and 520 em -1 (Si-C~s), indicating the presence of phenyl radicals
106
within the molecules. The absorption strengths of 1355 cm- 1 for

PC-TMS and PC-A 470 are higher than those of 1410 cm- 1 for
PC-B 3·2 and PC-B 5·5. This indicates a difference in the
number of Si-CH3 molecules with respect to Si-CH2-Si. A
comparison of 2100 cm- 1 and 2970, 2910 cm- 1 shows that PC-A
470 has a significantly higher absorption strength than PC-TMS,
PC-B 3.2, or PC-B 5.5, indicating the large number of Si atoms
with Si-H bonds. Thus it can be seen that the molecular
structure of polycarbosilane differs somewhat depending on the
method of synthesis.
5.3.1.3 Nuclear Magnetic Resonance Spectra

References 16 and 17 were referred to during the identification of
NMR spectra. In the lH NMR spectrum, one peak was observed
around 0 ppm and another, smaller one observed at 4-5 ppm.
The former is due to C-H bonds of Si-CH3' Si-CH2-Si, etc.,
while the latter is due to Si-H bonds. Next, the proton coupling
and proton decoupling methods for 29Si NMR spectra are shown
in Figs 5.6 and 5.7, respectively. In both figures, a positive value
for chemical shift ({) indicates the low magnetic field direction
from tetramethylsilane (TMS). The proton decoupling spectra
show downward peaks due to a negative nuclear Overhowser
effect (NOE), as shown in Fig. 5.7. A comparison of Figs 5.6 and
5.7 shows that the -0'75ppm peak in both PC-TMS and
PC-470 remains unchanged regardless of the coupling or
decoupling with a proton, suggesting that the peak is due to 29Si
not coupled to lH. Since the peaks at -9·13 ppm and
-24·39ppm become a single peak at -17·50 upon proton
decoupling, this peak is due to 29Si coupled to one lH. In the
same way, in PC-B 3.2 and PC-B 5.5 the peak at 0·5 ppm is due
to 29Si which is not coupled to lH, and the peaks at -8·72 ppm
and -23·81 ppm are due to 29Si coupled to lH. Thus the number
of hydrogen atoms which bonded with silicon atoms is either 0 or
1. The peaks not coupled to lH correspond to the silicon atoms
that bonded with four carbon atoms (SiC4), while those peaks
coupled to lH correspond to the silicon atoms that bonded with
three carbon atoms and one hydrogen atom (SiC3H). The
structural units of each are shown in Fig. 5.8. In PC-B 3.2 and
PC-B 5.5, a peak was observed near -38 ppm. This peak is the
107
Kiyohito Okamura
Fig.S.6. 29Si C
NMR spectra of
polycarbosilanes. C - Si-C
I
C
PC-8S.S
~
PC-BJ.2
~
PC-A470
~ (ppm)
result of silicon atoms which formed chain-shaped polysilane

skeletons. Furthermore, from the fact that this peak remained
unchanged under proton decoupling, it can be inferred that it
was the result of silicon atoms not possessing a side chain of
hydrogen atoms, i.e. those which bonded with X carbon atoms
and (4 - X) silicon atoms (SiCx Si4 _ x )' The corresponding
structural unit is shown in Fig. 5.8. In the case of the 13C NMR
spectrum, however, only a broad peak was observed, between
-8·7 ppm and 16·7 ppm, centered around 4·7 ppm. This was
categorized as a peak due to C bonded with Si, but detailed
analysis proved impossible.
108
Fig.S.7. IH de-
coupling 29Si
NMR spectra of
polycarbosilanes.
I
C - Si - C
I
H
40 20 o -20 -40 -60

o(ppm)
The molecular structure of polycarbosilane was analyzed using

infrared absorption spectra and NMR spectra. Proportions of the
various structural units present in each polycarbosilane are
shown in Table 5.2. These structural units are connected in
chains, and between each unit it is thought that a C-H bond
equivalent to C~ has been removed from between a methyl
group and a methyl group or between a methyl group and a
methylene group, and concentrated. The bridge may be a
Si-CH-bond in which the methane has been removed from
between the methyl group and the methylene group, or it may be
a Si-CH2-bond in which the methane has been removed from
109
Kiyohito Okamura
Fig.S.S. CH 3 CH 3 CH 3CH 3 CH 3 CH 3 CH 3
Structural units I I I I I I
-CH2-~i-CH2-.-CH2-~i-CH2-.-CH2-~i-~i- or -~i-~i-Si-
and chemical
structural CH 3 H CH~H3 CH 3 CH 3 CH 3
model of
polycarbosilanes.
Structural units of Polycarbosilane
Chemical structural model of Polycarbosilane
between the methyl group and the methyl group. A model of the
type shown in Fig. 5.8 is proposed for the molecular structure of
polycarbosilane. Among the structural units of polycarbosilane,
SiC3H and SiCxS4-x are closely tied to the unfusing mechanism
in the synthesis process of SiC fibers, and they have a large
impact on SiC fiber properties. 12,18
5.3.2 Unfusing Mechanism of Polycarbosilane

Thermal oxidation-induced weight gain for various polycar-
bosilanes showed a tendency to increase in the following order:
PC-TMS (2,28%), PC-A 470 (7·63%), PC-B 5.5 (13,48%), and
PC-B 3.2 (16·84%). In addition, TG-DTA curves in air at
Table 5.2
Fractions of Polycarbosilane SiC.. SiCP SiCxSi.._"
the Structural PC-A 450 0·38 0·57 0·05
Units in PC-A 460 0·49 0·46 0·05
Polycarbosilanes PC-A 470 0·53 0·47 0
PC-B 3.2 0·40 0·16 0·44
PC-B 5.5 0·44 0·15 0·41
PC-TMS 0·82 0·18 0
110
temperatures below 500°C showed that an oxidation reaction

occurred in each of the polycarbosilanes at 100-2000C, with the
polycarbosilane being cross-linked and unfused by the oxygen
taken in. In fact, the oxygen contained in each polycarbosilane as
observed by chemical analysis (atomic ratios) of the various
fibers increased upon unfusing, from SiClo77H30100ooo3 to
Silo63H30340oo20 in the case of PC-A 470, and from
SiClo88Hso030oo19 to SiC1-16~o160oo68 in the case of PC-B 3.2, and
there were corresponding reductions in the number of C atoms
and H atoms with respect to Si atoms. This change in the
molecular structure of polycarbosilane unfused by thermal
oxidation can be estimated from the infrared absorption spectra
shown in Fig. 5.9. New peaks are observed near 3670 em-I (O-H
stretching) and 1740 cm - I (0=0 stretching). Another charac-
teristic change is the decline in the strength of the 2100 cm- I
(Si-H stretching) absorption peak to a level lower than other
peaks. The mechanism responsible is oxygen-induced cross-
linking between polycarbosilane molecules. From the above, it is
thought that the unfusing mechanism for polycarbosilane is such
that, in the molecular structure of polycarbosilane shown in Fig.
5.8, the Si-H bonds are severed by oxidation, Si-O-Si bonds
PC-A470 Fig. 5.9. IR

Cured PC-A470 Fiber
spectra of poly-
carbosilane (a)
PC-A470 and (b)
cured PC-A470 fi-
bers, heat-treated
at various tem-
peratures in a
vacuum.
(a) (b)
4000 3000 2000 1400 1000 600 250
4000 3000 2000 1400 1000 600 250 1800
1800
ii (em"')
ii (cm-1 )
111
Kiyohito Okamura
Fig. S.10.
Oxidation curing
mechanism of
polycarbosilane
fiber.
+02
+ ----+
form, and pairs of molecules are cross-linked. A model of this

mechanism is shown in Fig. 5.10. This model is also supported by
the results of high-resolution NMR performed on solid 29Si. 19
5.3.3 Conversion of Polycarbosilane to SiC

5.3.3.1 Thermal Decomposition of Polycarbosilane
The thermal decomposition processes for various polycar-
bosilanes have been studied, but all show virtually the same
process. Infrared absorption spectra and TG-DTA for the
thermal decomposition products obtained from PC-A 470 are
shown in Figs 5.9 and 5.11, respectively. The thermal decom-
position process for polycarbosilane is shown in Fig. 5.12 by the
Fig. S.l1. TG- Polycarbosilane Cured Polycarbosilane Fiber

DTA curves of (a) 100..--....,..,----------, 1ool~~:::;;;;;::::~---1
polycarbosilanes
and (b) cured
t90
!l
't:J
polycarbosilane ·iii 80 PC-B3.2~::::::::::::3:::::
~ PC-BS.S
fibers in N2 gas
~70
flow. Ol
i~
E PC-TMS
~~
~~
~ ~S DTA
.r; -
~c:
GI
o 200400600800 100012001400 0!,-200=,-4OO~,--;6.-:0"'0,...,8~0:=0....,.10:t:00=-:-12:::oo::=-!1400
T(°Cl T(°Cl
(a) (b)
112
Relationship between gas evolution and tensile strength Fig. S.U. Gas
evolution process
of polycar-
bosilanes and
PC cured polycar-
bosilane fibers,
and tensile
strength of SiC
fiber against
PC Fiber pre-heated heat-treatment
in air (cured PC fiber) CO([) temperature.
I 1 1 1 I I I I I
o 200 400 600 800 1000 1200 1400 1600

Temperature (OC)
thermal decomposition-induced gas evolution process for poly-

carbosilane. This figure shows the gas evolution process for
polycarbosilane fibers unfused by thermal oxidation together
with the relation between unfused polycarbosilane film baking
temperature and tensile strength. IS During the thermal decom-
position of polycarbosilane under a flow of inert gas, weight loss
occurs at temperatures of less than 350°C due to volatilization of
low-molecular-weight components contained in the polycar-
bosilane, and the number average molecular weight of polycar-
bosilane increases. However, there are no changes in molecular
structure. At 350-500°C, the molecular weight of polycarbosilane
increases, while at the same time dehydrogenation, a de-
hydrocarbonation condensation reaction, and radical polymeri-
zation due to the thermal decomposition of the polysilane
skeleton occur. In this temperature range, a reaction accom-
panies a change in the molecular structure such that the
carbosilane skeleton becomes virtually 100% of the molecules.
At 500-800°C, mostly dehydrogenation and demethanation
113
Kiyohito Okamura
reactions occur due to thermal decomposition of the Si-Hand

Si-CH3 bonds of the polycarbosilane side chains. In addition, H2
gas and C~ gas are generated and evolved. Furthermore,
recombination of the formed radicals results in the formation of
Si-CH2-Si bonds, and as the temperature rises, cyclization and
three-dimensionalization occur due to the reactions participated
in by the -CH2- bond of these bonds, leading to the formation
of a ceramic structure consisting of Si-C bonds. At 800-1000°C
the network of an SiC skeleton develops, and at lOOO-1200°C a
dehydrogenation reaction occurs, hydrogen gas is evolved and a
fJ-SiC amorphous structure is formed. The state of the carbon
generated as a product of thermal decomposition at temperatures
of lOOO°C and above cannot be identified by infrared absorption
spectra, X-ray diffraction, or observation with an electron
microscope. However, characterization is possible using Raman
spectroscopic analysis alsO.2O At temperatures of 1200°C and
above, fine-crystal fJ-SiC forms, while at the same time carbon
develops as a C6 -ring structure. At temperatures of 1500°C and
above, the reaction between oxides formed by the oxygen
contained as an impurity in the polycarbosilane and carbon,
results in the formation of CO (H) gas, and the crystallization of
fJ-SiC and carbon is promoted. 18
There are slight differences in the thermal decomposition
processes for various polycarbosilanes. Increase in the molecular
weight of polycarbosilane as a result of heating occurs in the
order PC-TMS<PC-B 5.5<PC-A 470<PC-B 3.2, and the
temperature at which the conversion to an inorganic compound is
transformed from one via the vapor phase to one via the solid
phase increases. Polymers capable of maintaining this conversion
via the liquid phase up to high temperatures facilitate molecular
movement and tend to crystallize as fJ-SiC at high temperatures.
5.3.3.2 Synthesis of SiC Fibers
In the production of SiC fibers from polycarbosilane on an
industrial scale, unfusing is pedormed by thermally oxidizing
melt-spun polycarbosilane fibers in air at lOO-190°C and baking
at a temperature of lOOOOC or more under a flow of inert gas.
The thermal decomposition process for polycarbosilane fibers
unfused by thermal oxidation will be discussed in comparison
with that of polycarbosilane itself. In polycarbosilane cross-
linked by oxygen, cross-linking proceeds even further due to the
114
dehydrogenation reaction at temperatures below 600°C, but the

amount of volatile low-molecular-weight polycarbosilane is low
and significant weight loss does not occur. At 600-750°C,
thermal decomposition of the polycarbosilane side chains results
in greater evolution of gas, the structure becomes inorganic, and
fiber density increases rapidly. The skeleton of this inorganic
structure contains Si-C bonds and C-C bonds, and cross-
linkages of oxygen atoms are present between the molecules
consisting of these skeletons. At 750-1200°C, the dehydrogena-
tion reaction no longer occurs, and hydrogen gas is no longer
generated. The thermal decomposition of the polycarbosilane
side chains is almost complete, and as the baking temperature
rises there is a remarkable increase in strength. Although the
structure is amorphous, it also contains fine crystals (crystallite
size: approximately 20 A) at 1200°C. The oxygen introduced
during unfusing acts to inhibit fJ-SiC crystallization. At 1200-
1400°C, the silicon oxides formed by oxygen introduced during
unfusing react with the carbon present as a product of thermal
decomposition to form CO(I) gas In addition, fJ-SiC crystal-
lization is promoted. SiC fiber strength is highest at 1200-1300°C
and drops rapidly at temperatures of 1300°C and above. At
temperatures of 1400°C and above, the silicon oxides (chiefly
those formed by the oxygen contained as an impurity in the
polycarbosilane itself) react with the carbon to once again form
CO(II) gas, and fJ-SiC crystallization is promoted.
The relationship between baking temperature and tensile
strength for SiC fibers prepared from various unfused polycar-
bosilane fibers will now be discussed. The relationship was
virtually the same for all varieties, and those for PC-B 3.2 and
PC-B 5.5 are shown in Fig. 5.13. Next, the relationship between
oxygen introduced during unfusing (weight gain ratio, A W /W)
and tensile strength was investigated for PC-B 5.5. The results
are shown in Fig. 5.14. As AW /W increases, the tensile strength
of SiC fibers decreases. In order to improve the properties of SiC
fibers, the increase in oxygen introduced during unfusing must be
minimized. As described above, at baking temperatures of
1300°C and above, the tensile strength of SiC fibers drops rapidly
together with CO (I) gas evolution and fJ-SiC crystallization. The
temperature at which crystallization begins is approximately
200°C higher for nitrogen and argon atmospheres than for
vacuums (Fig. 5.13). Hence, baking in nitrogen or argon gas
11S
Kiyohito Okamura
Fig.5.13. Tensile 300r-----------------------~
strength of SiC o PC-B3.2 in vac.

fibers obtained by • PC-B5.5in vac.
"'~ II PC-B5.5 in N2
the heat treat-
'E II PC-B5.5in Ar
ment of cured E
polycarbosilane 0, 200
(PC-B) fibers ;;;
.c
in various ~
atmospheres.
~
ti
.!!
'iii 100
c
~
OL-~~-L ___ L-__L_~_ _~_b.~

200 400 600 800 1000 1200 1400 1600
TCOC)
atmospheres inhibits P-SiC crystallization up to high tempera-

tures, and fibers baked at high temperature do not lose as much
of their strength as fibers obtained by baking in a vacuum. Since
there is a mutual correlation between CO (I) gas evolution and
P-SiC crystallization, control over the oxygen content of the fiber
is fundamental to improving the properties of SiC fibers.
5.4 SUMMARY
The structure of polycarbosilane, the unfusing of polycar-

bosilane, the conversion of polycarbosilane to SiC fibers, and the
Fig. 5.14. Effect 400
,
"'~
of AW/Win the 'E
!f f +ti
curing process on ~ 300
01
tensile strength of ;;;
SiC fiber obtained .c
by the heat treat- ~ 200
c
G.I
ment of cured ....'-
polycarbosilane OIl
100
.!!
(PC-B 5·5) fibers .iii
c
in a vacuum at ~ 0
1200"C. 8 10 12 14 16 18
AWIW COlo)
116
properties of the resulting SiC fibers were discussed. SiC fibers

are playing an important role in the development of composite
materials, but several problems have been pointed out, and the
future development of composite materials will require that these
be resolved. Recently, much attention has been focused on
research concerning the synthesis of ceramic materials from
organic metal polymers, and the method of synthesizing SiC
fibers from polycarbosilane is expected to provide a foundation
for these efforts. We hope that this chapter will be of use in these
efforts.
ACKNOWLEDGEMENTS
Portions of this chapter were taken from Silicon Carbide
Materials: New Synthesis Methods and Applications, CMC
Company Ltd, 1985. We would like to thank the individuals at CMC
for their permission. In addition, figures and tables were
reprinted from publications of the Japan, Chemistry and
Industrial Chemistry and the 1. Mater. Sci. We would like to
express our appreciation to the people at both of these
organizations for their cooperation.
REFERENCES
1. Yajima, S., Hayashi, J. & Omori, M., Continuous silicon carbide
fiber of high tensile strength. Chem. Lett. (1975) 931-4.
2. Yajima, S., Okamura, K., Hayashi, J. & Omori, M., Synthesis of
continuous SiC fibers with high tensile strength. J. Am. Ceram.
Soc., 59 (7-8) (1976), 324-7.
3. West, R., David, L. D., Djurovich, P. I. & Yut, H., Polysil-
astyrene: phenylmethysilane-dimethylsilane copolymers as precur-
sors to silicon carbide. Am. Ceram. Soc. Bull., 62(8) (1983),
899-903.
4. Yajima, S., Hayashi, L. & Okamura, K., Pyrolysis of a polyboro-
diphenylsiloxane. Nature, 226(5602) (1977), 521-2.
5. Seyferth, D., Wiseman, G. H. & Prod'homme, C., A liquid silazane
precursor to silicon nitride. J. Am. Ceram. Soc., 66(1) (1983),
C-13-C-14.
6. Legrow, G. E., Lim, T. F., Lipewitz, J. & Reaoch, R. S., Ceramic
from hydridopolysilazane. Am. Ceram. Soc. Bull., 66(2) (1987),
363-7.
117
Kiyohito Okamura
7. Yajima, S., Iwai, T., Yamamura, Y., Okamura, K. & Hasegawa,

Y., Synthesis of a polytitanocarbosilane and its conversion into
inorganic compound. J. Mater. Sci., 16 (1981), 1349-55.
8. Galasso, F., Basche, M. & Kuell, D., Preparation, structure and
properties of continuous silicon carbide filaments. Appl. Phys. Lett.,
9(1) (1966) 37-9.
9. Fitzer, E., Kehr, D. & Sahebkar, M., CVD-SiC on carbon fibers.
In Silicon Carbide-1973, ed. R. C. Marshall, J. W. Faust, Jr & c.
E. Ryan The University of South Carolina Press, Columbia, SC,
1974, pp. 33-41.
10. Lamicq, P. J., Bernhart, G. A., Dauchier, M. M. & Mace, J. G.,
SiC/SiC composite ceramics. Am. Ceram. Soc. Bull., 65(2) (1986),
336-8.
11. Fritz, G. & Mate, E., Carbosilanes. Springer-Verlag Berlin,
Heidelberg, 1986.
12. Hasegawa, Y. & Okamura, K., Synthesis of continuous silicon
carbide fibre, Part 4. The structure of polycarbosilane as the
precursor. J. Mater. Sci., 21 (1986), 321-8.
13. Nagajina, A. & Hosono, M., Molecular nature of polymer. Kagaku
Dojin Clnc., 1 (1969), 314.
14. Kamiya, K., Yoko, T. & Sakka, S., Preparation of oxide glasses
from metal alkoxides by sol-gel method-investigation on the type
of the siloxane polymers produced in the course of hydrolysis of
Si(OCzHs)4. Yogyo-Kyokai-Shi, 92(5) (1984), 242-47.
15. Anderson, D. R., In Infrared, Raman and Ultraviolet Spectroscopy
in Analysis of Silicones ed. A. L. Smith, Robert E. Krieger
Publishing Company, Malabar, Florida, 1983, pp. 247-323.
16. Williams, D. E., Nuclear magnetic resonance spectroscopy. In
Infrared, Raman and Ultraviolet Spectroscopy in Analysis of
Silicones, ed. A. L. Smith. Robert. E. Krieger Publishing
Company, Malabar, Florida, 1983; pp. 287-323.
17. Fritz, G., Grobe, J. & Kummer, D., Carbosilanes. Adv. Inorg.
Chem. Radiochem., 7 (1%5), 349-418.
18. Okamura, K., Silicon Carbide Materials-New Synthesis Methods
and Application. CMC Company Ltd, 1985.
19. Taki, T., Maeda, S., Okamura, K., Sato, M. & Matsuzawa, T.,
Oxidation curing mechanism of polycarbosilane fibres by solid-state
29Si high-resolution NMR. J. Mater. Sci. Letter, 6 (1987), 826-8.
20. Sasaki, Y., Nishina, Y., Sato, M. & Okamura, K., Raman study of
SiC fibres made from polycarbosilane. J. Mater. Sci., 22 (1987),
443-8.
118
6 Preparation and
Sintering Properties of
Ultrafine Silicon
Carbide Powder
Obtained by Vapor
Phase Reaction
MORINOBU ENDO &
NOBUAKI URASATO
ABSTRACT
The preparation methods, structure and sintering behavior of

ultrafine SiC powders obtained from the vapor phase reaction
process are briefly reviewed.
High-purity ultrafine silicon carbide powders with /3-type struc-
ture have been prepared by the vapor phase process using thermal
decomposition or plasma systems through the reaction of sub-
stances such as silane and methane. These ultrafine SiC powders,
less than several hundred nanometers in diameter, have macro-
scopic and microscopic structural features. The diameter and
carbon Isilicon molar ratio of the powders can be controlled by
changing the pyrolysis conditions of reactants.
These ultrafine powders show rather good sinterability. For
pressureless sintering, boron and carbon additives are also re-
quired as with conventional powders, but powders having a CISi
molar ratio greater than 1 can be sintered at a temperature in the
region of 2050°C by the addition of boron powder alone. SiC
ceramics prepared from ultrafine powders have a much finer
texture than those obtained from conventional powders.
It is concluded that powders obtained by CVD could be .
applicable to functional and high-performance SiC ceramics which
require well-controlled starting materials.
119
Morinobu Endo, Nobuaki Urasato
6.1 INTRODUCTION
In recent years, silicon carbide (SiC) has attracted attention for

its application to high-temperature, heat-resistant structural
elements and as a ceramic with high insulation and large thermal
conductivity, as an environment-resistant semiconductor mate-
rial, and as a leading-edge composite. Active basic and applied
research is being conducted. Silicon carbide is said to have been
discovered by chance during an experiment in diamond synthesis
by Edward G. Acheson in 1890. Since it rarely occurs naturally,
all silicon carbide materials currently in use are synthesized
industrially as an artificial and inorganic substance.
Silicon carbide powders are manufactured industrially by an
established method, the Acheson method, in which bulk silicon
carbide is ground and undergoes prescribed processing. 1 This
type of method, however, requires a grinding step, and has
problems such as the difficulty of controlling the particle size and
shape and the ease with which impurities are introduced.
Therefore it is difficult to prepare high-performance fine ceramic
materials using conventional silicon carbide.
In vapor-phase powder formation techniques, which involve
vapor-phase thermal decomposition and synthesis, SiC powder
is produced by vaporizing the raw materials, placing them in the
reaction furnace, and decomposing or reacting them using heat
or plasma. These techniques are promising as a means of
manufacturing high-grade ceramics materials. SiC is formed
directly using a mixed gas (consisting of SiCl4 or SiH4 as a silicon
source and C~ as a carbon source) as the raw material and using
an electric furnace or excitation by plasma or lasers to cause a
vapor phase reaction or thermal decomposition. Ultrafine
crystallization of the SiC powder and uniform doping of sintering
aids are facilitated, thereby allowing preparation of powders with
good sinterability and control over the sintered structure.
Increased functionality, beginning with the high-strength sintered
bodies unique to SiC, can therefore be expected. It is said that
the mechanical properties of sintered bodies improve remarkably
with finer particle sizes, and as finer powders are also required
for finer structures, the vapor phase methods have attracted a
great deal of attention. 2 ,3 Higher-grade powders are also made
possible through higher purity, greater particle sphericity, and
sharper particle size distributions. Despite the range of possible
120
Preparation and Sintering Properties of SiC Powder
applications for the vapor phase method, however, there remain

numerous unresolved problems, including powder fabrication
methods, sinterability, and a lack of investigation at the
industrial level and evaluation from a commercial standpoint.
However, ultrafine SiC prepared by the vapor phase method has
strong possibilities for application as a fine ceramic material with
numerous superior characteristics, and it is developing into a
useful industrial technology. In contrast to the conventional
Acheson method, the vapor phase technique allows wide-ranging
design of material properties, making possible raw materials with
the characteristics necessary to produce ceramics having certain
desired properties. Furthermore, although the high cost of this
method has been a disadvantage in the past, methods for
effective utilization of tetramethyldisilane (TMDS) , methyltri-
chlorosilane, and other byproducts of the silicon industry are
being established, and with increased scale of production it
should be possible to reduce costs to reasonable levels.
This chapter will discuss the fabrication and structure of
ultrafine SiC powders obtained by vapor phase reaction and
thermal decomposition with an emphasis on the formation of
ultrafine SiC by the vapor phase method. In addition, the
pressureless-sintering properties of ultrafine SiC will be intro-
duced. SiC powders prepared by the vapor phase method are
excellent materials possessing good sinterability and capable of
providing a fine, uniform sintered structure. Future expectations
are high.
6.2 FORMATION AND STRUCTURE OF SiC

POWDERS PREPARED BY THE VAPOR PHASE
MEmOD
Figure 6.1 shows a comparison of vapor phase and Acheson

powder formation processes. The CVD (Chemical Vapor
Deposition) process is extremely simple. Its main advantages are
as follows: (1) low-temperature synthesis is possible because the
reaction occurs in the vapor phase; (2) high-purity powders can
be obtained due to the ease of refining at the raw material stage;
(3) spherical fine particles can be obtained because of precipita-
tion from the vapor phase; (4) both microscopic and macroscopic
structures can be controlled; (5) the chemical reaction system can
Ul
Fig. 6.1. Conventional method Vapor phase method

Comparison of (silica,coke,industrial salt)
SiC powder fabri- ~--- .....
cation techniques:
conventional and
vaporpbase
methods. Incomplete reaction
products
be selected because of the numerous possible combinations of

raw material gas; and (6) powders doped with necessary sintering
aids as well as premixed powders can be synthesized. The CVD
method also, however, suffers from the following disadvantages:
(1) it often requires the handling of toxic, corrosive and volatile
gases; (2) the materials constituting the reaction crucible and
other equipment must be carefully selected because halogen gas,
etc., reacts easily at high temperatures; and (3) related chemical
engineering technologies must be developed in order to achieve
continuous large-scale production.
6.2.1 Formation of SiC Powder by the Vapor Phase

Method
Vapor phase techniques can be divided into reaction and thermal
decomposition techniques according to the raw material used. A
vapor-phase reaction technique in which halogenated silicon and

a hydrocarbon are reacted has long been known, and SiC powder
can be synthesized by the following processes: 4,s
7SiC4 + (qHs + lOH2---+ 7SiC + 28HCl
SiC4 + CH4---+ SiC + 4HCl
For example, fJ-SiC powder can be obtained by mixing SiCl4 and
(qHs at a molar ratio of 2: 3 and heating at 1500-2000°C. The
formation of fJ-SiC by mixing SiCl4 and CCl4 at a molar ratio
ranging from 1 to 2 and reacting at 1300-1600°C using a
hydrogen carrier gas has also been reported. 6
Methyltrichlorosilane (CH3SiCI3) and (CH3)4Si have been
extensively studied as raw materials for the vapor phase thermal
decomposition method. s,7 H2 is commonly used as a carrier gas,
but N2 or Ar gas may also be employed. fJ-SiC has been formed
in the CH3SiCl3 + H2 system by reacting CH3SiCl3 at 1470°C.
Alkyl compounds and aryl compounds can also be used as raw
materials. Table 6.1 shows several examples of compounds
studied as raw materials for the vapor phase method. 2 A concrete
example using the recently-developed TMDS (tetramethyldisi-
lane) will be described below. 8-10
Table 6.2 shows the molecular formula and fundamental
properties of TMDS. The TMDS had a purity of approximately
90% as measured by gas chromatography. Among the main
impurities contained were several varieties of alkylhydrogen
polysilane, which resembles TMDS but has a higher boiling
point, but these impurities had virtually no observed effect on the
formed SiC powder. 10
Figure 6.2 is a diagram of typical vapor phase method
devices (thermal decomposition method,3,n plasma method 12).
High-purity hydrogen is generally used as a carrier gas for
thermal decomposition. The partial pressure of the reaction gas
(such as TMDS) in the hydrogen atmosphere can be controlled
by changing the flow volume of the carrier gas such as H2 and N2.
The resulting powder is naturally deposited in a glass trap located
in the rear portion of the device. Raw material purity is
extremely important to precision synthesis. One of the merits of
this method is that since TMDS is originally a byproduct of a
high-purity Si process and contains virtually no metal impurities,
a refining process is not always required. 10 With the plasma
method, as shown in Fig. 6.2(b), the reaction is performed by
t ~
l
~
~
~
[-.
!:i=
Table 6.1
Synthesis of Silicon Carbide by Vapor Phase Methods ~
S
Method TypiCtlI raw Reaction formulas Method of
materials excitation
Carbon reduction Silica 3C + Si02= SiC + 2C02 Electric furnace

of oxides Carbon 2C + SiO = SiC + CO heating
Silica C+Si=SiC Electron beam
Laser
Sputtering
Vapor phase Silicon tetrachloride, SiCl4 + CH. = SiC + 4HCI Electric furnace
thermal silane, methane and 7SiCl4 + ~H8 + 10H2 = 7SiC + 28HCI heating
decomposition other hydrocarbons, SiC~ + CC~ + 4H2 = SiC + 8HCI Laser
and synthesis carbon 3SiH. + ~Hs = 3SiC + lOH2 Plasma
tetrachloride Sill. + CH. = SiC + 4H2
Methyltri- CH3SiCl3 = SiC + 3HCI
chlorosilane
Tetramethyl (CH3)4Si2H2- 2SiC + 2CH. t + 3H2 t
-disilane
Table 6.1
Name 1,1,2,2-tetramethyldisilane Properties of
Molecular formula H[Si(CH3hhH TMDS
Molecular weight 118·23
Density (d~ 0.7202 g/cm3
Boiling point 86-87°C/700 mmHg
passing the raw material gas through the central portion of the
Ar plasma, and a black P-SiC ultrafine powder is obtained. 12
Ultrafine SiC powders prepared by the vapor phase method
may be black, brown, yellow, light blue or grayish white
depending upon the partial pressure and thermal decomposition
temperature of the decomposition gas. Figure 6.3 shows typical
X-ray diffraction patterns for such powders. In addition to the
broad 111 diffraction peak for p-SiC, 220 and 311 diffraction
lines were observed, and it can be seen. that these SiC powders
Electric furnace Fig. 6.1. Vapor
C><l
Raw material gas for SiC powder
decomposition and synthesis phase method de-
vices. (a) Thermal
decomposition
Thermocouple .. method; (b)
plasma method.
1><1
(a)
Plasma gas
Inert gas for protection

of reactor walls _..---;,. Water
Hi g h -frequency
.......-"""""-_....1 oscillator (3.6 MHz)
'---C:oollant water
Flow volume
control valve
(b)
us
Morinobu Endo, NobUIJki Urasato
Fig. 6.3. X-ray 300.----------------------------------------,

diffraction pat-
terns of typical
ultrafine-grain ~ 200 SiC III
o
SiC obtained by
i_c
UJ
vapor phase ther-
mal decomposi- 100 /'\ SiC 220 SiC 311
tion of TMDS. ,,"'~...·hh
1.'
f-wlo-.........,.....,,"'. '·'>I,' ..~...."'.I...........,......
ftl\f
....4...I.'r......
L' ... ,"-- .
"-r\I,
O~~ __~--~--~--~--________~--~____~
~ m ~ ~ ~ ~ ~ ~ ~ ro ~
28 (0)
consist of fJ-type microcrystals, as opposed to the a-type crystals

found in powders prepared by the Acheson method. 10
6.2.2 Structure of Ultrafine-grain SiC

Table 6.3 shows typical properties of powders prepared by the
plasma decomposition method. 13 Ordinarily, SiC prepared by the
Table 6.3
Typical Properties
Property Sample P-'1AY'
of a Powder Pre- Specific surface area (m2/g) 22·0
pared by Plasma Mean particle size I'm Volume average 0·17
Thermal Number average 0·054
Decomposition X-ray crystallite 0·054
Method size
Chemical composition SiC 95·6
(wt%) FreeC 1·0
Free Si02 1·5
Total 98·1
Metal impurities Ca 6
(ppm) Al 13
Fe 45
Total 186
Total oxygen (0) (%) 1·1
Hydrogen (H) (%) 0·067
Nitrogen (N) (%) 0·025
Chlorine (Cl) (%) 0·34
Bulk density g/cm3 0·35
aMethyltrichlorosilane was decomposed in Ar high-frequency plasma.

Source: Masataka Yamamoto, Proc. of Jrd Symposium on Next-
Generation Industrial Key Technologies, Vol. 10, 1985.
vapor phase method has a mean particle size of less than several
hundred nanometers and is characterized by a large specific
surface area (approximately 20-S0 m2/g).
Figures 6.4(a)-(c) are high-resolution transmission electron
microscopy (TEM) images of SiC powder prepared by the vapor
phase method. 8 ,lO (a) is a light field image, (b) is a 111 dark field
image, and (c) is a selected-area electron diffraction image. The
111, 220 and 311 rings of diffused P-SiC can be clearly observed
in the selected-area electron diffraction image. In addition, the
bright field image shows that particle size varies in the range
10-300 nm, depending on the conditions of thermal decomposi-
tion, and that particle shape ranges from irregular to perfectly
spherical (Fig. 6.4(a». Figure 6.4(d) is a TEM image of an a-SiC
powder prepared by a conventional method for purposes of
comparison. As long as formation conditions remain constant,
the vapor phase method can provide extremely high uniformity
of particle size and shape as well as good reproducibility.
Furthermore, judging from the luminescent spots on the dark
field image using P-SiC and 111 diffraction lines, the microcrys-
tals appear to be randomly distributed throughout each particle,
and given the size of these spots the crystallites appear to be
1-3 nm in size.
Figure 6.S shows change in crystallite size as a function of
thermal decomposition temperature. SiC fine powders were
formed with the vapor phase method while varying the thermal
decomposition temperature from 800°C to 1400°C and applying
the Scherrer formula to the half-value width of the P-SiC 111
X-ray diffraction pattern of the resulting powders. The estab-
lishment of particles which developed together with the increase
in thermal decomposition temperature can be observed. A rapid
increase in crystallite size can also be seen, from approximately
1 nm at 800-11000C to 2 nm at 1200°C and 3 nm at 13S0°C.
Figures 6.6(a)-(c) show infrared absorption spectra for the
powders obtained. In contrast to the SiC of Fig. 6.6(a), which
was formed at 1400°C and for which only absorption by SiC
stretching vibration in the region of 8S0cm- 1 was observed,
absorption by both SiC and Si-H were observed for the SiC of
Fig. 6.6(b), which was formed at 11OO°C, and absorption by both
Si-H and Si-CH3' though minimal, was observed for the SiC of
Fig. 6.6(c), which was formed at 82SoC. In other words, powders
formed by thermal decomposition of TMDS at temperatures of
U7
al 17"':. \ '.1 I~
" s·
~
~
I::
~
~
~
~
s
~
~
~
s
Fig. 6.4. TEM images of SiC powders prepared by vapor phase method and Acheson method. (a) Light field image of
vapor phase SiC powder; (b) 111 dark field image of same; (c) selected-area electron beam diffraction image of same;
Acheson method SiC powder.
Fig. 6.5. Relation

3 between thermal
decomposition
~ temperature to
E
c crystallite size.
~ 2
'iii
II
,,!:::
ii
+'
~ 1
'-
U
0~8~0-0--~~~~--~--~--~
1000 1200 1400
Thermal decomposition temperature (oel
less than 900°C can be treated as SiC fine crystals containing

organic polymer-like elements having numerous Si-H and
Si-CH3 bonds. In order to synthesize pure SiC powders which
are free of Si-H and Si-CH3 bonds with a raw material of TMDS
or other organic silicon, thermal decomposition must be carried
out at temperatures of 1200°C and above. These organic bond
components are also important when attempting to identify the
sintering behavior of a powder.
Because it makes use of high-purity substances as raw
materials, the vapor phase method facilitates the preparation of
high-purity products, and this is why it is promising as a method
of fabricating materials for use in fine ceramics. Table 6.4 shows
metallic impurities contained in a powder prepared by the vapor
phase method and commercial powders prepared based on the
Acheson method. The latter method requires more steps during
the manufacturing process, including synthesis, grinding, and an
acid wash, and removal of impurities is not complete, with metal
element concentrations exceeding 100 ppm. This forms a major
obstacle to developing or providing functionality. With the vapor
phase method, metal element concentration, with the exception
of Cu (18 ppm) and Fe (24 ppm), was below the detectable limit,
this without any special attention being paid to impurities during
the fabrication process. As also demonstrated by the plasma
method powder in Table 6.3, vapor-phase powders are generally
of extremely high purity.
129
Fig. 6.6. Infrared

spectra and
change in thermal
decomposition
temperature.
(a)Thermal
decomposition temperature 1400·C
3000 2000 1600 1200 800 400

Wave number (cm-1)
Si-H
+
(b)Thermal
3000 2000 1600 1200 800 400

Wave number (cm-1 )
(c)Thermal
3000 2000 1600 1200 800 400

Wave number(cm-1 )
130
Table 6.4
Element
Impurities Con-
Powder AI Cr Cu Fe Mg Ni Ti V tained in SiC
Powder (ppm)
Vapor-phase <10 <10 18 24 <5 <10 <10 <10
ultrafine-
grain SiC
(TMDS)
Conventional 120 100 <10 550 13 190 920 370
SiC (X Corp.)
Conventional 1000 <10 <10 100 <5 <10 180 170
SiC (Y Corp.)
6.2.3 Control over SiC Fine Powder Macroscopic and

Microscopic Structures
The sinterability of a ceramic is affected by the crystallographic
structure and macroscopic particle shape of the raw material
powder. Therefore, control over microscopic and macroscopic
structures is extremely important to the formation of sintered
body ceramic raw materials. The possibility of such control is one
of the greatest merits of the vapor phase method. Specifically, it
is possible to form a SiC powder having certain desired physical
and chemical characteristics by controlling the decomposition-
reaction atmosphere and temperature and the reaction gas Fig. 6.7. Relation
concentration. between thermal
Figure 6.7(a) shows particle size for a powder, formed with a decomposition
constant TMDS concentration and varying thermal decomposi- conditions and
tion temperatures, as obtained from TEM observation. Particle particle size. (a)
Relation between
0.2 0.2,-------------, thermal
decomposition
E E temperature and
.5 .5 particle size (de-
N
Q) Q)
N
composition gas
'iii 0.1 'iiiO.1~ concentration is
U
Q)
~
u
constant). (b) re-
:;; :;; lation between
'- '-
<1J
a.
<1J
a. TMDScon-
0 o~~_~~~~_~~~~ centration and
800 1000 1200 1400 o 2 3 4 5 6 7 particle size
Thermal decomposition TMDS concentration (vol "/0) (thermal decom-
temperature (Oe) position tempera-
(a) (b) ture is constant).
131
size decreases together with thermal decomposition temperature.

Figure 6. 7(b) shows the increase in particle size which results
from an increase in TMDS concentration at the same decomposi-
tion temperature. As particle size decreased, there was an
observed shift in particle shape from regular spheres to irregular
shapes. 10
With the vapor phase method, it is possible to vary the molar
ratio C/Si of carbon and silicon in the range 0·9-1·2 for TMDS l l
and 1·03-1·18 for (CH3)4Si14 by changing the raw material gas
and reaction conditions. Kijima & Konishi have reported that
with ultrafine SiC formed in the Ar-SiH4-C~ system by a
plasma method the elemental ratio of C and Si can be controlled
by modifying the conditions of formation. 12 There are two
possible cases: one in which the carbon consists of free particles
and is deposited as a carbon layer on the SiC; and another in
which the carbon is present as a deviant form of the SiC
stoichiometric ratio. In the case of TMDS, no free carbon can be
observed by X-ray diffraction or TEM observation in powders
having a C/Si molar ratio greater than 1.
Figure 6.8 shows change in C/Si molar ratio when the TMDS
concentration of H2 was varied and the thermal decomposition
temperature set at 1300°C and 1400°C. 10 It is clear from this
figure that the C/Si molar ratio tends to increase with TMDS
concentration. The C/Si molar ratio is also slightly affected by
.the linear rate of the carrier gas in the reaction tube, shown as a
parameter in this figure. No free carbon could be observed by
X-ray diffraction or careful TEM observation under high
magnification in powders prepared from TMDS in which
Fig. 6.8. Relation (a) (b)

between C/Si 1.4 1.4
ratio to thermal
2 .2
decomposition 1.3
~
1.3
~
conditions. Ther- ~
la 1.2
mal decomposi- (5 '"E
(5 1.2
tions: Hz. Thermal E Ui 1.1
Ui 1.1
decomposition "-
0
'-
0
temperature (a) 1.0 ,, ~
1300"C, (b) 14OO"C.
0.9 0.9
2 6 10 2 6 10
TMDS concentration (vol.%) TMDS concentration (vol.%)
132
C/Si> 1, of interest in applications. Even in powders whose

composition is the highest, e.g. C/Si = 1·2, there were no
soot-like carbon particles nor any carbon film or other coating on
the SiC particles. This is at great odds with the belief that
ultrafine SiC obtained in the CH3SiHr H 2 system has a carbon
component that precipitates uniformly on the SiC particle
surface. In any case, ultrafine SiC whose C/Si molar ratio has
been adjusted to an optimal value can be pressureless-sintered by
the addition of boron alone, as will be described in the following
section, and this is an important characteristic for a ceramic raw
material powder to be used in sintering.
6.2.4 Formation Mechanisms of Ultrafine SiC

Numerous techniques have been used in the formation of vapor
phase SiC powders. The method involving thermal decomposi-
tion of an organic silicon compound, however, is industrially
advantageous as it offers a lower formation temperature than
vapor-phase reaction techniques and does not require the use of
corrosive gases. The reaction formula for the formation of SiC by
thermal decomposition of TMDS, for example, is as follows:
(CH3)4Si2H2~ 2SiC + 2CH4(gas) t + 3H2(gas) t
Analysis by gas chromatography of the exhaust gas at a reaction
temperature of 1250°C indicates the presence of CH4 gas, thus
lending support to this reaction formula. The actual reaction,
however, is not this simple; in fact, a complex and multi-stage
reaction mechanism is believed to exist. The reaction mechanism
by which SiC is formed from TMDS is thought to be as shown in
Fig. 6.9.10 During the initial stage of thermal decomposition, i.e.
at temperatures below 700°C, TMDS undergoes radical decom-
position (Figs 6.9(a)-(c». Next, these radical products (1)-(3)
and TMDS undergo repeated polycondensation together with
dehydrogenation and demethanation and are transformed into
high-molecular-weight polysilanes (4) and (5). SiC is formed as
these polysilanes undergo further dehydrogenation and de-
methanation. There is virtually no powder formation at thermal
decomposition temperatures of less than 700°C and, given the
fact that mainly polymethylpolysilanes, which are viscous liquids,
form, and that there are residual Si-H and Si-CH3 bonds in
133
Fig.6.9.
Formation mech- (a)
anismsof
ultrafine-grain
SiC.
CH 3 CH 3
--- ..
I I
H-Si-Si- +-H
I I
CH3 CH 3
(2)
CH 3
I
(c) 2 H-Si-
I
CH 3
(3)
(d) (1) • (2) • (3)
(e)
CH 3
I
( - S i - CH -)n
I ~ 2
(-CH - Si-)m. etc.
I
CH 3
..
(4) (5)
(f) (4). (5) -------

A
-H 2 • -CH4
SiC
powders formed at temperatures below llOO°C, it is believed that

reactions (a)-(d) occur in the region of 7000C; reactions (d) and
(e) at 800-1100°C; and reaction (f) at temperatures of llOOOC
and above. Clarification of this reaction process will be important
in controlling powder formation and in the design of industrial
processes.
134
6.3 SINTERING PROPERTIES
Like silicon nitride (ShN4)' SiC is a covalent compound, and its

crystal structure makes possible highly functional ceramic
materials with excellent strength, hardness, hejlt resistance, and
thermal conductivity. On the other hand, it is a very difficult
substance to sinter, and pressureless sintering, as shown in 1975
by Prochazka, normally requires the heterogeneous addition of
several percent of boron and carbon as sintering aids. Pressure-
less sintering is the most practical method of manufacturing
sintered body ceramics. Because this technique requires a
powder with high sintering activity, these vapor-phase SiC
powders are very promising. As described above, control over
the formation conditions of vapor-phase SiC fine powders allows
the preparation of powders having desired physical characteris-
tics, such as particle size and shape, and C/Si molar ratio. Their
sintering behavior is of great interest. In particular, it has
become clear that pressureless sintering of powders with a C/Si
molar ratio of 1 or greater is possible with the addition of boron
alone,14-18 thereby eliminating the need for the addition of a
carbon component, which is comparatively difficult to disperse.
Thus these powders are capable of simplifying the manufacturing
process and providing highly uniform ceramics whose sintered
bodies have controlled structures. This section will discuss the
effect of sintering aids and sintering temperature on the sintering
of vapor phase powders. It is interesting to note that, despite the
fact that the crystallinity of vapor-phase raw material powders
varies greatly depending on powder formation conditions, no
significant effect on sintering behavior has been observed.
6.3.1 Sintering Temperature

Figure 6.10 shows sintering temperature vs. relative density
(compared with theoretical density: 3·21 g/cm3) when sintering
temperature was varied in the range 1700-2200°C. The C/Si
molar ratio of the powder as determined by chemical analysis
was 1·08, and 1 wt% boron was uniformly added as a sintering
aid. There is a tendency for relative density to increase together
with sintering temperature, and at temperatures of 19OQOC and
above relative density exceeds 90%. Figure 6.11 shows
135
Fig. 6.10. 100.-----------~

Sintering tem-
perature versus
relative density.
95
...,.,
'OJ;
~ 90
u
Q)
...>
r:I 8 additive: 1 wtoJo
Ji 85
80~~_~-L_~~~~~
1600 1800 2000 2200
Sinteri ng t(:mper .. tu~ e (oc)
differences in sintering state due to changes in sintering

temperature as observed by cross-sectional SEM of the sintered
bodies. In Fig. 6.11(a), it can be seen that sintering is insufficient
at 1700°C, with numerous pores being present. From the X-ray
diffraction patterns shown in Fig. 6.12, only a p-phase is present
at 20000C (Fig. 6.12(a», while at 2200°C a partial transformation
to the a-phase can be observed (Fig. 6.12(b», and needle crystal
formation and other abnormal grain growth resulting from this
p-a transformation can be observed in Fig. 6.11(d). Therefore,
the optimal sintering temperature for ultrafine SiC is thought to
be approximately 2000-2100°C (Fig. 6.11(c», which is somewhat
lower than the temperatures typically used in sintering commer-
cial P-SiC powders.
In addition, Kato et al. have shown that an SiC powder with a
particle size of 100-200 nm obtained by vapor-phase thermal
decomposition of Si(CH3)4 will produce a good sintered body
with relative density of 95% at a sintering temperature of
2050°C. 14 ,15 When boron alone was added to SiC having a large
O/Si ratio (C/Si = 1·03; O/Si = 0·08), sintering for 30 min at
2050°C produced a relative density of only 46%, and this raw
material powder required the addition of carbon. On the other
hand, SiC powders having a small O/Si ratio (C/Si = 1·03;
O/Si = 0-07 or C/Si = 1·03; O/Si = 0·05) can produce a relative
136
~
I~
I:)
i:l
§.
§
1:1..
c.,
S·
~
;::!
;:sO
I)Q
~
~
~
~
51l m ...
~
~
Fig. 6.11. SEM image of SiC sintered bodies for different sintering temperatures. Sintering temperature: (a) 1700"C; (b) M
19OO"C; (c) 2050°C; (d) 2200°C. cl'~
!}
s ...
Fig. 6.12. X-ray (a) 2000'C

diffraction P-SiC III Boron Iwt%
patterns of SiC
sintered bodies.
P-SiC 220
P-SiC 311
P-SiC 200
P-SiC 222
(b) 2200'C
Boron Iwt%
30 40 50 60 80
28(' )
density of 97% with the addition of boron alone. This shows the
importance to the sintering of vapor phase SiC of controlling the
C/Si molar ratio with respect to the oxygen content of the
powder. This corresponds with the notion that, when conducting
thermal decomposition of TMDS or another organic silicon
compound, it is important to minimize the amount of siloxane
compounds contained in the raw material.
6.3.2 Boron Concentration

Figure 6.13 shows sinterability of a vapor phase SiC powder at
2050°C when added boron content was varied from 0 to 5 wt%.
Figure 6.14 shows differences in sinterabiIity resulting from
changes in boron concentration as observed by SEM. In samples
to which no boron was added, coarsening of the grains proceeded
with priority, thereby obstructing densification, numerous pores
remained, and there was virtually no sintering (Fig. 6. 14(a».
Even when only 0·05 wt% of boron was added, signs of sintering
appeared (Fig. 6.14(b». Relative density exceeded 90% at a
boron concentration of 0·2 wt% and peaked at a concentration of
1 wt% (relative density: 97% and above; Fig. 6.14(c», indicating
138
100 ~-----------"I Fig. 6.13. Boron

concentration
versus sintering
density,
o 95
o
...
>..
'iii
c
III
U 90
III
...ra
,~
Sintering
~
cr: temperature
85 2050'C
2 4 6
Boron conumtratlon (wt 0,.)
the improvement of sinterability with boron. When boron

concentration was raised to 3 wt%, however, remarkable grain
coarsening could again be observed (Fig. 6.14(d», an a-phase
transformation occurred, and sufficient densification was not
achieved. In addition, X-ray diffraction has shown that a sintered
body of fJ-SiC alone can be obtained with a boron concentration
of 0·1-1 wt% (Fig. 6.15(a», which appears to be optimum.
Higher or lower concentrations will result in insufficient den-
sification, and a partial a-phase transformation has also been
observed (Fig. 6.15(b». In ultrafine SiC prepared by CVD and
containing no sintering aid, grain growth occurs unaccompanied
by densification; the addition of carbon and boron is necessary in
order to obtain a good sintered body. One characteristic of vapor
phase powders with controlled C/Si molar ratios is that they can
produce good sintered bodies with the addition of boron alone
(although at roughly the same concentration as with conventional
powders 19).17
6.3.3 C/Si Molar Ratio and Sinterability

As described previously, it is possible to control the C/Si molar
ratio of vapor phase SiC powders during formation. A knowl-
edge of the relation between sinterability and the C/Si molar
139
il --- I~
s·
<:)
~
I::
~
~
~
~
is
;0;-
-.~
~
1::0
S
Fig. 6.14. SEM images of SiC sintered bodies with different boron concentrations. Added boron concentration: (a) 0 wt% ;
(b) 0·05 wt% ; (c) 1 wt%; (d) 3 wt% .
(a) 2000"0 Fig. 6.15. X-ray

Boron Iwt% diffraction
P-SiO III
patterns of SiC
sintered bodies.
P-SiO 220
P-SiC 3"
P-SiO 200 P-SiC 222
(b) 2000'C
Boron 3wt%
30 40 50 60 70
28( ' )
ratio is therefore necessary. Figure 6.16 shows the change in

sinterability when the macroscopic structure of the powder was
kept constant and the C/Si molar ratio was varied from 0·99 to
1·10, i.e. the relation of C/Si molar ratio to sintering density. 18
Sintering temperature was 2050°C and boron concentration
1 wt%. Cross-sectional SEM images of the sintered body for
various C/Si molar ratios showed that sinterability improved with
an increased C/Si molar ratio. In Si-rich powders where
.z;..
100~---------------' Fig. 6.16. C/Si
molar ratio versus
sintering density .
'iii 95
c
11.1
'0
11.1
-~
~ 90
ii
Q:
Chemical composit ion ratio

(C/Sd
141
C/Si::s 1, there was virtually no sintering, as has been known.

Signs of sintering appeared at C/Si = 1·02, and fairly good
sintered bodies were obtained with C/Si ~ 1·04. X-ray diffraction
showed that the fJ-SiC 111 diffraction pattern peak gradually
grew sharper as the C/Si molar ratio increased from 0·99 to 1·08,
and it is thought that fine fJ-SiC particles with low crystallinity
underwent a molecular transfer, with densification proceeding in
the process in which these particles grew into sub-lJ.IIl-order
microcrystals.
It has been reported that when ultrafine-grain fJ-SiC prepared
by gas evaporation was used as a raw material and pressureless
sintering performed in an Ar atmosphere, grain growth occurred
unaccompanied by densification. 20 With this powder as well, it
has been confirmed that the conventionally-known method of
sintering with boron and carbon is effective in promoting
densification. Here, it is possible to use the free carbon contained
in the raw material powder. When the free carbon content was
adjusted to 4·3 wt% and sintering conducted at 2200°C with
1·0 wt% boron added as a sintering aid, a maximum density of
97% was obtained. 20
An optimal sintered body can be obtained by shifting the C/Si
molar ratio for sintering of vapor phase SiC powder in the
direction of a carbon-rich mixture. Vapor phase powders, which
tend to be rich in silicon, are extremely difficult to sinter and are
not appropriate for use as ceramic powders. Thus, control over
the C/Si molar ratio of the formed powder can serve as a useful
index for the evaluation of vapor phase method raw materials
and processes.
6.3.4 Optimal Content and Sintering Mechanisms for

Carbon and Boron
According to Tanaka et al., the sintering of fJ-SiC powder
generally requires a boron concentration of approximately
0·15-0· 2 wt%, with the optimal carbon concentration falling in
the range 1-2 wt%.19 In addition, Miyaji et al. have reported that
with premixed powders to which boron was added in the vapor
phase during formation a sintering promotion effect appears with
only trace amounts of boron (0·1 wt% ).15 In a powder having an
optimal C/Si molar ratio for sintering (C/Si= 1·04-1·08, as
described previously), for example, the added carbon content of
142
this powder will be equivalent to approximately 1·18-2·34 wt% if

all of the excess carbon acts as a sintering aid. However, the
concentration of methane in the Ar exhaust gas during sintering
of a vapor phase powder increases in the temperature region
lOOO-1500°C, and it is thought that in fact a great deal of the
excess carbon decomposes and is released from the system.
Therefore, the excess carbon contained in the raw material
powder is thought to be roughly equivalent to the 1-2 wt%
added carbon content required for sintering. Depending on the
powder fabrication method, addition of up to -2 wt% boron
may also be required. This is because of differences in P-SiC
sinterability resulting from differences in the raw materials,
particle shape, and oxygen concentration of the powder.
Generally speaking, high-quality pressureless-sintered bodies
cannot be obtained from an SiC powder by the addition of
carbon or boron alone; instead, they must be added together.
With vapor phase powders, however, addition of boron alone is
sufficient to produce a good sintered body. This removes the
need for the addition of carbon, which is comparatively difficult
to deal with from a technical standpoint. It is thought that the
addition of boron inhibits SiC surface diffusion and coarsification
of particles while allowing the sintering driving force to be
maintained up to high temperatures and making possible
densification by grain boundary or volume diffusion. Excess
carbon contained in the raw material and boron form a
carbon-boron system substance on grain boundaries during the
heating process, thereby promoting grain boundary diffusion.
Here, the carbon component present in vapor phase powders has
a different effect from the particulate carbon which is intention-
ally added and dispersed and is thought to result in better
sinterability. This can also be seen from the fact that, even with
the same carbon component, differences in sinterability can occur
due to the morphology and dispersion of added substances.
Figure 6.17 shows SEM images of the structure of an ultrafine
SiC sintered body prepared by this method and a commercial
sintered body prepared by a conventional method after etching
with molten KOH. A clear difference in structural density can be
observed, reflecting the differences in starting materials. 18 Figure
6.18 shows a TEM lattice image of a sintered body prepared
from a vapor phase powder; sintering resulted in good develop-
ment of the P-SiC 111 lattice, creating a crystal morphology
143
Fig. 6.17.
Structure of vapor
phase SiC and
commercial SiC
sintered bodies
(KOH etching;
SEM images). (a)
Vapor phase SiC;
(b) commercial
SiC.
remarkably different from that of the amorphous raw material

powder.
It is desirable that the pellets used in sintering have as high a
green density as possible. Thus the green compact must be
prepared at as high a pressure as possible. Rubber pressing,
vibration pressing and wet pressing are all effective methods with
respect to vapor phase ultrafine powders. In addition , it has been
confirmed that use of a ball mill or similar device to break down
secondary flock particles is very effective in improving green
density and sintering density. Here, the selection of ball material
is important from the standpoint of impurities because of the
144
Fig. 6.1S. Lattice

image of a vapor
phase SiC sin-
tered body.
large impact on sinterability and ceramics properties. The green

density of vapor phase powders is relatively low (relative density:
approximately 45%), but grinding and rubber pressing can bring
the relative density to 50% or more . Some post-treatment should
also be considered, even in the case of vapor phase powders.
Other molding methods that have been studied include slip
casting, doctor blades and extrusion molding, and their useful-
ness has been confirmed.
In summary, the relatively good sinterability of vapor phase
SiC powders is thought to be a reflection of physical and
chemical properties such as small particle size (on the order of
several hundred nanometers) and a deviant C/Si molar ratio.
This is also clear from the fact that a good ceramic with density
of at least 3·10 g/cm3 can be obtained by hot-pressing a TMDS
system ultrafine powder without the addition of a sintering aid .
6.4 SUMMARY
p-type silicon carbide ultrafine powders with narrow particle size

distribution can be obtained by the vapor phase method, and
145
these powders are of great interest from the standpoint of

possible applications. Compared with the ordinary vapor-phase
reaction method, in which a chloride or monosilane is reacted
with a hydrocarbon to form a powder, the thermal decomposi-
tion method, which uses an organic silicon compound, is
advantageous because it does not involve chlorine compounds
and other reaction products that are relatively difficult to process
and because it provides a high yield. Ultrafine SiC powders such
as those prepared by the vapor phase method with good
sinterability and sharp particle size and shape distributions are
also extremely important from the standpoint of possible
applications to SiC fine ceramics. Because it is difficult to obtain
pure SiC powders using conventional methods, fine-structure SiC
ceramics for structural elements are particularly promising as
electronic ceramics, a field plagued by difficulties in the design of
material properties. As yet there have been no discoveries in the
field of vapor phase powders capable of overturning conventional
SiC ceramics concepts, but these new powders are helping to
bring about recognition for technological progress that will lead
to improvements in SiC ceramic functionality and expansion of
the range of applications. Fulfillment of the various conditions
required for commercial application, such as development of
mass production systems and control over cost and powder
properties, would mean that industrial-scale production could
become possible in the near future. Further investigation of
sintering conditions and fields of application for the ceramics
obtained will allow vapor phase SiC powders to develop into
high-performance, highly functional SiC ceramics with a broad
range of practical applications.
REFERENCES
1. Scace, R. I. & Slack, G. A., Silicon Carbide, ed. J. R. O'Connor &

J. Smiltens. Pergamon Press, Oxford, 1960.
2. Kijima, K., Zairyou Kagaku 19(1) (1982), 12-18 (in Japanese).
3. Katou, A., Formation of ultrafine powders by vapor phase
reactions. Ceramics Japan, 13(8) (1978) (in Japanese).
4. Kendall, J. T., J. Chem. Phys., 21 (1953), 821.
powders by a vapor phase method. J. Less-Common Met., 68,
(1979), 29-41.
146
6. Sedaka, N. & Kawashima, C., Yogyo Kyokai Shi, 76 (1968),154 (in

Japanese).
7. Patrich, L., Hamilton, D. R. & Chcyke, W. J., Phys. Rev., 143
(1966), 2526.
8. Endo, M., Moriyama, Y. & Urasato, N., Ultra-fine silicon carbide
prepared by CVD method. Ohyou Buturi, 53(1) (1984),70-73 (in
Japanese).
9. Endo, M., Urasato, N., Nakao, M. & Shiraishi, M., Carbon '84,
Bordeaux, France, p. 428.
10. Endo, M., Sano, T., Mori, K., Urasato, N. & Shiraishi, M.,
Preparation of ultrafine SiC powders by pyrolysis of tetramethyldisi-
lane. Yogyo Kyokai Shi, 95(1) (1987), 104-9 (in Japanese).
11. Okabe, Y., Hojo, J. & Kato, A., Formation of silicon carbide
powders by the vapor phase reaction of the SiH.-CH.-H2 system.
Nihon Kagakukai Shi, No.2, (1983), 188-93 (in Japanese).
12. Kijima, K. & Konishi, M., Preparation of ultrafine SiC powders by
the plasma CVD under reduced pressure, J. Ceramic. Soc. Japan,
93(9) (1985),511-16 (in Japanese).
13. Yamamoto, M., Present situation of SiC powder. Ceramics Japan,
22(1) (1987), 46-51 (in Japanese).
14. Okabe, Y., Miyachi, K., Hojo, J. & Kato, A., Sintering behaviour
of ultrafine silicon carbide powders obtained by a vapor phase
reaction. Nihon Kagakukai Shi, No.9, (1981), 1363-70 (in
Japanese).
15. Miyaji, K., Okabe, Y., Hojo, J. & Kato, A., Sintering of ultrafine
silicon carbide powders by using boron and carbon as sintering aids.
Nihon Kagakukai Shi, No.1, (1983), 28-33 (in Japanese).
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Meeting for Kantou Area, 22 (1985), (in Japanese); 21(1985), (in
Japanese).
17. Endo, M., Mori, K., Yamamoto, H., Kiyono, J. & Urasato, N.,
Annual Meeting of Ceramics Society of Japan, 2Ft6 (1986) (in
Japanese).
18. Endo, M., Mori, K., Yamamoto, H., Urasato, N. et al., 25th
Symposium of Ceramics Society of Japan, 12 (1987) (in Japanese).
19. Tanaka, H., Inomata, Y., Tsukuda, H. & Hagimura, A., Normal
sintering of II-SiC powder, amounts of boron and carbon additives.
Yogyo Kyokai Shi, 92(8) (1984), 461-5 (in Japanese).
20. Ohkouchi, M. & Ando, M., Pressureless sintering of ultrafine SiC
powder produced by gas evaporation method. Yogyo Kyokai Shi,
94(1) (1986), 26-34 (in Japanese).
147
7 Sintering Behavior of
Ultrafine Silicon
Carbide Powder
lUNICBI BOlO
ABSTRACT
The pressureless sintering of ultrafine SiC powder (average

particle size: 0·01-0·12!l1n) obtained by vapor phase reaction
method was investigated with an emphasis on the effects of powder
properties and sintering aids.
The ultrafine SiC powder showed a remarkable densification in
the presence of both carbon and boron as sintering aids, but the
sintering aids were indispensable to densification. The homoge-
neous addition of sintering aids was important to enhance the
effects thereof. The deposition of an adequate amount of free
carbon and boron from the vapor phase was available on the
preparation of SiC powder, and the resulting SiC powder showed
very high sinterability due to the widespread dispersion of
sintering aids on the surface of SiC particles. When the atomic
ratio (C-O)/ Si was near 1·0, SiC powder had high sinterability
because free carbon accelerated SiC sintering by removal of the
surface oxide layer of SiC particles while excess carbon retarded
sintering.• The effect of the particle size of the starting powder was
significant: a particle size below 0'05!l1n was required for
densification above 95% of theoretical by 2050°C sintering. The
binary mixing of SiC powders with different particle sizes
improved sinterability, being especially effective in promoting the
densification of coarse powders.
In conclusion, the conditions for SiC powder with good
sinterability are the reduction of particle size, the control of
chemical composition, and the homogeneous addition of sintering
aids.
149
Junichi Hojo
7.1 INTRODUCTION
Among the methods of manufacturing silicon carbide (SiC)

sintered bodies are pressureless sintering, reaction sintering and
hot-pressing. Of these, pressureless sintering is the best suited to
efficient, large-scale production of dense, high-strength sintered
bodies with complicated shapes. Because of its strong covalency,
however, SiC is difficult to sinter, and it has been reported! that
sintering at 2500"C under a pressure of 20 kbar is required to
bring a pure SiC powder to theoretical density. As a result,
research has been conducted on a variety of sintering aids. In
1973 Prochazka2 reported that the simultaneous addition of small
amounts of carbon and boron to submicron-grade SiC resulted in
a remarkable sintering promotion effect.
Since this work by Prochazka, 2 a pressureless sintering method
for SiC using carbon and boron as sintering aids has been
awaited. The manufacture of high-density sintered bodies by
pressureless sintering in the presence of carbon and boron has
been studied with SiC fine powders produced by the vapor phase
reaction method3 •4 or by the siliconization of carbon black. 5 It is
also known that aluminum is as effective a sintering aid as
boron. 6 Pressureless sintering requires finely divided SiC with
good sintering activity. If finer powder improves sintering activity
so that the quantity of the sintering aid can be reduced,
high-strength sintered bodies possessing the superior characteris-
tics unique to SiC can be produced. Furthermore, since the
strength of the sintered body improves in inverse proportion to
the size of the sintered grains, the use of finely divided starting
materials is important in achieving a finer structure.
Methods of synthesizing SiC powders can be broadly divided
into solid-phase reaction, using silica and carbon as raw
materials, and vapor phase reaction, which use volatile silicon
compounds. The latter type is better suited to the synthesis of
ultrafine powders. Since powders produced using the vapor phase
method are of high-purity less aggregated and ultrafine, ex-
tremely high sinterability can be achieved. The authors have
obtained ultrafine SiC powders with a particle size of approxim-
ately 0·01 JLm using the vapor phase reaction method. 7- 9 When
carbon and boron are added to this powder and pressureless
sintering pedormed, sintered bodies densified to above 95% of
theoretical can be manufactured at a sintering temperature of
150
Sintering Behavior of Ultrafine SiC Powder
about 2000"C. 10--13 This chapter will introduce the results of

research conducted on the sintering properties of ultrafine SiC
powders and discuss the relationship of SiC powder properties
and sinterability as well as the sintering promotion effect of
carbon and boron.
7.2 SYNTHESIS METHODS AND PROPERTIES

OF SiC POWDERS
SiC powders are synthesized by the following three reaction

systems:
H2
Si(CH3)4 9S0--14OO"C ~ SiC (S systemf (1)
H2
Si~+C~
14OO"C ~ SiC (H system)8 (2)
H2
Si(CH3)CI3 Plasma
~ SiC (P system)9 (3)
Table 7.1 summarizes the synthesis conditions and properties of

SiC powders. Particle size and chemical composition were
controlled by varying reaction temperature, reaction gas con-
centration, and total gas flow rate. A commercial SiC fine
powder (C-1) was also used for purposes of comparison.
TEM photomicrographs of vapor phase method powders are
shown in Figs 7.1, 7.2 and 7.3. SiC powders produced using the
vapor phase reaction method have a narrow particle size
distribution and consist of virtually spherical particles. Hollow
SiC particles are formed in the H system: H-1 consists almost
entirely of such particles, and about half of the particles
comprising H-2 were also hollow. Figure 7.4 shows particle size
distribution curves for vapor phase method powders and a
commercial powder. The commercial powder consists of irregu-
larly shaped particles and has a larger particle size and broader
particle size distribution than the vapor phase method powders.
Figure 7.5 shows X-ray diffraction patterns for the vapor phase
method powders. SiC powders of the S, H, and P systems were
all of crystalline phase f3. The diffraction lines grew sharper in
the order of systems S, Hand P, with the P-system sample
15t
~
N_
Table 7.1
Preparation Conditions and Properties of tJ-SiC Powder
Preparation conditions" Properties
Sample Si source Concentration Concentration Temp- Chemical composi- Pamcleb Density or
o/Si source o/CH4 erature tion (in mol) size sintered body
('Yo) ('Yo) ('C) (pm) ('Yo)
CISi OISi (C-O)ISi
S-l 2 1200 1·03 0·08 0·95 0·01 92d

S-2 2 1250 1·03 0·07 0·96 0·02 97
S-3 2 1300 1·03 0·05 0·97 0·02 96
S-4 2 1350 1·07 0·06 1·01 0·02 94
S-5 2 1400 1·08 0·06 1·03 0·02 91
S-6 Si(CH3 )4 8 1200 1-14 0·13 1·01 0·02 96
S-7 5 1200 1·12 0·11 1·01 0·06 92
S-8 6 1200 1-18 0·08 1·10 0·06 75
S-9 6 1000 1·14 0·13 1·01 0·08 87
S-lO 8 950 1·21 0·15 1·06 0·12 84
H-1 3 1400 0·95 0·02 0·93 0·05 75d
Si~ g
H-2 2·5 1400 0·96 0·06 0·90 0·02 92d
P-1 Si(CH3 )CI3 6 plasma 1·00 0·16 0·84 0·01 95'
SB-1e Si(CH3)4 2 1400 1·09 0·12 0·97 0·01 95'
90'
C-1 Commercial tJ-SiC powder 1·02 -0 1·02 0·18 68
tJ Gas composition was balanced with hydrogen.
b Median diameter of particle size distribution curve on number base.
C Sintering temperature and time: 2050"C, 30 min. Boron added: 1 wt%. Green density of powder compact (by rubber pressing): S
series -40%; H-1-30%; H-2-35%; P-1-50%; C-l-60%.
d Carbon powder (2 - 5 wt%) was added to SiC powder so that (C-O)/Si = 1·02_
• BCl3 (0·1 vol%) was added to gas phase.

f Sintered at 19OO"C without additives.
Fig. 7.1. TEM

photograph of SiC
powder obtained
by vapor phase
reaction using
Si(CH3)4'
5-7
L-=-~_________________
~ 0.2
_~ __
having high crystallinity. In the P-system sample trace amounts

of a-phase material could be observed in addition to the
p-phase. The commercial powder was also of the p variety, and
trace amounts of a-phase material were present.
SiC powders contain free carbon and impurity oxygen in
Fig. 7.2. TEM

photograph of SiC
powder obtained
by vapor phase
reaction using
Si~andC~.
H-l
~~~------------------
~ 0.2 m
153
Junichi Hojo
Fig. 7.3. TEM

photograph of SiC
powder obtained
by plasma tech-
nique using
Si(CH3)CI 3 •
P-l
~~------------------
...- 0.2 m
addition to SiC. In the synthesis of SiC powders by the vapor
phase reaction method, free carbon is produced as a byproduct
of the thermal decomposition of hydrocarbon eliminated from
the organic silicon compound or of methane mixed in reaction
system. The quantity of free carbon can be controlled with
reaction conditions. The inclusion of impurity oxygen is due to
oxidation of the SiC surface by oxygen or water vapor during
handling in the air, and vapor phase method powders having
large surface areas contain large quantities of impurity oxygen.
The SiC powders were molded in a steel die (0·5 t/cm 2) and
rubber-pressed (5 t/cm2 ) to form a green compact. Green
Fig. 7.4. Particle ( -1

size distribution
curves of SiC
powders.
....,
I-
g 50
Q)
>
....,
Cl
:::J
E
:::J 0.2 0.3 0.4
U
Particle si ze ( ~ m)
154
S-5
a-SiC
l
a-Sic <Ill)
l
,
a-SiC (200)
Fig. 7.5. X-ray
diffraction pat-
terns of SiC
powders.
H-l
P-l
35 40 45 50
29 (CoKa) (deg)
compact density was about 40% for the S-system, 30-35% for
the H-system, about 50% for the P-system, and about 60% for
the commercial powder. The S- and H-system samples had poor
moldability. The H-system sample had a lower green compact
density than the S-system sample because it contained hollow
particles. The reason why the P-system sample had better
moldability than the S-system sample may be that its high
crystallinity gives it a low particle surface activity and good
fluidity. The commercial sample had even better moldability,
probably as a result of its large particle size and broad particle
size distribution.
These green compacts were then placed in graphite containers
and sintered using high-frequency induction heating. Firing up to
14OO"C was performed in a vacuum to remove gas from the
samples, and at higher temperatures was performed in argon gas
of about 40 kPa in order to inhibit SiC decomposition. Relative
densities of the sintered bodies obtained at typical sintering
conditions are summarized in Table 7.1.
7.3 SINTERABILITY OF SiC POWDERS

7.3.1 The Eft'ect of Sintering Aids
When SiC powder was sintered without a sintering aid, even at
2050"C no densification occurred but grain growth progressed.
155
Junichi Hojo
Even ultrafine SiC powders synthesized with the vapor phase

reaction method require a sintering aid for pressureless sintering.
Therefore, the author investigated the effect of addition of
carbon and boron, two of the representative sintering aids used
with SiC.
7.3.1.1 Effect of Carbon and Boron Content
In order to determine optimum sintering aid concentrations,
carbon powder (mean particle size 0·14 fUll) and boron powder
(mean particle size 0·13 fUll) were added to sample S-1, which
was then sintered at 2000-2050"C. Figure 7.6 shows change in
sintered body density as a function of carbon and boron content.
When either carbon or boron alone was added, virtually no
densification occurred, but when the two were added together
densification progressed remarkably. The optimum concentra-
tions were 2 wt% for carbon and 1 wt% for boron. Addition of
these elements in greater amounts resulted in some inhibition of
densification. In Fig. 7.6, rubber-pressing was not performed
during molding of the green compact, resulting in a low green
compact density and a maximum density of approximately 80%
for the sintered body. When green compact density was
increased by rubber-pressing, sintered body density rose to above
90% under the presence of optimum concentrations of carbon
and boron (see Table 7.1).
Fig. 7.6. EtIect of

additives on sin-
tering of SiC 100
powders. Sample:
S-l. Green ~
density: -30%
(non-rubber pres- ....>-
sing). Heating: Ul
c::
2000" - 2050"C, OJ
u
30 min. Addi- OJ
tives: 0; addition >

....c
ofBpowder, £;
addition of C
powder in a pre-
-
OJ
a::
sence of 2 wt% B
powder, 0; addi-
tion of B powder 0
in a presence of 0 1 2 3 4 5
2wt% Cpowder. Additive (wt%)
Table 7.1 shows the density of SiC sintered body obtained at

2050°C using sintering aids. Many of the samples exhibited
densification with the addition of boron powder alone. In these
cases, the free carbon contained in the SiC powder seems to act
as a sintering aid in place of carbon powder.
7.3.1.2 Effect of the Uniform Addition of Carbon
The uniform addition of a sintering aid to SiC powder allows a
large sintering promotion effect with only a small quantity of
sintering aid. Uniform addition is particularly important in the
case of carbon because of its slow rate of diffusion. Binder pitch
was added to SiC powder (S-1) using an organic solvent, and the
effect of uniform addition of carbon was studied. Boron powder
was added at a concentration of 1 wt%, and sintering was
performed at 1900°C. The results are shown in Table 7.2. When
benzene was used as the solvent for the binder pitch, the sintered
body had a low density and there was no difference from the case
when carbon powder was added. When highly soluble tetrahydro-
furan was used as the solvent for the binder pitch, however,
sinterability improved remarkably, and the density of the
sintered body reached 90% at 1900°C. Prochazka 14 has also
reported obtaining high sinterability by adding polymethyl-
phenylene to SiC powder using an organic solvent. These results
support the conclusion that the uniform addition of carbon
makes a major contribution to the improvement of SiC
sinterability.
Table 7.2
Carbon source Solvent Temperature Carbon Density of Effect of
of mixing added sintered Homogeneous
("C) (wt%) body Addition of
(%) Carbon
Carbon powder 2·0 56
Binder pitch Benzene Room 2·2 56
temperature
Binder pitch Tetrahydro- Room 2·3 68
furan temperature
Binder pitch Tetrahydro- 50-60 2·2 90
furan
Sample, S-1; boron added, 1 wt%; green density, -40%; sintering

temperature and time, 19OO"C, 30 min.
157
Junichi Hojo
7.3.1.3 Sintering Promotion Mechanism of Carbon and

Boron
As the sintering promotion mechanism of carbon with respect to
SiC, it has been proposed that removal of the surface oxide layer
of SiC particles causes an increase in surface energy. 14 When
boron alone is added, there is little densification of the SiC
sintered body, and the need for removal of the surface oxide
layer by carbon has been generally accepted. As the sintering
promotion mechanism of boron, it has been proposed that
segregation onto the grain boundaries causes a reduction of grain
boundary energy14 or that a substance of the carbon-boron
system forms to promote grain boundary diffusion. 15 SiC
sintering requires the presence of boron, and absolutely no
densification occurs without it. Furthermore, as will be described
below, boron acts to inhibit SiC grain growth caused by surface
diffusion, and it is difficult to accept the premise that the
presence of boron at the grain boundaries promotes grain
boundary diffusion. Therefore, the sintering promotion effect of
boron is thought to be due to the thermodynamic effect of
reducing SiC grain boundary energy.
Another proposed mechanism for the sintering promotion
Fig. 7.7. Effect of

additives on grain I?
::I.
growth and den-
sification in the
course of heating.
N
.-
Ql
en
2
Sample: S-l.
Heating rate: c-
c::
L..
<!>
1
-20"C/min.
Heating duration: 0
1 min at 18OO"C ;;; 100
and 19OO"C, 30 ~
min at 2050"C. ....>- 80

Additives: 0; en
c::
undoped, .; Ql
"0
C(2wt%),6;B Ql 60
>
(1 wt%),e; ....
B(1 wt%) + C(2 wt%). c
-Ql
c:: 40
1800 1900 2000

S!ntering temperature (OC)
158
effect of carbon and boron is that of grain growth inhibition. 3 ,15

Specifically, carbon and boron inhibit SiC grain growth caused by
surface diffusion during increasing temperatures, thereby main-
taining the driving force of sintering up to the high temperatures
at which volume diffusion-induced densification becomes active.
Figure 7.7 shows changes in relative density and mean grain size
of sintered bodies during the heating process for S-1 samples
containing no additives, carbon only, boron only, and both
carbon and boron. Addition of carbon and boron resulted in
remarkable inhibition of SiC grain growth. In particular, when
carbon and boron were added together there was remarkable
control of grain growth during increasing temperature. This is
thought to contribute to densification. When carbon or boron
was added alone, however, grain growth was inhibited but
densification did not progress. Thus it can be seen that grain
growth inhibition plays a supplementary role to the sintering
promotion mechanism.
7.3.2 Influence of Synthesis Method of SiC Powders

Sinterability for SiC powders of the systems S, Hand P, each
having different reaction systems during vapor phase synthesis,
was compared (see Table 7.1). Most of the samples produced
sintered bodies with a relative density of 90% or more and had
good sinterability. The poor sinterability of S-8, S-9 and S-10 is
attributable to large particle sizes and large quantities of free
carbon. The poor sinterability of H-1 is due to a low green
compact density, resulting from hollow SiC particles, and its
large particle size. H-2, which in contrast to H-1 has few hollow
particles and small particle size, showed roughly the same degree
of sinterability as S-1. P-1 has high crystallinity, but there was no
major difference in sinterability with S-1. This is due to the fact
that in all the samples crystallinity increases to approximately the
same extent at the high temperatures at which densification
proceeds rapidly.
In this way, there was little difference in sinterability due to
production system among the SiC powders.
7.3.3 Eft'ect of Vapor Phase Addition of Sintering Aids

During synthesis of SiC powders by the vapor phase reaction
method, it is possible to precipitate an appropriate amount of
159
lunichi Hojo
Fig.7.S. 100~----------------~-,
Variation of rela-
tive density with
sintering tem- 80
perature.
-
>-
.....
Samples: 0, S-l,
0; S-3,.; H-l,
( /)
c
.; P-l. C added; ~ 60
S-l; 2·0 wt%, S-3; Cll
>
Owt%; H-l; .....
2·6wt%, P-l; o 40
Cll
4·8wt%. B c:::
added: 1 wt%.
Heating: 30 min.
1400 1600 1800 2000
Sintering temperature (Oe)
free carbon. There is a high probability that carbon precipitated

from the vapor phase will diffuse uniformly on the SiC particle
surface, and a large sintering promotion effect can be expected.
As shown in Table 7.1, samples S-2, S-3 and S-6 produced
sintered bodies with relative densities of 95% and over with the
addition of boron powder alone. Thus they had better sin-
terability than SiC powder to which carbon powder was added.
This can be attributed to the effect of uniform addition of free
carbon during vapor phase synthesis. Figure 7.8 shows change in
sintered body density as a function of sintering temperature.
Densification becomes significant from around 1800°C in the case
of S-3 and from around 1900°C in the case of S-1, H-1 and P-l.
The reason for the higher densification temperature in the case of
the latter samples, which used carbon powder as a sintering aid,
is the slow diffusion of carbon into the SiC particle surfaces. In
the case of S-3, to which free carbon was uniformly added during
synthesis, the carbon becomes effective at low temperatures.
Figure 7.9 shows change in the mean grain size of sintered bodies
as a function of sintering temperature. The sintered body density
of S-3 reached 90% at 1900°C, and because of the low
temperature grain size was less than 0·5 J.UD. In order to obtain
SiC sintered bodies with high density and fine-grain structures,
highly active powders such as S-3 should be sintered at low
temperatures, at which grain growth proceeds at a slower rate.
In the case of boron as well, the effect of uniform addition in
the vapor phase reaction system can be expected. SB-1 in Table
160
Fig.7.9.
Variation of grain
size with sintering
1.0 temperature.
Samples and sin-
tering conditions
are the same as in
Q)
N Fig. 7.8.
0.5
-
U)
c
c
.....
<.!)
o 1600
S!nter!ng temperature (Ge)
7.1 is an SiC powder to which boron was added using B03

during vapor phase synthesis. SB-1 provided a sintered body with
a relative density of 95% after sintering at 1900°C without the
addition of carbon powder and boron powder and showed better
sinterability than S-3, to which boron powder was added.
Uniform addition of boron is also effective. SB-1 has a boron
content of approximately 0·1 wt%. It can thus be seen that
uniform addition allows sintering promotion with only a small
amount of boron.
7.3.4 Effect of the Chemical Composition of SiC

Carbon added as a sintering aid reacts with the surface oxide film
of SiC particles during firing according to the following reaction:
SiOx + (1 +x)C~SiC+xCO (4)
Table 7.1 shows differences in the C/Si and O/Si molar ratios of
SiC powders. When (C-O)/Si = 1, the composition after firing is
the stoichiometric one for SiC, but when (C-O)/Si < 1 there is
residual surface oxygen, and when (C-O)/Si> 1 there is residual
free carbon. Figure 7.10 shows the relationship between sintered
body density and grain size and the (C-O)/Si molar ratio of the
raw material powder. SiC powders with a (C-O)/Si ratio near 1
exhibit good sinterability. When the (C-O)/Si ratio is less than
161
Junichi Rojo
Fic. 7.10. Effect

of chemical com-
_.....
~
position of SiC It<!
..... -
powder on den- ~>-
sification and
grain growth. ~~
Samples: 0, .; S .!l:! ~ 50 r----:--
series, 6., A; H
series, 0, .; P
series (the filled 2
symbols indicate
-
Q.)
N
the addition of
carbon powder as
sintering aid). SiC
~
01::
-
.....
Q.)O
(/) 1
~ :;. 0 ~,-----J,--_ _-L_--'-_~""

particle size:
0.9 1.1
O·Ol-O·06!Ull. B
added: 1 wt%. (C-O) IS 1 (in mol)
Heating: 2050"C,
30 min.
0·95, sinterability drops remarkably and there is considerable
grain growth, but this is virtually unaccompanied by densifica-
tion. Even in samples like this with insufficient carbon, addition
of an appropriate amount of carbon powder improved sin-
terability. These results strongly support the effectiveness of
removal of the surface oxide layer of SiC by carbon. When
carbon powder is added, however, the optimal content is
(C-O)/Si = 1~02, with a slight excess of carbon being required.
The deterioration in sinterability when (C-O)/Si > 1 may be due
to the segregation of excess carbon on the grain boundaries.
The relationship in Fig. 7.10 is based on results obtained from
SiC powders having different production systems. Regardless of
the method of synthesis, it is important from the standpoint of
improving sinterability of SiC powder to balance carbon and
oxygen contents such that (C-O)/Si becomes 1.
7.3.S Etfect of SiC Particle Size

From sintering data of vapor phase method powders and
commercial powders at 20500C, the relationship between the
particle size of the raw material powder and sintered body
density is summarized in Fig. 7.11. Particle size has an extremely
large impact on SiC sinterability, with increases in particle size
bringing remarkable reductions in sintered body density. In
162
Fig. 7.11. Effect

of particle size of
SiC powder on
the sinterability .
>-
Samples: 0; S
...- series,.; P
en
c: series, t::,; com-
Q)
"0 mercial powder
Q)
>
(C-l). C added:
0-5wt%
«C-O)/Si =
O·95-H16). B
added: 1 wt%.
Heating: 2050"C,
30 min.
o 0.05 0.10 0.15 0.20
Particle size (~rn)
order to produce a SiC sintered body with a relative density of

95% or over by pressureless sintering at 2050°C, an ultrafine raw
material powder with particle size of less than 0·05 !.Im is needed.
Figure 7.12 shows SEM photomicrographs of SiC sintered
bodies. The commercial powder (C-l), with its large particle size,
produced sintered bodies with low density accompanied by
S-3(d r =96 Fig. 7.12. SEM

photographs of
fracture surfaces
of SiC sintered
bodies (dr: rela-
tive density). B
added: 1 wt%.
Heating: 2050"C,
30 min.
163
Junichi Hojo
remarkable grain growth. The high-density sintered body ob-

tained from the vapor phase method powder (S-3), on the other
hand, possesses a uniform microstructure consisting of grains
approximately 1 J.Ull in size.
7.3.6 Effect of Particle Size Blending

Fine powders have poor compactability during molding, but the
blending of powders with different particle sizes makes possible
an increase in green compact density and an accompanying
improvement in sinterability. The effect of particle size blending
on SiC sintering was investigated using vapor phase method
powders and commercial powders. Figures 7.13 and 7.14 show
change in relative density of green compact and sintered body as
a function of powder blending ratios for the systems P-1
(0·01 J.Ull) + S-9 (0·08 J.Ull) and P-1 (0·01 J.Ull) + C-1 (0·18 I'm),
respectively. Measured values for green compact density were
close to values calculated assuming an unblended state. Thus the
effect of particle size blending on green compact density is small,
but an increase in sintered body density was observed. In the
case of P-1 + S-9, sinterability improved remarkably with 85 wt%
large particles. In the case of P-1 + C-1 as well, C-1, with its large
particle size, has very poor sinterability, but blending with a SiC
FIg. 7.13. Effect ~
~
of binary mixing ~
on compactability -: 100 P-1<O.0lIlm)

"0
70 0c
and sinterability 0 c.
.0 +S-9<O.08Ilm) E
of SiC powder "0
0
u
(P-1 + S-9 Q)
"- 90 60 :u
system). -----, .....
.- I
Q)
"0
c:
theoretical curve rn
of relative density ..... 80
j50i
of powder com- o
pact calculated on >-
.....
a basis of non- rn
c:
mixing state. C Q)
"0
70 ~
40 "0
added: 0-5 wt% Q) Q)
«C-O)/Si = 1·02). .....

> ~
B added: 1 wt%.
Heating: 2050"C, -
c 60
Q)
0:
0 50
30 t;
100 i
30 min. Fraction of coarse powder (wt%)
164
Fig. 7.14. Effect

N
of binary mixing
»100 70 '0 on compactability
"t:l c
0
.c c.
E and sinterability
"t:l
o of SiC powder
--L!.--I'<-o~60 u
(P-1 + C-1
OJ
I- I-
.....
OJ OJ
"t:l system). Sintering
C ~
8. conditions are the

'" same as in Fig.
~
0 SO 50 t;
» »
7.13.
..... .....
'"c 70
OJ 40 @
(/)
"t:l "t:l
OJ
>
.....
c 60
L-. _ _ _ _L -_ _ _----'
.-
>
OJ
30 -::;
OJ
0::: 0 50 100 cu
0:::
Fraction of coarse powder (wt%)
fine powder promotes densification. This effect of blending

particle sizes was explained using two mechanisms: particle
rearrangement and inhibition of grain growth by fine particle
blendingY Figure 7.15 shows the relationship between relative
density and mean grain size of sintered body for the system
P-1 + C-1, and it can be seen that blending of P-1 inhibits the
grain growth of C-l.
Fig.7.lS.
Relationship be-
6 C-I P-I<1S%)+ tween grain size
C-HS5%)
~ and density in
,,
~
;J.
binary mixing
,,, system. C added:
-4
OJ
,,
N
O-Swt%
, «C-O)/Si = 1·02).
-
(/)
c ,
I
c I B added: 1 wt%.
l-
Heating: 1600-
I
CI I
I
OJ
CI
20SO"C, 30 min.
cI-
2
OJ
«>
SO 100
Relative density (%)
165
lunichi Hojo
7.4 SUMMARY
Ultrafine SiC powders (mean particle size: 0·01-0·12~)

synthesized by the vapor phase reaction method were
pressureless-sintered, and the following conclusions were drawn
concerning the relationship between SiC powder properties and
sinterability and the effect of sintering aids.
(1) Simultaneous addition to ultrafine SiC powders of carbon
and boron as sintering aids results in remarkable densifica-
tion. Without the addition of a sintering aid, however,
there was no densification. SiC sintering requires the use of
a sintering aid.
(2) In order to achieve good sinterability, the uniform addition
of a sintering aid is important. With the vapor phase
reaction method, it is possible to precipitate an appropriate
amount of free carbon during synthesis of the SiC powder.
Vapor phase addition of boron is also possible. In this way,
SiC powders to which carbon and boron have been added
in the vapor phase have extremely good sinterability
because of the uniform dispersion of the sintering aid on
SiC particle surfaces.
(3) Free carbon exhibits a remarkable sintering promotion
effect by removing the surface oxide layer of SiC particles.
Since excess carbon inhibits sintering, however, it is
important to balance the carbon and oxygen contents of
the raw material powder. SiC powders with a (C-O)/Si
ratio of 1 exhibit good sinterability.
(4) The particle size of the raw material powder has an
extremely large impact on SiC sintering, and an ultrafine
powder with a mean particle size of less than 0·05 ~ is
required to obtain a sintered body with relative density of
95% or more by pressureless sintering at 2050°C.
(5) The blending of powders having different particle sizes can
improve sinterability. The blending of ultrafine SiC
powders is effective in promoting the sintering of SiC
powders having a large particle size.
In summary, the improvement of SiC sinterability requires
finer raw material powders, control over chemical composition,
and uniform addition of sintering aids. Recently, there has been
increasingly active research concerning the synthesis of SiC fine
166
powders offering improved sinterability. 16 The utilization of

ultrafine raw material powder will make possible the practical
application of high-performance SiC materials.
REFERENCES
1. Nadeau, J. S., Very high pressure hot pressing of silicon carbide.
Am. Ceram. Soc. Bull., 52(2) (1973), 170-4.
2. Prochazka, S., Sintering of silicon carbide. In Ceramics for High
Performance Applications, ed. J. J. Burke, A. E. Gorum & R. N.
Katz. Brook Hill Publishing Co., Chestnut Hill, 1974, pp. 239-52.
3. Greskovich, C. & Rosolowski, J. H., Sintering of covalent solids. J.
Am. Ceram. Soc., 59(7-8) (1976), 336-43.
4. Backer, W. & Hausner, H., Observations on the sintering
characteristics of submicron silicon carbide powders. Science of
Ceramics, 9 (1977), 168-75.
5. Hase, T. & Suzuki, H., Sinterability of submicron P-SiC prepared
from siliconization of carbon black. Yogyo-Kyokai-Shi, 86(12)
(1978),606-11.
6. Backer, W., Landfermann, H. & Hausner, H., Sintering of alpha
silicon carbide with additions of aluminum. Powder Met. Int., 11(2)
(1979), 83-5.
powders by a vapor phase method. J. Less-Common Met., 68(1)
(1979), 29-41.
8. Okabe, Y., Hojo, J. & Kato, A., Formation of silicon carbide
powders by the vapor phase reaction of the Si14-C14-H2 system.
Nippon-Kagaku-Kaishi, (2) (1980), 188-93.
9. Kato, A., Okabe, Y. & Hojo, J., Application of plasma jet for the
preparation of ultrafine silicon carbide powders by vapor phase
reaction. Funtai-Oyobi-Funmatsuyakin, 27(1) (1980), 32-4.
10. Okabe, Y., Miyachi, K., Hojo, J. & Kato, A., Sintering behaviour
of ultrafine silicon carbide powders obtained by a vapor phase
reaction. Nippon-Kagaku-Kaishi (Special Articles on Chemistry of
Inorganic Materials), (9) (1981), 1363-70.
11. Miyachi, K., Okabe, Y., Hojo, J. & Kato, A., Sintering of ultrafine
silicon carbide powders by using boron and carbon as sintering aids.
Nippon-Kagaku-Kaishi, (1) (1983), 28-33.
12. Hojo, J., Miyachi, K., Okabe, Y. & Kato, A., Effect of chemical
composition on the sinterability of ultrafine SiC powders. J. Am.
Ceram. Soc., 66(7) (1983), Cl14-15.
13. Tsuda, H., Hojo, J. & Kato, A., Effect of binary powder mixing in
sintering of fine silicon carbide. Funtai-Oyobi-Funmatsuyakin, 31(1)
(1984), 1-7.
14. Prochazka, S., Sintering of silicon carbide. In Materials Science
Research, Vol. 9, Mass Transport Phenomena in Ceramics, ed. A.
167
lunichi Hojo
R. Cooper & A. H. Heuer. Plenum Press, New York, 1975, pp.

421-31.
15. Hase, T. & Suzuki, H., Initial-stage sintering of tJ-SiC with
concurrent boron and carbon additions. Yogyo-Kyokai-Shi, 88(5)
(1980), 258-64.
16. Yamamoto, M., Present situation of SiC powder. Ceramics lapan,
22(1) (1987), 46-51.
168
8 Grain Boundaries in
High-Purity Silicon
Carbide
YOICHI ISIDDA, HIDED
ICHINOSE & YOSHIZO
INOMATA
ABSTRACT
Grain boundaries in high-purity silicon carbide bicrystals prod-

uced by sublimation-deposition at 2800 K were examined by
high-resolution transmission electron microscope (HRTEM). Two
asymmetric tilt boundaries with a rotation of 70.50 about [1100],
i.e. a 6H polytype boundary parallel to (0001) of one of the
crystals and a 6H /15R hetero-polytype boundary were observed.
Both boundaries were without an amorphous layer. The periodic
arrangement of atoms in the boundaries was analyzed using the
geometrical coincidence-site lattice model, while the actual atomic
structure of the boundary was modeled from the HRTEM images.
8.1 INTRODUCTION: CRYSTAL GRAIN

BOUNDARY mICKNESS
The crystal grain boundaries of silicon carbide normally consist

of substances that are different in composition and structure from
the matrix. Not only silicon carbide but most materials prepared
by sintering a powder have this kind of structure. In samples
produced using a sintering additive, the additive tends to remain
on the grain boundaries and forms a thick grain boundary layer,
thereby degrading the mechanical properties of the material.
This is not true, however, for high-purity silicon carbide. It has
been shown that the grain boundary is thin and not much
169
Yoichi Ishida, Hideki Ichinose, Yoshizo Inomata
different in thickness from that of a metal. 1 ,2 Metals usually have

a thin crystal grain boundary, with a layer of at most a few
atomic spacings having an arrangement different from that of the
matrix phase. It was long believed that this was due to the
difference in bonding properties between metal bonds and
ceramic bonds which are largely covalent. Recently, however, it
has become apparent that this direct factor is not the main cause
of this phenomenon.
The presence of thick amorphous or ultrafine-grain layers on
grain boundaries has been observed even with metallic materials,
including the sintered magnetic alloy FeNdB that has been
attracting a great deal of attention recently. It is thought that
because of the presence of this kind of layer, there is no
distortion of the matrix phase near the grain boundary, thereby
inhibiting nucleation of the magnetic domain, and a large
coercive force is placed on the magnetic alloy. Ordinarily, metals
have high solubilities with impurity elements, resulting in a
strong tendency for the impurity elements to be taken into the
matrix phase. A high ductility of metal influences as well. The
crystal grain boundaries are more often formed by cold work and
recrystallization than by sintering. The two features appear to be
the reason for these seemingly conflicting impressions. Although
it is predicted in theory that the nature of the bonding will have
an influence on the thickness of the intercrystalline grain
boundary, this appears not to be the determining factor. Instead,
the origin of the grain boundary and the concentration of
impurities thereon appear to be more important in determining
grain boundary thickness. Clarification of this problem requires
investigation using high-purity silicon carbide. Here, observa-
tions will be confined to grain boundaries with a thickness on the
atomic level.
8.2 PROBLEMS IN CROSS·SECflONAL

OBSERVATION OF CRYSTAL GRAIN
BOUNDARIES
8.2.1 Inftuences of the Surface Damage Layer

A high-resolution electron microscope image of the crystal grain
boundary of a high-purity silicon carbide sintered body is shown
170
Grain Boundaries in High-Purity Silicon
Fig. 8.1. Electron

microscope lattice
image of a large-
angle crystal grain
boundary in a
high-purity silicon
carbide sintered
body prepared by
CVD. Macro-
scopically, it
appears to be
parallel to the
(0001) plane of
one of the
crystals. There
are no poor-
quality layers
present on the
grain boundary.
in Fig. 8.1. 1 Because of the high purity of the silicon carbide, no

special phase of any kind can be observed on the grain boundary.
The overall distortion of this image is due to the fact that SiC is a
semiconductor and as such cannot be processed into thin films
using electrochemical techniques such as electropolishing. Hence
ion polishing is used, but the formation of damaged layers on the
upper and lower surfaces of the thin film due to ion implantation
cannot be avoided. This in turn brings about local turbulence in
the image. With high-resolution cross-sectional observation of an
interface, the thinner the film the better the locality of the
information provided. However, a thinner film also increases the
ratio of the surface damage layer to the thickness of the whole,
hence creating turbulence in the image. Development of a
damage layer-free polishing method is an important area that will
have a great impact on the future of high-resolution observation.
Although Fig. 8.1 is not perfect, it does provide sufficient
information for the time being. It appears, for example, that
there are no special layers on the grain boundary.
171
Yoichi Ishida, Hideki Ichinose, Yoshizo Inomtlta
8.2.2 Scope of Lattice Image Observation

Another problem involved in observation of crystal grain
boundaries by high-resolution electron microscope is limited
resolution, which in tum limits the orientations which can be
observed. Specifically, observation is possible only for crystal
orientations in which the atoms are densely lined up, such that
both crystals are facing the direction of the relatively large space
between atomic chains. Given this limitation, only crystal grain
boundaries whose orientations lie in a special relationship can be
observed. In the case of thin samples, fortunately, lattice images
can be viewed even when the crystal is tilted slightly to one side.
In other words, perfect orientation is not required for lattice
image observation. Recent improvements in the resolution of
electron microscopes have allowed considerable increases in the
orientation range of this kind of observation and have enabled a
certain degree of structural analysis, making it possible to
determine, for example, whether an amorphous layer is present
or not.
8.2.3 Conditions for Identification of Gnin Boundary

Structure
The lattice image described above is not, however, sufficient to
identify the atomic arrangement structure of a crystal grain
boundary. Conditions are just as demanding as for the matrix
phase. Specifically, the orientations of both crystals must be in a
special relationship, the sample must be positioned such that the
electron beam enters in a direction parallel to the dense atomic
chains of both crystals, and the voltage and current centers of the
electron microscope must be precisely adjusted for the condi-
tions. Here, it is also required that the surface of the grain
boundary be parallel to the incident electron beam. Only special
types of the crystal grain boundary, such as the tilt grain
boundary, can be observed. With this kind of grain boundary,
image calculations should be performed based on numerous
parameters, including thin film thickness and orientation of the
thin film surface, and these calculations then compared with the
actual series of photographs taken using various focal positions
and sample orientations in order to identify the atomic
configuration of the grain boundary.
172
8.3 OBSERVATION OF CRYSTAL GRAIN

BOUNDARIES OF SILICON CARBIDE
BICRYSTALS GROWN IN THE VAPOR PHASE
8.3.1 Observation of Regular Grain Boundaries
The a-SiC single crystals prepared by decomposition-sublimation

of high-purity silicon carbide at 2800 K followed by deposition
are generally plate-like crystals with a thickness of 200 ~ and a
length of 2-3 mm. Among these, bicrystals having one more
crystal with the (1120) plane attached to the crystal plane (0001)
of the first crystal (Fig. 8.2) are observed with relatively high
frequency. 2 Such a bicrystal was cut with a diamond cutter
perpendicular to the plane (and the common axis [1100]),
reduced to a thickness of 50 14m using a diamond polishing fluid,
and finally ion-polished and observed. The results are shown in
Fig. 8.3. An image rooted in 6H SiC can be observed every third
layer, and the grain boundary is an asymmetrical tilt type grain
boundary parallel to the basal plane (0001) of one of the crystals.
Although the grain boundary is asymmetrical, it is interesting to
note that the same structure is repeated. Hence it is a periodic
regular grain boundary.
Fig. 8.1. Shape of

6H silicon carbide
bicrystals formed
by sublimation-
deposition. One
of the plate-like
crystals, each of
slice which has a thick-
ness of several
hundred IUD and a
length of several
millimeters, con-
tacts the other at a
70·5° angle.
173
Fig. 8.3. Electron

microscope lattice
iml!8e of the
[(1210] asym-
metrical angle
regular grain
boundary
(OOO1)A/(1012)B
of 6H silicon car-
bide bicrystals
grown by
sublimation-
deposition.
8.3.2 Coincidence-site Lattice Analysis

Periodic regular grain boundaries can be analyzed using
coincidence-site lattices. Since the structure has a long peri-
odicity, if translational unit lattices are defined and superimposed
to define a coincidence-site lattice, as shown in Fig. 8.4, it can be
seen that this grain boundary is a regular grain boundary whose
coincidence-site lattice is parallel to the densest plane, i.e. whose
periodicity spacing is the smallest. The black and white dots in
Fig. 8.4a indicate positions on the [1100] axis, with large dots
assumed to be carbon atoms and small dots to be silicon atoms.
The asymmetric tilt boundary at first glance appeared to have an
epitaxial relation to the basal plane of the crystals and no relation
to the coincidence-site lattice. It is in fact the most important
coincidence-site type grain boundary. The fact that its existence
could have been predicted using coincidence-site lattices was
surprising, and this reconfirms the usefulness of the old
coincidence-site lattice theory.
174
8.3.3 Structure of the Basal Plane Epitaxial Interface

(OOOI)A/ /(1120)8
Concerning atomic arrangement, which constitutes the weak
point of coincidence-site lattice theory, the superimposed crystal
lattice plots of Fig. 8.4 play an important role. This is because
the 6H structure is based on the twin relationship which occurs
every three atomic layers. When an appropriate superimposition
is found a portion of the lattice points are in complete
coincidence, and if there is a twist grain boundary, the grain
boundary is expected to form an interface with numerous
single-crystalline 'windows'. In the case of tilt type grain
boundaries as well, open-windowed interfaces are possible
depending on the selection of the interface.
For example, if crystals A and B in Fig. 8.4 are in contact at
broken line of Fig. 8.4c (1), this type of tilt type interface will be
formed. In fact, the grain boundary is divided at the position
indicated by broken line (2), as shown in Fig. 8.3. It can be seen
that this is not the type (1) structure, in which single crystal and a
poorly-matching 1: = 9 coincidence-site lattice boundary struc-
tural units alternate, but rather the type (2) structure, consisting of
alternating coherent twin boundaries and units of good-matching
1: = 9 coincidence-site lattice boundaries. Although this may be
surprising at first glance, the bicrystal formation which occurs
every three atomic layers in this 6H polytype crystal actually
reduces the internal energy of the crystal, and the difference in
internal energies between the structural units of the coherent
twin and those of the matrix is small enough to be affected by
surrounding structures. Investigation of the arrangement shows
that, of the type (1) non-matching bicrystal boundary structure
and the type (2) unit structure, the latter closely resembles the
1: = 9 coincidence-site lattice grain boundary structure proposed
by Bourret & Bacman3 as the result of their observation of
germanium bicrystal grain boundaries. The latter type of
structure is very likely to have a low energy level.
Since the covalency of bonding chain differs between ger-
manium and silicon carbide, Bourret's hypothesis in Si, which
assumes the reconstruction of the bonding chains, cannot
necessarily be applied in SiC. As long as the lattice image is
Viewed two-dimensionally from the standpoint of layering,
however, it is certain that type (2), described in Fig. 8.5, which
175
Fig.8.4a.
Translationallat-
ticein 6H
polytype crystal
structure (solid
line). Large and
small circles in the
crystal lattice in-
dicate silicon and
carbon atoms,
respectively,
while black and
white indicate
differences in
their position.
can be described as the closest point of contact between five- and

seven-membered rings, is a low-energy interface. Although it is
surrounded by a matching bicrystal structure and its atomic
positions are restrained, there are several possibilities for this
structure when one takes into consideration Bourret's restruction
of the bonding chains, which includes a double periodicity
Fig.8.4b.
Superimposed di- (+ + + + ) and a shear deformation (++t+ ) in the [1100]
agram oftransla- direction, besides the possibility of dangling bonds, and the
tionallattices. segregation of impurity elements. In Fig. 8.3 only the central
The double circles
indicate
coincidence-site
lattice points. The
interface orienta-
tion in Fig. 8.3 is
parallel to the
vertical thick line,
and this is the
direction with the
smallest spacing
between
coincidence-sites
i.e. the direction
allowing an or-
dered structure
with the shortest
periodicity.
176
Fig.8.4c.
Superimposed di-
agram in which a
portion of the
crystal lattice sites
coincide. The
translational ope-
ration allows sel-
ection of this kind
of positional re-
lationship. When
the grain bound-
ary is described by
the vertical solid
line, the structure
is like the one
shown in Fig. 8.3.
When the grain
boundary is de-
scribed by the
broken line in-
stead, the struc-
ture is one in
which a portion of
the interface is an
extension of a
single crystal 3
atom spacings in
thickness.
(1) (2)
position of the ring-like structure appears as a white image, and

since more detailed information is not available, given the fact
that the white dot at the position corresponding to the
five-membered ring is small and its center sticks out in the
direction of the crystal on the opposite side, together with the
fact that the seven-membered ring positions below are the widely
spread white dots off to the side, it would appear possible to
argue that this does not contradict the structural model of Fig.
8.5. More detailed analysis will have to await the development of
electron microscopes capable of producing higher-resolution
photographs. Although Fig. 8.5 is not entirely sufficient, it does
show the possibilities of this. Six-membered rings of Si and C can
be partially distinguished (Fig. 8.6). The combination of a good
177
Fig. 8.5.
Structural analysis
of the ordered
grain boundary of
Fig. 8.3 by the
reconstruction
model of Bourret
& Bacman/
where (++++)
indicates a bond-
ing chain with a
double p"eriodicity
in the [11(0)
direction while
(++++ ) is one
which has also a
double periodicity
bonding chain in
the same (1100)
direction with a
component of
shearing,also
along [11(0).
..+ ...~+~+ 0
Fig. 8.6. Electron

microscope lattice
image with infor-
mation of a silicon
carbide six-
membered ring
structure shown in
the crystal on the
right.
178
photograph with image calculations would allow more detailed

investigation of the above structural model.
8.3.4 Structural Analysis of the Polytype Interface

(6H//15K)
Silicon carbide exhibits various polytypes. Some bicrystals exhibit
interfaces on which two varieties of polytype have been joined.
One example is shown in Fig. 8.7. Although this polytype
boundary is a heterogeneous phase boundary, the chemical
composition is identical, and it is of great interest as a point of
departure for the expansion of coincidence-site lattice theory to
heterogeneous interfaces. First let us refer to the caption for
Fig. 8.7. This can be more easily understood if it is viewed as a
difference in twin spacing such as is shown in Fig. 8.8. This
bicrystal consists of a roof-like single crystal, the right side being
a three- and left a two-atomic layers. The other two crystals each
in twin relationships and three-atomic-layer in thickness are piled
up every other layer sandwiching the roof-shaped single crystals.
If both the right and left sides of the roof-shaped single crystals
are three atoms in thickness, the grain boundary becomes a
symmetrical tilt type grain boundary, and the crystals on both
sides are 6H polytype. If the macroscopic direction of the grain
,~
• .•
~-.;,~
... ·t,
I
. ~. ......
L'''
•
••••
,,~ •• f'."'~~'
fIj"#i:
~
~.'• " ...
....,:~",.~.,
~.:":"--~';.-."!.#":"I~"'-
._;
~"..
'" II," ... ., • • ~ ' .•.
. , - . ,,.....
~""...
. . • • • ".
~ ~
<if_.' - . .:\~>,-~-
• " " ••
- , .... ~
. . .:-- ' ••. - .'.
~" "",.~~.A'·. ,,". , .... • .,. .• • ... , ..... ' ,. . • ..... •

... - ,
•• t •• •
• • • -......
• • ......... . . . . .
f.· ......,.... ,..
..... • , • • I
.,.,. .. ,. •
Fig. 8.7. Electron
microscope lattice
imageofa
6H/15R hetero-
..... 4·····,-.,····· .~. ~~,.. "," ~ .•.....

• .. . _ . .... •••• _• ••.•• r- • I • . . . .•. .•.•. .-. . . ..,..., ...... .
'." ........... 9 . • ' . , , , · . .· , , · . . ..
.. C 1-
polytype crystal
~ ~
,-'. ,. . . . . . . . . . . . . . . . . . . . . . ., •• .. '.' .- •• • #> .- . . . . . ,,"" .
• e'. ....... . . , ., •• " • •• • • • ' .... '.' . . . . . ..... , grain boundary

..... : •.• < • • • , ..... • . • • • • • • • ., . . . . . . . " •• , ...
observed in sili-
,. •••_ • .... .. •••• 1.. •.• .. ..•...•..:.1.
, . . . . .' • ' . ' . t ' • '..
••. ..... ~ .•" "~ ~.
• . . . . Oil
.,,,
,....
con carbide bicry-
' • .' ~ • ..... •••••• ~
If. ..,..... • • .., tt. • • • . . . . . .,,'"
•• '''.'f# . '• • . • . , ..... • • . . ., ••' -••••• _. stals formed by
·~· ••·t· '.' ... /.... ' ..••.•
••••• I • • • •• • ".' .'
-,.••.. ". ",'

-.*.."... ....
".....
sublimation-
...... . ........
, . : .. I."e •. ' . ' ' / ; . ' ••
~-
1·' .• ·••·• .. , ..
' ••• :
,
••
~. • • •"•.I!./.J.••••.•..•
". . . . . . . . . . . .
' , ''':..
•
deposition. For a
I' 4 . . '
1. .... . . '.. . .. . • ,... .• ...
,', .
~,.
tI .. • .• " •
.
.. ""''- • _.. .,. • •• .. -1 _. III. '" • #-t structural analysis
..... ; .• '. ".': :" ':l.-.. . ,._."...; ," : •. ' : ..... ,.. :-, see Fig. 8.8.
> •• .'.,. ' •• ' ... ' . ... • •• ' •••
• •r • .'.,. ., •••• '.... •••..•••• ..' ,...... •

•
.',0 ........ '. 0/ 4 ............. , . f
•••••••.•••••••• , .......... " , "f
.
•
......
•. .... ,'. •. ' ........
.' . . ' . f."
•• ,,". ,,,". 'J" • •" •••••"., ':.-: ••
..-"
~ • • .. " '" •
: .', :' '. ---.: .......'
_ . " ..._.. • • •
". . .
.. • t • 411 .. ~.,",.....
'" L
~ ••
••
•
.. ! ~ ....
179
Fig. 8.8.
Structural model
of the 6H/15R
interface of Fig.
8.7. The left side
shows6H
polytype crystals;
while the right
side,15R
polytype crystals.
The double circles
indicate the
coincidence-site
lattice points.
boundary surface deviates from the symmetrical orientation the

twin spacing changes accordingly, and various polytype combina-
tions should develop. In any case, however, a l: = 9 coincidence-
related grain boundary unit structure that has larger periodicity
spacing than the one described above should form on the
interface. A roof-type structure having crystals of three atomic
layers on both sides is formed and sandwiched between thin
single crystals of the same type, and a polytype crystal having a
fixed and matching twin spacing period on both sides is formed.
With this type of periodic ordered interface, application of
coincidence-site lattice theory is possible even if the structures
are different. Translational lattices such as the ones shown by the
black dots in Fig. 8.8 can be defined for 6H and 15R polytypes,
respectively. The superimposition of these results in a
coincidence-site lattice unit like the one shown by the double
circles. Although a large translational lattice inevitably results in
a large superimposed lattice, the spacing, orientation and period
of the periodically ordered interface can be determined by this
method. The ability of the coincidence-site lattice to predict
ordered interface is preserved. Certain adjustments are required,
180
however. By locally changing the twin spacing it is possible to

build steps on the grain boundary surface and change the grain
boundary orientation macroscopically. This type of structure is
absent in an ordinary grain boundaries. The DSC lattice defines
the Burgers' vector of the grain boundary dislocation, another
fundamental element of the coincidence-site lattice theory, and
chooses a l: = 9 unit structure as its location. Consequently,
analysis considers the l: = 9 DSC lattice to be the basic lattice,
while a grain boundary dislocation having a specific Burgers
vector is defined as a structure which forms a bicrystal having
specific spacing on both left and right and, in some cases, forms
steps on the grain boundary surface. Reports on this type of
grain boundary dislocation analysis are insufficient. The l: = 9-
structure unit, which constitutes the basic structure, has yet to be
identified. Since it is surrounded by coherent twins, the analysis
should be relatively easy, as described above, but current
electron microscopes have insufficient resolution to identify.
8.4 SUMMARY
High-resolution electron microscopes were used to analyze the

structure of two bicrystals for high-purity silicon carbide (a-SiC)
grown by sublimation-deposition methods, without surrounding
restraint, and the following conclusions were drawn.
(1) The asymmetrical tilt type grain boundary, which when
viewed macroscopically appears to be parallel to the based
plane of one of the crystals and on which the other crystal
appears to have been epitaxially formed, has a periodically
ordered structure when viewed microscopically and is a
twin-type crystal grain boundary based on the densest
coincidence-site lattice.
(2) The other interface, which when viewed macroscopically
appears to be a virtually symmetrical tilt type grain
boundary, is actually a heterogeneous interface formed
between polytype crystals referred to as 6H and 15R. This
interface also has a periodic ordered structure and is a
crystal grain boundary described by a coincidence site
lattice.
(3) The grain boundary atomic structure is surrounded by
181
crystals whose structure is well understood, leading one to

assume that its identification would be relatively easy.
Identification, however, requires further improvements in
the resolution of electron microscopes.
REFERENCES
1. Ishida, Y., Ichinose, H. & Inomata, Y., Structural analysis by high

resolution electron microscopy. Report on researches of the surface
and interface controlling technique for the development of functional
high tech materials. Science and Technology Agency, 1986. 10, pp.
227-37.
2. Ichinose, H., Inomata, Y. & Ishida, Y., HRTEM analysis of ordered
grain boundaries in high purity alpha-SiC. Proceedings of Ceramic
Microstructure's 86: Role of Interfaces (to be published by Plenum).
3. Bourret, A. & Bacman, J. J., Defects structure in the 1: = 27, 11 and
(21T) 1: =3 symmetrical grain boundaries in germanium. Proceedings
to JIMIS-4, Trans JIM 27 Supplement 125-134 (1986).
4. Inomata, Y., Inoue, Z. & Uemura, Y., Yogyo-Kyokai-Shi, 70
(1982), 87-94.
APPENDIX: GRAIN BOUNDARY
Shortened form of crystal grain boundary. In cases in which an

impurity is intentionally added to a sintered body or in which the
raw material contains impurities, a second phase, generally
having a composition different from that of the particles, is
formed between the particles constituting the sintered body.
Even when this second phase is not formed, impurity segregation
and abnormalities in composition can be observed in the
proximity of the crystal bond interface.
Consequently, when discussing grain boundary structure or the
phenomena that occur at the grain boundary, it is important to
examine the purity, impurity type and concentration, the
presence or absence of a second phase on the grain boundary,
composition of this second phase, and composition abnormalities
on the bonding interface. Concerning grain boundary structure,
different conclusions are sometimes obtained from the same
182
system upon examination, but it is thought that the structure is

usually determined by the contribution of impurities, as de-
scribed in this chapter. With continuing progress in methods of
microscopic analysis, a more detailed explanation is expected in
the near future.
183
9 Grain Boundary and
mgh-Temperature
Strength in SiC
HIROAKI KURISHITA, HIDEO
YOSHINAGA & YUICHI
IKUHARA
ABSTRACT
The nature of grain boundaries in pressureless sintered SiC with

and without sintering aids is presented in connection with the
absence and presence of strength loss at high temperatures. The
absence of strength loss may be attributed to the occurrence of an
'extended grain boundary', whereas the remarkable loss in strength
is due to the existence of an amorphous-like second phase at
the grain boundaries. This extended grain boundary is not of a
special phase but simply of a relaxed structure with some
extension, and is most likely composed mainly of SiC itself. It is
shown that the concept of extended grain boundaries can explain
the observed behaviour in SiC.
9.1 INTRODUCTION
Together with Si3N4 , SiC is one of the most promising of the

high-strength structural ceramics. However, these materials are
known for their poor-sinterability, making the addition of a
sintering aid necessary for densification. Addition of a sintering
aid contributes remarkably to densification and hence the
strength of the sintered body, but generally it also results in the
formation of a second phase at the grain boundaries which
frequently shows viscous fluidity at high temperatures, causing
grain boundary sliding. Although this sliding is one form of
185
Hiroaki Kurishita, Hideo Yoshinaga, Yuichi Ikuhara
plastic deformation, because of its non-uniformity it does not

relax the stress concentration; instead, it causes stress concentra-
tion at grain boundary triple points and results in a remarkable
loss of strength. In Si~4' on the other hand, it has been reported
that crystallization of the grain boundary amorphous phase can
suppress the strength loss at high temperatures. 1 It has also been
reported that when a B4C (or B and C) sintering aid is used with
SiC, high room-temperature strength (approximately 0·8 GPa
with pressureless sintering and 1·0 GPa with hot-pressing) can be
obtained, and there is no loss of strength up to approximately
1900K.2
According to TEM observation by Ogbuji,3 no grain boundary
phase is confirmed from the lattice image in either pressureless
sintered SiC with B and C (hereafter to be referred to as SCC) or
hot-pressed SiC (hereafter to be referred to as HPSC), and it is
thought that the absence of strength loss at high temperatures is
due to the absence of second phase.
During sintering, however, the rotation of individual grains is
restrained, so that the orientation of each grain in the SSC and
HPSC is random. Consequently, the probability of the existence
of high-energy random grain boundaries is far larger than that of
low-energy grain boundaries such as coincidence lattice bound-
aries. Furthermore, since SiC is a material with an especially high
covalency (approximately 90%4), the energy of random grain
boundaries in SiC is expected to be remarkably high. Inomata et
al. have concluded from a series of model calculations~ that the
relaxation of sudace energy caused by grain boundary formation
is extremely small in SiC. These arguments suggest that the grain
boundaries of SSC and HPSC are extremely weak and easily
fractured. Consequently, without any mechanism to reduce the
grain boundary energy, such as formation of a grain boundary
phase, the measured fracture strength would be extremely low
and grain boundary fracture would be dominant regardless of
densification. Even in cases where a grain boundary phase was
not observed, however, actual measured strength was quite high,
as described above, and fracture occurred more often trans-
granularly than intergranularly. This suggests that some relaxa-
tion mechanism operates for high-energy boundaries in these
materials and consequently that a unique type of grain boundary
bonding may exist in covalent ceramics.
This type of bonding depends on the presence or absence of a
186
Grain Boundary and High-Temperature Strength in SiC
sintering aid as well as the type of aid used and is thought to

affect high-temperature strength properties. Consequently, clar-
ifying the grain boundary structure in connection with the
presence/ absence and type of sintering aid and its relationship
with high-temperature strength is necessary to the development
of superior materials which do not exhibit strength loss at high
temperatures. This chapter will discuss the relationship between
grain boundary structure and high-temperature strength based on
recent reports. 9 ,10
First, Section 9.2 will discuss strength properties at tempera-
tures of up to 2070 K for three materials: SSC with Band C, SSC
with B, C and AlN, and SSC without any sintering aids. Section
9.3 will provide examples of observation of these grain
boundaries by high-resolution electron microscopy and introduce
the extended grain boundary model proposed by the authors as a
grain boundary structure unique to covalent materials. In Section
9.4, the validity of this model will be examined based on
experimental results.
9.2 HIGH-TEMPERATURE STRENGm OF

PRESSURELESS SINTERED SiC
The fracture strength of a sintered body is strongly dependent on

such factors as the size, shape, density and distribution of
residual pores, grain size and grain boundary properties (bonding
strength). However, current technology does not allow control
over all of these factors. As is well known, these factors are
affected by the particle size and purity of the raw material
powder, type of impurity, and sintering conditions, so Sections
9.2 and 9.3 will mainly describe details of the samples to be used.
9.2.1 Samples
A :O.owchart of sample fabrication is shown in Fig. 9.1. The
sample to which B and C were added as sintering aids is called
A; the one to which chie:O.y AlN was added, B; and the sample
without additives, C. The SiC raw material was a-type
high-purity powder (chie:O.y 6H structure) with a mean particle
size of 0·2 f.U11 and total metal impurities of less than 0·1 mass%.
187
Hiroaki Kurishita, Hideo YoshiMga, Yuichi Ikuhara
Fig. 9.1. MATERIAL A MATERIAL B MATERIAL C

Fabrication
a-SiC (-0.2tlm)
process for the a-SiC (- 0.2tlm) a-SiC (-0.2tlm)
samples A, B and
+ + +
C. 9 1.8mass% AIN
0.6mass% B No Additives
0.1 B
3
" C " '--
3 C
6
" PCS "
---- 6
" PCS
--
I
t --
Isostatic Press
140MPa, 300s
~
Sintering
2370K, 3600s
in I atm. Ar
The B used as a sintering aid was an amorphous powder with a

mean particle size of less than 1 J.Ull, the C source was phenol
resin, and the AlN was a crystallized powder with a mean
particle size of less than 1 J.UIl. AlN was added to sample B with
the objective of improving sinterability. According to Soeta &
Maedall AlN suppresses grain growth and decomposes at
temperatures above 2170 K to diffuse into the SiC grains and
bring about rapid densification.
PCS (polycarbosilane),12 which was added to samples A and B
at a concentration of 6 mass%, prevents the abnormal grain
growth13 that is problematic for pressureless sintering of SiC, and
promotes densification. PCS is an organic silicon polymer with a
main skeleton chiefly of Si and C, and at high temperatures it
forms SiC fine grains of less than 0·1 J.Ull. Since this fine-grain SiC
is formed between the raw material SiC particles, it is effective in
suppressing grain growth and is absorbed by the raw material SiC
particles to promote densification.
The amount of additives is shown in Fig. 9.1. The B and C
concentrations in the material used by Ogbuje described above
were both 0·5 mass%, close to the boron content of sample A
and significantly less than the carbon content thereof. After
mixing and drying, these powders were compacted for 5 min
under a hydrostatic pressure of approximately 140 MPa and then
188
Fig.9.2. SEM
micrographs of
pressureless-
sintered bodies.
A,Bande
correspond to
samples A, Band
c. 9
sintered for 3·6 ks (1 h) at 2370 K under 99·999%-pure argon gas

of one atmospheric pressure.
Typical structures of the resulting samples A, Band Care
shown in Fig. 9.2, with relative densities (sample
density/theoretical density) recorded in Table 9.1. When PCS is
not added and the remaining composition is the same as samples
A and B, abnormal grain growth is frequently observed. Samples
to which 6 mass% of PCS had been added, however, exhibited a
uniform grain size, as seen from Fig. 9.2(A) and 9.2(B). The
mean grain sizes for samples A and B were both approximately
211m, and their microstructures were very similar. As shown in
Table 9.1, however, addition of AlN resulted in a slightly higher
relative density than sample A in spite of the extremely small
amount ofB.
In sample C without any sintering aid, as shown in Table 9.1,
there was no densification, and the largest pore diameters are
much larger than those in samples A and B. Mean grain size,
however, was approximately 211m, the same as for samples A
and B.
It should be noted that even when no sintering aid was added
bonding occurred between SiC particles despite low density (see
Fig. 9.13). According to studies by Hase et al. 14 concerning the
sintering process for P-SiC green compacts without additives, on
heating up to 2370 K, the same sintering temperature used with
the present samples, regions with high density close to theoretical
Table 9.1
A B C Relative Density
(%) of Samples
96.6 97.8 50 A,BandC. 9
189
appeared locally due to grain agglomeration, but overall there

was no densification. The situation may be the same for a-SiC.
9.2.2 Mechanical Properties

Three-point bend tests were conducted for specimens prepared
from the above-described sintered bodies (0·6 mm x 4 mm x
15 mm) over a temperature range from room temperature to
2070 K with a crosshead speed of 8·3 x 10-7 m/s (0·05 mm/min)
under a vacuum of approximately 2·7 x 10-3 Pa (2 x 10-5 torr).
The results are shown in Fig. 9.3. The distance between the
bending supports was 9 mm, and the radius of curvature of the
supports and load tip was 1·5 mm.
Room-temperature strength of sample A, to which Band C
had been added as sintering aids, was 420 MPa, and there was
virtually no change in this value up to 1100 K. At higher
temperatures, however, this strength increases, rising to 580 MPa
at 1670 K and 700 MPa at 2070 K, the maximum test
temperature.
In the case of sample B, to which AIN had been added, both
the strength and its temperature dependence agree with those of
sample A within experimental error up to 1100 K. The strength
increases from 1100 K to 1770 K, but the increasing rate is
somewhat smaller than for sample A. Above 1770 K there is a
remarkable reduction in strength, in contrast to sample A, with
the strength at 2070 K only about half that at 1770 K.
Despite its extremely low density, sample C without additives
Fix. 9.3. l?700 -+-A (B-C-PCS) /

Temperature :I: -o-B (B+C-AIN-PCS)
dependence of ;600
-6-C (No A~itlveS)....-;:;..Q
bending strength ~500 v- ~ \
for samples A, B
andC. 9 ~400 ~ - \
~300
'6
~ 200
100~ {;,,_ _ _ _ _ _ _ _-£>l:;.
O~-~--~-~--~-~
200 600 1000 1400 1800 2200
Temperature I K
had a room-temperature strength of approximately 80 MPa, and

there was no reduction in strength up to the maximum test
temperature of 2070 K.
It is well known that when the temperature rises and plastic
deformation by dislocation motion occurs even in brittle
materials, this plastic deformation reduces the stress concentra-
tion at the crack tip, thereby resulting in increased fracture
strength. On the other hand, when the grain boundary weakens
at high temperatures and a non-uniform deformation such as
grain boundary sliding occurs, the stress concentration at grain
boundary triple points increases, and fracture strength drops.
The dominant corresponding fracture mechanism is transgranular
in the case of the former and intergranular in the case of the
latter.
According to studies conducted concerning SiC polycrystals,
when the grain boundary fracture mechanism is dominant no
increase in strength is observed at high temperatures; instead,
the strength drops.15--17 This indicates that even if the stress
concentration at the grain boundary crack tips is reduced at high
temperatures by microscopic plastic deformation due to disloca-
tion motion, the effect is smaller than that of the grain boundary
weakening at high temperatures. When the strength loss is not
observed at high temperatures, therefore transgranular fracture
is thought to be dominant.
Figure 9.4 shows SEM micrographs of the fracture surfaces of
samples A, Band C at three representative test temperatures. As
can be seen from the micrographs, the main fracture mode for
sample A is transgranular in all test temperature regions. The
fracture mode of sample B, on the other hand, is dependent on
temperature: at room temperature transgranular fracture is the
main mode, but at 1670 K grain boundary fracture coexists, and
at 2070 K grain boundary fracture becomes dominant. Accord-
ingly, transgranular breakdown is dominant in the temperature
range in which the strength increase is observed, i.e. up to the
maximum test temperature for sample A and up to 1770 K for
sample B, and the temperature at which the strength reduction
occurs in sample B corresponds to the temperature at which the
grain boundary fracture becomes dominant. As described above,
grain boundary fracture is thought to be due to grain boundary
sliding, which in tum is caused by weakening of the grain
boundaries at high temperatures. In contrast to the grain
191
Hiroaki Kurishila, Hideo Yoshinaga, Yuichi lkuhara
Fig.9.4. Cross-
sectional SEM
micrographs of
fracture surface at
room tempera-
ture, 1670 K and
2070 K. A, Band
C correspond to
samples A, Band
C. 9
boundaries in sample A, therefore, those in sample B flow in a

viscous manner and weaken at high temperature.
In the case of sample C, it is difficult to identify the fracture
mode from SEM observation. As is clear from Fig. 9.4, however,
the same fracture mode is exhibited in all test temperature
regions. As described above, the strength of SiC showing grain
boundary fracture drops at high temperature. Therefore, the fact
that sample C does not lose its strength at high temperatures
suggests that the dominant fracture mode is not grain boundary
fracture but rather transgranular fracture. Furthermore, that
sample C continues to exhibit a strength of approximately
80 MPa at high temperatures despite the absence of densification
indicates that its grain boundaries are quite strong. In other
words, a grain boundary with strong bonding can be obtained
without addition of sintering aids.
Figure 9.5 shows stress-strain curves for samples A, Band C;
Fig. 9.6, temperature dependence of their apparent Young's
moduli. The arrows in Fig. 9.5 indicate the stress at which the
first deviation from the initial linearity was observed on the
stress-strain curves, i.e. the beginning stress of macroscopic
Fig.9.S. Stress-
strain curves for
samples A, B and
C until fracture. 9
._---_._._- - - - - - .
Fig.9.6.
400 • Temperature
dependence of
~ -0~)
apparent Young's
modulus for
samples A, Band
300
C.
o Material A (B+C)
• Material B (B+C+AIN)
200
/.!l Material C (No additives)
100
----.
9§r---------------------~E~
~~----
~
o200 ------~'~----~~'~------~IL_-----~----~
600 I 000 1400 1800 2200
Temperature/K
193
plastic deformation. The apparent Young's modulus in Fig. 9.6

was determined by subtracting the contribution of elastic
deformation of the portions other than the specimens from the
gradient of the initial linearity of the stress-strain curve.
It was stated earlier that the strength increase at high
temperature is due to plastic deformation caused by dislocation
motion. From the stress-strain curves shown in Fig. 9.5, virtually
no plastic deformation is observed up to 1770 K, where both
samples A and B show strength increases. According to research
on SiC single Crystals,18,19 however, the critical resolved shear
stress for basal slip is, for example, approximately 14 MPa at
1670 K and 9 MPa at 1870 K. At the fracture stress, therefore, at
least the basal slip is operating in samples A and B. In other
words, microscopic plastic deformation due to dislocation motion
is occurring in the grains before fracture. The reason for the lack
of macroscopic yielding is thought to be that there are too few
independent slip systems active in a-SiC to satisfy the Von Mises
criterion for polycrystals to be plastically deformed. At even
higher temperatures, however, dislocation mobility increases,
and some plastic strain is recognized on the stress-strain curves.
The result for sample A at 2070 K is an example of this.
In the case of sample B, the plastic strain is clearly observed at
temperatures of 1870 K and above. Deformation behavior,
however, differs significantly from that of sample A. For
example, the stress at which the plastic deformation begins is
much lower than for sample A, and the work hardening rate is
also small. In addition, there is a remarkable reduction in
apparent Young's modulus. In the case of sample B, therefore, it
is necessary to consider a different plastic deformation mechan-
ism from that in sample A. As described above, the fact that the
grain boundary weakens at high temperature to cause grain
boundary fracture suggests that the main plastic deformation
mechanism of sample B is grain boundary sliding. Furthermore,
from the fact that some grain boundary fracture is observed at
1670 K in sample B, the reason why the increase in strength of
sample B up to 1770 K is somewhat less than that for sample A
may be the grain boundary sliding.
In sample C, no plastic deformation is observed from the
stress-strain curves. At 80 MPa, the fracture stress at 2070 K,
however, it is thought that the basal slip is active, taking into
consideration the critical resolved shear stress at this tempera-
ture. In addition, considering that sample C has a large

maximum pore diameter and there should be a large stress
concentration at these pores, it would make sense for micro-
scopic plastic deformation to occur in grains at 2070 K. The
reduction in apparent Young's modulus at this temperature is
thought to be the result of this microscopic plastic deformation.
9.3 GRAIN BOUNDARIES OF PRESSURELESS

SINTERED SiC
The most reliable method of determining the presence or

absence of a grain boundary phase is observation of the grain
boundary with a high-resolution electron microscope. Two
conditions must be fulfilled in order to conduct the high-
resolution observation: first, the grain boundary must be parallel
to the incident electron beam; and second, the Bragg condition
must be satisfied simultaneously for the two grains adjacent to
the bo'@..dary. The work to be described below is based upon the
observations of grain boundaries that meet both of these
conditions, with each sample having at least five boundaries
being observed.
Figure 9.7 is a TEM micrograph of a grain boundary in sample
B which weakens at high temperature. (b) is a low-magnification
micrograph of the region containing the boundary, and (a) is a
diffraction pattern taken therefrom. The pattern shows that the
two grains adjacent to the boundary have a 6H structure, and
this structure was observed in samples A and C as well. (c) and
(d) are high-resolution micrographs of the outlined region in (b).
For (d), the specimen was tilted approximately 1° from the
orientation -of (c). As can be seen from the micrographs, an
amorphous-like layer with a thickness of approximately 3 nm is
present. Therefore, the strength reduction in sample B at and
above 1870 K is thought to be due to the viscous flow of this
layer.
This type of strength loss at high temperature is invariably
observed in samples containing Al. 16,17,20 It is therefore believed
that a second phase with a composition similar to that of
low-melting-point phase Al8B4~ (melting point: approximately
2070 K21) is present on the grain boundary, thereby causing
Fig. 9.7. TEM

micrograph of
sample B,9 (a) is a
diffraction pattern
of grain boundary
region (b), (c) and
(d) are high-
resolution micro-
graphs of the out-
lined area in (b);
(d) was taken
after tilting the
sample in (c)
approximately 10 •
weakening of the grain boundary. While in these cases the

strength loss has already been observed at temperatures of
1573 K16 and 1773 K,17·20 however, the strength of sample B
increases up to 1770 K and begins to drop only after the
temperature reaches 1870 K. This suggests that the grain
boundary phase observed in sample B has a higher melting point

than AI8B4~. It is probably a compound of the AlN-B-C-Si
system.
The next question is whether there really is nothing special
present on the grain boundaries in cases of no strength loss at
high temperatures, such as samples A and C.
Figure 9.8 is a TEM micrograph of sample A, which exhibits
no reduction in strength up to the maximum test temperature of
Fig.9.S. TEM
micrograph of
sample A ,9 (a) is a
diffraction pattern
of grain boundary
region (b), (c) is a
high-resolution
micrograph of the
outlined area in
(b).
197
2070 K and in fact records a significant increase. (c) is a

high-resolution micrograph. Contrary to the conventional as-
sumption, an amorphous-like layer is clearly observed on the
grain boundary. However, from the difference in additives and
high-temperature strength properties, it is clear that this layer is
different from the one in sample B. This is the first time that such
a grain boundary layer has been observed in a material sintered
with Band C.
Since PCS is added to sample A in addition to Band C, one
possible explanation for the presence of this grain boundary layer
is the effect of PCS. As described in Section 9.2.1 above, PCS
forms SiC fine grains at high temperature, so any problem should
be the result of impurities contained within the PCS. Inevitably
some impurities are also contained in the high-purity raw
material powder used, and these would be susceptible to
segregation and precipitation on the grain boundary, but it is
difficult to accept the existence of an impurity phase that does
not cause remarkable viscous flow at 2070 K under the extremely
high stress of 700 MPa.
The next possibility is that this layer is a phase whose main
components are B and C and which has good high-temperature
strength. According to Suzuki & Hase22 and Suzuki,23 B has
virtually no solubility in P-SiC up to approximately 2220 K, so
that a second phase with thickness of approximately 1 nm
(thought to be a B-C compound) is observed at the grain
boundaries by high-resolution TEM in SiC with Band C added
and heated to 2220 K. When the temperature exceeds 2220 K and
the solubility of B increases, however, this grain boundary phase
dissolves into SiC grains and disappears. Since B has a solubility
limit of 0·2-0·3%, excess B is dispersed throughout the material
in the form of spheres. 23 Boron concentration in sample A
(0·6%) is lower than that (1%) of the sample of Hase et al., and
no inclusion is observed by TEM in sample A. As they stated, if
no B-C compound is present on the grain boundaries of SSC
prepared at a temperature exceeding 2220 K, the grain boundary
layer of sample A does not contain B and C as its main
components. However, Band C may segregate on this grain
boundary layer.
The final possibility is that this amorphous-like grain boundary
layer reflects the structural relaxation of the high-energy grain
boundaries unique to ceramics with high covalency. In other
words, the grain boundary with a thickness of 2-5 nm observed

in sample A is a relaxed structure reducing the originally high
grain boundary energy. Ikuhara et al.24 have performed high-
resolution TEM observation of reaction-sintered ShN4 without
any additives and demonstrated the possibility that the crystal
lattices of two grains with a misorientation as large as 400
smoothly connect to each other by gradually changing the
orientation (smooth lattice bending).
These two examples demonstrate the possibility that, when
grain boundaries are formed in covalent ceramics such as SiC and
Si3N4 , the grain boundary energy is reduced by forming an
amorphous-like layer or by lattice bending. In other words, the
boundary energy is reduced by boundary extension. Here, the
composition of the extended grain boundary would be close to
that of the mother phase (impurity segregation is allowed),
unlike the case of sample B. Whether the extended grain
boundary has an amorphous-like or bent-lattice structure would
be determined by which of the two has the lower energy. Such a
bend-lattice structure as observed in ShN4 has never been
observed yet in SiC. This may be due to the relatively high
Young's modulus of SiC (approximately 400 GPa, in contrast to a
value of approximately 300 GPa for Si3N4),25 which provides a
possibility that the elastic energy resulting from the lattice
bending is higher than the energy for the amorphous-like
structure formation.
If the grain boundary has such a low energy as coincidence
lattice boundaries have, there should be no need for extension. It
is therefore expected that the higher the energy of the grain
boundary, the greater the width of extension. As mentioned in
Section 9.1, it is believed that the orientation relationships of
adjoining grains in a sintered body are random. Hence, the width
of the extended grain boundary should change in accordance
with that relationship. The fact that the grain boundary layers in
sample A have thicknesses ranging from 2 nm to 5 nm is thought
to reflect this. It has also been reported that no grain boundary
layers have been observed on the grain boundaries of SiC
prepared by CVD.26-28 In the CVD technique, as opposed to
SSC or HPSC, vapor molecules precipitate without restraint from
their surrounds in such an orientation relationship that the
precipitates have an energy as low as possible with respect to the
substrate or the SiC crystal plane. As a result, it is highly
probable that low-energy grain boundaries such as coincidence

lattice and plane-matching boundaries will be formed .
If it is assumed that the grain boundary layer in sample A is an
extended grain boundary, it should not be unusual for such
boundaries to be observed also in sample C without any
additives, which like sample A does not show any loss of strength
up to 2070K.
Figure 9.9 is a TEM micrograph of a grain boundary in sample
C. As is clear from high-resolution Fig. 9.9(c), an amorphous-
Fig.9.9. TEM
micrograph of
sample e,9 (a) is a
diffraction pattern
ofregion (b), (c)
is a high-
resolution micr-
ograph of the out-
lined area in (b).
200
like grain boundary layer with a thickness of approximately 3 nm

is observed. Here as well, the thickness of the grain boundary
layers was 2-5 nm.
Discussion thus far has been based upon the premise that the
grain boundary layers in samples A, Band C were amorphous-
like, but the question of whether these layers are actually
amorphous is an important one. With observation by micro-beam
diffraction (electron beam diameter: approximately 20 nm),
however, the diffraction strength was too weak to obtain any
information. Dark field observation, in which an objective
aperture was placed in various locations, was also attempted, but
Fig.9.10. (a)
Bright field image
and (b) dark field
image of the same
grain boundary
layer.9
201
it proved impossible to form an image of the grain boundary

layer. When both bright-field and dark-field images taken at a
variety of tilt angles were observed, however, the grain boundary
layer invariably showed a white contrast in the bright field image
(Fig. 9.10(a» and a black contrast in the dark field image (Fig.
9.10(b». Since these contrasts were not dependent on the tilt
angle, it is inferred that the observed grain boundary layers are
really amorphous-like and do not cause a Bragg reflection.
9.4 VALIDITY OF mE EXTENDED GRAIN

BOUNDARY MODEL
9.4.1 structure Change in the Gnin Boundary Layer

under Electron Irradiation
Figure 9.11 shows the process of structure change in the grain
boundary layer resulting from electron irradiation in an AlN-
polytype siaion, one of the covalent ceramics.29 Although not the
case of SiC, the observed structure change does support the
extended grain boundary model as described below.
Fig. 9.11. In-situ

observation by
high-resolution
TEM of structure
change in grain
boundary layer
under electron
irradiation. The
material is an
AIN-polytype
sialon.
Grain Boundory and High- Temperature Strength in SiC
In the as-prepared sialon the crystal lattices on the two sides of

the grain boundary have failed to connect directly at the
boundary and structure relaxation has occurred over a thickness
of approximately 2 nm. As a result, the strain contrast due to
restraint of the surrounding grains is observed along the
boundary (Fig. 9.11(a». When the electron beam irradiates the
sample, the boundary layer, in which the atomic arrangement is
disturbed, is preferentially sputtered, and hence thin regions are
formed non-uniformly along the boundary. Since the thicker
remaining regions are surrounded by thinner regions, the
constraining of the surroundings decreases, and crystallization
proceeds (regions indicated by arrows in Fig. 9.11(b». The
crystallization increases the strain in the thin regions. As a result,
sputtering is accelerated (Fig. 9.11(c» and holes are opened (Fig.
9.11(d» there. Figure 9.12 is enlarged micrographs of a thick
region before and after the crystallization.
In summary, the observation that the crystal lattices in the two
grains sandwiching the grain boundary layer grow into the
originally amorphous-like layer strongly suggests that the grain
boundary layer is not of an impurity phase but rather a
structurally relaxed one with virtually the same chemical
composition as the mother phase, i.e. an extended grain
boundary.
Fig. 9.12.
Growing of crys-
tal lattices into an
amorphous-like
grain boundary
layer. Enlarged
photographs (a)
before and (b)
after crystal-
lization of the
layer. 29
203
Hiroaki Kurishita, Hideo Yoshinaga, Yuichi lkuhara
9.4.2 Poor Sinterability and Grain Boundary Energy

Two theories have been proposed to explain the poor sin-
terability of SiC. Inomata et al. 5 •30 suggested that SiC has a too
small driving force for densification. Since the interatomic bonds
of covalent materials like SiC have a strong directionality,
ordinary grain boundary energy is extremely high, and there is
little relaxation of surface energy due to grain boundary
formation. The other theory, found in the papers of Greskovich
& Rosolowski,31 Hase et al. 14 and SUZUki,23 suggests that the
driving force is sufficiently large and that instead diffusion is
responsible. Since the surface diffusion prevails over the grain
boundary diffusion and bulk diffusion, grain growth occurs as the
result of surface diffusion before grain boundary and bulk
diffusion is activated, thereby preventing densification.
The latter theory's assumption that the driving force is
sufficiently large is based on the results of 'dihedral angle'
measurements. The dihedral angle cJ> must be larger than 6(f in
order for densification to occur during sintering (this corresponds
to
Ygb/Ys = 2 cos(cJ>/2) < V3
where Ygb and Ys are grain boundary energy and surface energy,
respectively). According to the measurements of Greskovich &
Rosolowski31 and Hase et al., 14 the dihedral angle is 100° and
above31 and most frequently 92°,14 respectively, even in SiC that
shows no densification, thereby fulfilling the thermodynamic
conditions for densification.
On the other hand, Inomata30 disagrees with this theory,
proposing that, unlike in isotropic substances, in a substance such
as SiC with strong anisotropy of the interatomic bonds the grain
boundary energy changes with the orientation of the grain
boundary, making it wrong to apply the concept of dihedral
angle. This argument is based on the conventional idea that,
because the interatomic bonding energy for SiC is extremely
strong, structural relaxation is unlikely to occur, i.e. that the
formation of an amorphous phase at boundaries will not be
allowed. 30 Assuming this to be true, Inomata's concept is quite
rational, and the argument for a large driving force for
densification loses its grounding.
From the observations described in Section 9.3, however, this
supposition does not appear to be correct, as even in sample C
without any additives a layer believed to be relaxed and

amorphous is present on the grain boundary. Since an amor-
phous layer is necessarily isotropic, the concept of dihedral angle
described above would be valid. Figure 9.13 is an example of
pores observed in sample C. In Fig. 9.13 the dihedral angle is
greater than 90". This fulfills the above-described thermodynamic
conditions for densification and indicates that even undensified
sample C has a large driving force for densification.
Fig. 9.13.
Examples of
pores observed in
sample C (no
additives).9
Thus we would like to emphasize that the reason behind the

large driving force in SiC despite its high covalency is the
existence of extended grain boundaries.
A large driving force means that the diffusion is responsible for
poor sinterability. Consequently, by inhibiting SiC decomposi-
tion at high temperatures through the application of high
pressure and performing sintering with a rapid enough heating
rate so that the surface diffusion-induced grain growth is
inhibited up to the temperature at which the grain boundary and
bulk diffusions become dominant, densification should be
possible even without the addition of a sintering aid.
9.4.3 Orientation Dependence of Grain Boundary

Strength
According to model calculations by Inomata et al. concerning SiC
without structural relaxation, s-s grain boundary energy varies
greatly according to grain boundary orientation. Furthermore,
according to research by the authors32-3S concerning molybde-
num~ which is one of the metals with the highest covalency, the
grain boundary fracture strength is remarkably dependent on
grain boundary orientation. The situation is different, however,
when the grain boundary is present as an amorphous layer having
a certain thickness (as in the SiC introduced in this work); in this
case, the grain boundary strength is determined mainly by the
interatomic bonds within the boundary layer. The grain bound-
ary energy can change as the result of change in layer thickness
even when the properties of the amorphous layer remain the
same. Since the grain boundary fracture occurs as a result of the
breaking of interatomic bonds mlayers with disturbed structures,
it is thought that as long as layer properties are the same, the
fracture strength will remain virtually unchanged and independ-
ent of grain boundary orientation, regardless of some change in
grain boundary energy .
. Figure 9.14 was prepared to clarify this point. Two 6H SiC
single crystal (0001) planes were stacked and bonded at a variety
of twist misorientations to prepare a bicrystal having a [0001]
twist grain boundary. Bonding was conducted in a vacuum at
2270 K under a pressure of 40 MPa. 10 No sintering aids were
used.
(0001) Fig. 9.14.

Illustrating the
preparation of
SiC bicrystals
having a (001)
twist grain
boundary with
00
misorientation
angle 9. 10
Figure 9.15 shows the strength of the resulting bonding

interlace as measured by a three-point bend test at room
temperature. The strength is plotted against the twist misorienta-
tion angle 8. The fracture occurred invariably in a brittle manner
at the bonding interlace. Although there is large data scattering,
the strength, when viewed at the upper limit of the scattering, is
approximately 200 MPa virtually independent of 8. Unbonded
regions were observed on the interlace. The data scattering is
thought to be due to these unbonded regions. That the upper
limit of the measured values shows a virtually constant value
independent of 8 seems to indicate that, with respect to these
high values, the effect of unbonded regions was small, and the
intrinsic strength is almost 8-independent. The 8-independence
corresponds well with the earlier-described prediction of the
extended grain boundary model.
Fig. 9.15.
Relation of bend-
~200 ing strength Of to
twist angle 9 for
& SiC bicrystal
.s:;.
without any
2'
Go additives.
"-
Vi 100
2'
]
0L-~0--------1~0--------2~0------~30~~
Twist Misorientation eI deg

Fig.9.16. TEM (a )
image of bonding
interface for SiC
bicrystals. 10 (a)
8=0"± 1°; (b)
8 = 30°. Arrows
indicate the bon-
ding interface.
Figures 9.16 and 9.17 are low- and high-resolution TEM

micrographs, respectively, of the bonding interface. In both
cases, (a) corresponds to the interface for which (J = 0° ± 1°, and
(b) corresponds to the interface for which (J = 30°. In the
low-magnification photographs, periodic strain contrast can be
observed along the interface, for (J = 0° ± 1° the period being
short. In the high-resolution photographs, a layer (i.e. an
extended grain boundary) with a thickness of approximately 1 nm
Fig. 9.17. High-

resolution TEM
image of bonding
interface for SiC
bicrystals. 1o (a)
8=00±1°;(b)
8=30°.
and a disturbed structure is present on both interfaces. The

reason why the thickness of the layer, at about 1 nm, is smaller
than that of the layer observed in pressureless-sintered materials
(2-5 nm) is that the bicrystal grain boundary plane is the (0001)
low index plane and atomic matching is fairly good. The
incomplete connection even at 8 = 00 ± 10 is thought to be due to
the interface polarity. 10
9.S SUMMARY
Pressureless-sintered bodies of SiC containing Band C and SiC

without any additives exhibit no loss of strength up to 2070 K,
and this is thought to be due to the formation of 'extended grain
boundaries'. The extended grain boundary is not a second phase
but a boundary which has relaxed across a given thickness
(=:;;5 nm) in order to reduce the high grain boundary energy
rooted in covalency. The extended grain boundary has a
composition resembling that of the mother phase. From the
standpoint of this extended grain boundary qualitative explana-
tion is possible; for example, grain boundaries of the above-
described materials are strong at high temperatures, in SiC the
driving force for densification is sufficiently large despite the high
covalency, and the grain boundary strength of SiC bicrystals is
not significantly dependent on orientation.
In addition, a pressureless-sintered body containing AlN
exhibits a remarkable loss in high-temperature strength at
temperatures of 1870 K and above. Although the same type of
grain boundary layer is observed in this material as well, this is
not an extended grain boundary but a second phase which flows
viscously at high temperatures.
REFERENCES
1. Tsuge, A. & Nishida, K., High-strength hot-pressed Si3N4 with

concurrent Y203 and Al20 3 additives. Bull. Am. Ceram. Soc., 57(4)
(1978), 424-31.
2. For example, Kamigaito, 0., Structural ceramics. Bull. Japan Inst.
Metals, 24(6) (1985), 480-5.
3. Ogbuji, L. U., Grain boundaries in carbon- and boron-densified

SiC: examination by high resolution transmission electron micros-
copy. In Materials Science Research, Vol. 14, Surface and Interfaces
in Ceramics and Ceramics Metal Systems, ed. J. Pask & A. Evans,
Plenum Press, New York, 1981, pp. 713-23.
4. Verma, A. R. & Krishna, P., Polymorphism and Polytypism in
Crystals. John Wiley, New York, 1967.
5. Inomata, Y., Uemura, Y., Inoue, Z. & Tanaka, H., Energy stored
in a grain boundary formed by a rotation along a hexagonal lattice
plane in SiC crystals. Yogyo-Kyokai-Shi, 88(10) (1980), 628-33.
6. Uemura, Y., Inomata, Y. & Inoue, Z., A grain boundary of a-SiC
bicrystals. J. Mater. Sci., 16(8) (1981),2333-5.
7. Tanaka, H. & Inomata, Y., Observations of holes around
dislocation core in SiC crystal. J. Cryst. Growth, 53(3) (1981),
630-2.
8. Inomata, Y., Grain boundaries of high performance ceramics for
structural uses. Bull. Japan Inst. Metals, 22(2) (1983), 128-9.
9. Ikuhara, Y., Kurishita, H. & Yoshinaga, H., Grain boundary and
high-temperature strength of sintered SiC. Yogyo-Kyokai-Shi, 95(6)
(1987),638-45.
10. Ikuhara, Y., Miyazaki, H., Kurishita, H. & Yoshinaga, H., Grain
boundaries in SiC with no additives. Proceedings of the '87
International Symposium & Exhibition on Science and Technology
of Sintering, Tokyo, Japan.
11. Soeta, A. & Maeda, K., Study on sintering process of SiC ceramics
with BeO or AlN addition by analytical electron microscopy.
Yogyo-Kyokai-Shi, 93(10) (1985), 636-48.
12. Yajima. S.• Hayashi, J. & Omori, M., Continuous silicon carbide
fiber of high tensile strength. Chem. Lett., 45(9) (1975), 931.
13. Prochazka, S. & Charles, R. J., Strength of boron-doped,
hot-pressed silicon carbide. Am. Ceram. Soc. Bull., 52(12) (1973),
885-91.
14. Hase, T., Suzuki, H. & Tomizuka, I., Microstructure development
of undoped compact of /J-SiC during heating. Yogyo-Kyokai-Shi.
87(6) (1979), 317-21.
15. Gulden, T. D., Mechanical properties of polycrystalline /J-SiC. J.
Am. Ceram. Soc., 52(11) (1969), 585-90.
16. Tanaka, H., Inomata, Y. & Kawabata, H., Strength of hot-pressed
SiC from Al doped a-SiC powder. Yogyo-Kyokai-Shi, 88(3) (1980),
158-60.
SiC by the addition of Al and B. Yogyo-Kyokai-Shi, 88(9) (1980),
570-4.
18. Fujita, S., Maeda, K. & Hyodo, S., Dislocation glide motion in
6HSiC single crystals subjected to high-temperature deformation.
Phil. Mag., 55(2) (1987), 203-15.
19. Maeda, K., Dislocation glide induced plasticity of 6H SiC single
crystals. Yogyo-Kyokai-Shi, 94(8) (1986), 784-9.
20. Iseki, T., Arakawa, K., Matsuzaki, H. & Suzuki, H., Joining of
210
dense silicon carbide by hot-pressing. Yogyo-Kyokai-Shi, 91(8)

(1983), 349-54.
21. Inomata, Y., Tanaka, H., Inoue, Z. & Kawabata, H., Phase
relation in SiC-At.C3-B4 C system at 1800°C. Yogyo-Kyokai-Shi,
88(6) (1980), 353-5.
22. Suzuki, H. & Hase, T., Boron transport and change of lattice
parameter during sintering of tJ-SiC. J. Am. Ceram. Soc., 63(5-6)
(1980), 349-50.
23. Suzuki, H., Recent trend and theoretical background in sintering
process of silicon carbide ceramics. Ceramics, 18(1) (1983), 3-9.
24. Ikuhara, Y., Deno, H. & Yoshinaga, H., Mechanical properties of
newly developed Si3N4-SiC composite material with relatively high
flexibility. Yogyo-Kyokai-Shi, 93(8) (1985), 409-17.
25. For example, Abe, H., Kawai, M., Sugano, T. & Suzuki, K., In
Engineering Ceramics, Ceramics Science Series No.5, ed T.
Yamaguchi & H. Yanagida. Gihodo, 1984, p. 133.
26. Hiraga, K., Application of high resolution electron microscopy to
the study of structure defect and grain boundaries in Si3N4 and
SiC-a brief review. Sci. Rep. Ritu, A-32(1) (1984), 1-20.
27. Niihara, K., Mechanical properties of CVD non-oxide ceramics.
Bull. Am. Ceram. Soc., 63(9) (1984), 1160-4.
28. Ichinose, R., Inomata, Y. & Ishida, Y., RREM analysis of SiC
grain boundary structure. Yogyo-Kyokai-Shi, 94(4) (1986), 415-18.
29. Ikuhara, Y. & Yoshinaga, R., Change in grain boundary structure
of AlN-polytype Sialon by electron irradiation. J. Electron Microsc.,
36(6) (1987),408-10.
30. Inomata, Y., Joined crystal of silicon carbide. Yogyo-Kyokai-Shi,
90(5) (1982), 242-7.
31. Greskovich, C. & Rosolowski, J. R., Sintering of covalent solids. J.
Am. Ceram. Soc., 59(7-8) (1976), 336-43.
32. Kurishita, R., Kuba, S., Kubo, R. & Yoshinaga, R., Grain
boundary strength of molybdenum bicrystals with a (110) twist
boundary. Trans. JIM, 26(5) (1985), 332-40.
33. Kurishita, H., Oishi, A., Kubo, H. & Yoshinaga, R., Grain
boundary fracture in molybdenum bicrystals with a (110) symmetric
tilt boundary. Trans. JIM, 26(5) (1985), 341-52.
34. Kurishita, R. & Yoshinaga, R., Effects of interstitial impurities on
intergranular brittleness of molybdenum. Bull. Japan Inst. Metals,
22(11), (1983), 944-52.
35. Kurishita, R., Yoshinaga, R., Abiko, K., Suzuki, S. & Kimura, R.,
Grain boundary fracture in molybdenum bicrystals. In Grain
Boundary Structure and Related Phenomena, Supplement to Trans.
JIM, 27 (1986), 739-46.
211
10 Sintering of Silicon
Carbide
HIDEmKO TANAKA
ABSTRACf
Sintering behavior and sintering techniques of silicon carbide are

reviewed. Work on sintering experiments with silicon carbide
containing B-C and AI-B-C is referred to. First, the driving
energy of sintering, the non-sinterability of silicon carbide
powder, and the role of additives are explained by the free energy
theory of mass transport. Second, silicon carbide sintering tech-
niques are reported. In the case of B-C addition, it is emphasized
that optimization of added B content, sintering atmosphere and
heating rate are important factors controlling the density of the
sintered SiC. Sinterability of AI-doped SiC powder and sintering
by the addition of A12 0 3 , AI-C, Al-B-C and other compounds
are summarized.
10.1 INTRODUCTION
The first to report the sintering of SiC powders were Alliegro et

al. 1 They used hot-pressing and showed that additives are
required for the sintering of SiC and that the addition of metals
such as Fe, AI, Cr, Ca, Li, Ni, B, AI-Fe, and Zr-B was effective
in sintering. Later, in 1975, Prochazka2 discovered a method of
pressureless sintering which used the addition of trace amounts
of Band C. It was found that SiC sintered bodies possessed
superior strength at high temperatures, and it is well known that
they were seen as a promising heat-resistant structural material.
The main reason for the attention focused on ceramics as
213
Hidehiko Tanaka
possible structural materials is their heat resistance, but few

ceramics are capable of maintaining their strength at the high
temperatures which prohibit the use of metals, the exceptions
being covalent materials like Si3N4 and SiC, mullite, etc.
Approximately 87% of Si-C bonds are covalent, and this is the
source of the high strength of SiC sintered bodies. SiC is
fundamentally a brittle material. Its low fracture toughness
presents difficulties in application as a structural material, but
SiC sintered bodies are one of the few materials which can be
used at extremely high temperatures (e.g. 13OO°C and above).
Recently, they have seen wide application as a wear-resistant
material in mechanical components involved in sliding motion.
From this standpoint, active research has been conducted on
sintering methods for SiC powders, and numerous sintering
methods have been developed.
In this report, sintering of SiC is reviewed with an emphasis on
sintering aids. Sintering is explained based on the new free
energy theory for sintering. Sintering theory will first be
discussed. In this context, the non-sinterability of SiC powders
and the need for sintering aids will be explained. Next, sintering
techniques using a B-C or Al-B-C system aid will be discussed.
10.2 FREE ENERGY THEORY OF SINTERING3-5
The phenomenon in which a powder sinters and densifies is the

process in which interfaces are formed through diffusion (mass
transport) as particles are deformed. In order for sintering to
proceed, the following conditions must be met: first, formation of
a crystal grain boundary causes a reduction in particle surface
area, thereby decreasing the free energy of the system; and
second, diffusion of atoms must occur with a certain degree of
activity. The latter condition is ordinarily achieved by heating to
high temperatures. The former is dependent on surface and
interface energies Es and 2Eb and on the geometric shape of the
particles being joined. In other words, sintering is the process in
which surfaces are transformed into interfaces, the resulting
excess free energy driving densification-related mass transport.
According to Inomata's 'Free energy theory of diffusion-
controlled mass transport' ,3,4 the rate of mass transport within a
214
Sintering of SiC
Fig. 10.1.
Bonding model
for two particles.
x=Xr
given particle dv/dt can be expressed as follows: 3
dv = D (ax
dt x Ax
){l_ exp(6.G)}
RT
(1)
Here, Dx is the self-diffusion coefficient of the substance, ax and

Ax are the effective diffusion cross-sectional area and distance, R
is the gas constant, T is the absolute temperature, and 6.G is the
free energy relaxed by diffusion.
For the case of sintering in which no grain growth is assumed,
6.G can be expressed as:
6.G = 6.Gt - 6.Geq
Here, &Gt is the surface and interface energy possessed by the
system at time t as shown in Fig. 10.1, and 6.Geq is the same
energy in a state of pseudo-equilibrium an infinite time later after
the net growth has been completed. Specifically, 6.Gt and 6.Geq
can be calculated from surface and interface areas. From eqn (1),
the rate of shrinkage during sintering is as follows: 3
~ (1-~) = (DxEs V)(~)({l-

dt ro 4nRT Axr4
3(1-(1-X)2(2
X)
+ X)}213) 6.
1/J
(2)
Here, V is the molar volume, ro is the initial radius of the

particle, X is the ratio of the initial particle radius to the distance
x between two particles (X =x/r), and 6.1/J is the difference in
surface and interface energies between time t and the state of
pseudo-equilibrium (t = 00), i.e. the function Eb/ Es. Actual
calculations were performed in Ref. 3.
2IS
Hidehiko Tanaka
Fig. 10.2.
Relation of
shrinkage
(I1LILo), (Eb/ E.), 4l
and normalized ~
time B . t. The
two axes are
dimensionless,
with (Ebl E.) for
curves 1-7 being
0, 1/3, 1/2, 1/...;2,
\13/2, 0·910 and If sintering is controlled by volume diffusion, Dx is bulk
0·970, respec-
tively. Line 'a' diffusion constant and ax and Ax are proportional to r~ and ro,
corresponds to respectively. Therefore, the rate of shrinkage is inversely
the state in which proportional to r~. In the case of grain boundary diffusion, where
all pores have dis- lJ is taken to be the width of the grain boundary, ax is
appeared. Lines
'b', 'c' and 'd' are proportional to rolJ, and the rate of shrinkage is inversely
asymptotes for proportional to r~. The sintering curves obtained from eqn (2)
curves 5,6 and 7. 3 are as shown in Fig. 10.2.3 In the figure, several shrinkage curves
are shown for normalized time B with Eb/ E. as a parameter.
B= (~~~~C:;~)
It can be seen from Fig. 10.2 and eqn (2) that the following are
required in order to promote the sintering of a simple substance:
(1) Reduction of grain boundary energy.
(2) Increase in diffusion constant.
(3) Reduction of powder particle size.
Although this is only natural as a precondition to sintering, if
Eb/ E. approaches 1 and there is little relaxation of energy on the
grain boundary, the powder will not attain theoretical density
even if conditions (2) and (3) above are fulfilled.
Ordinarily grain growth cannot be avoided during sintering
because the disappearance of surfaces and interfaces encourages
grain growth. From the same argument as in the case of
sintering, grain growth rate can be expressed as follows,
assuming a mean particle diameter rex) for the system: 4
( dr!
d~ = D (3VE.b)(~)2-lIYI (X)
x 4RT Ax P m
(3)
Here, /m(X) is a particle size function which approaches 0 when
216
Sintering of SiC
there is a narrow particle size distribution and is equal to 0 in

cases of uniform particle size. Eob is the sum erEo + {JEb of surface
and interface energies, er and {J being the ratio of surfaces to
interfaces for each system. Therefore, grain growth is inhibited
by:
(4) Small gap in particle size (i.e. a narrow particle size
distribution); and
(5) small Eb values.
Reduction of the grain boundary energy amplifies the trend
toward reduction of system energy not by grain growth but rather
by sintering. In this way, conditions (3) and (4) above are
required of powders, while during sintering consideration should
be given to conditions (1) (or (5» and (2). Condition (1) in
particular is related to sintering additives.
In fact, however, fulfillment of each of the above five
conditions does not guarantee that sintering will result in
densification. This is because of technological problems such as
powder shape before sintering and heterogeneity of the compact.
With an extremely fine powder, for example, even if sinterability
can be improved, workability deteriorates, making it more
difficult to increase compact density. A certain degree of particle
size and particle size distribution are required in order to
increase compact density. Agglomeration in the powder to be
sintered and heterogeneity in the primary compact inhibit
densification remarkably. Heterogeneity includes fluctuations in
compact density, pores and inclusions, and non-uniform distribu-
tions. Grinding and mixing of the powder to be sintered comprise
one of the most important processes.
10.3 NON-SINTERABILITY OF SiC POWDERS

AND SINTERING ADDmVES
It was shown in Fig. 10.2 in Section 10.2 above that the

sinterability of a powder depends heavily on Ebl Eo. Furthermore,
Eb and Es directly reflect the chemical bonding conditions and the
structure of the material. Relaxation of the surface energy by
grain boundary formation is relatively easy in metal bonds, and
joining of the particles is likely to occur regardless of crystal
orientation. In the case of covalent materials such as SiC,
217
Hidehiko Tanaka
Fig. 10.3
Dangling bond
model for the
joining of (0001)
planes of hexago-
nal SiC. The black
and white tri-
angles indicate
lattice points on
the upper and
lower joining
surfaces, and the
11109 lattice
corresponds at a
twist misorienta-
tion of 10·99".9
however, even if grain boundaries are formed there is a strong

orientation to the bonds, making it impossible to expect much
relaxation of the surface energy. This can be understood by
taking into account a dangling bond model like the one shown in
Fig. 10.3. The model shows the twist grain boundary of the
(0001) plane of hexagonal SiC. If the relaxation of surface energy
is performed with corresponding bonds, the amount of relaxation
would be extremely small. For example, when one considers that
the coincidence-site lattice model has succeeded in explaining the
twist grain boundaries of gold6 and Mg07 as well as the (001)
grain boundary of BaTi03 , 8 as a first approximation the grain
boundaries of SiC crystals can be evaluated by the number of
dangling bonds formed thereon.
In fact, the twist misorientation of the (0001) grain boundary,
which is synthesized only rarely in high-purity 6H SiC, is well
explained by the model of Fig. 10.3. 9 Furthermore, joining of the
(0001) and (1010) planes of 6H SiC single crystals has been
observed to be performed with corresponding lattices. 1o,11 Figure
10.410,11 is one example of this. The mean amount of energy
relaxation for this kind of SiC twist grain boundary has been
calculated by Uemura et al. 12 from the model of Fig. 10.3. For
the (0001) plane twist grain boundary Eb/ E. was calculated to be
0·990-0·988. These results were based on a simple model, but
they are sufficient to suggest that the mean energy relaxation
218
Sintering of SiC
.., .....
J".
).
• ,
~
•
..
• ,.
'
,".
,.
•
..
••
•
~
•
;.- . ',-
• •
,,'"
"
. . . : .. _1. :.'
t .0" .. "
.'
"
.'
, ,. •
..
, ....
" •• 4
",.-
.. .. •
, .....'," .......
..........
,. .....
............
.." 110 ..
. . . . _.
'" .' ..... .; .'...
'
• •
Fig. 10.4. Joining
interface of the
(0001) plane and
1 •••• , . . . . . . . ' . , •• _. •• • • • • , •••
• .... : . : • • • • , ' : . . . . . . . . . . .'....... ,'. " •••••• " e .• (1012) plane of

' : : . : . , ..... " , . _ " , , a ' " " •••• " ' . - : " high-purity hexa-
..
.... " .,. ' .... I', ........... '.. .. •.. ,'.... .. ,'.. " :,o.. ,.... : •
,. ,': ... : ..... : , ." . ,fa! ,. ,••':-:~. ".'.-.' " ,t,,'. . .'.'''.' :'•• ,_ : .
·. ':1 •• .. .......... , ................ ...' .. ". ... .. .. ""
".'-" ',a •• \, •••. '0 .. •• " , .................", .. , ...... gonal (6H) SiC.
(A) Overall image
-,';;..t,.~ .:::.' .... : .. :; ...:..' ,".' \::,-: ~ ',':: .. ',," ';.":-- of the grain
• \~" .......... ~........ ~ •• , •• , .. :t•.•. .• ,1 boundary
..
............................ ' ..... .
.' t" .•:.'.' •• ':, •.••. III.,
J" ............ .... • •• .............................. ... . . . . . . . . . .,
structure;10 (B)
.................... ....." ,,,.......
.~. ~
....... ... " ......... -.......

atomic observa-
..
,
"... ....
• • • • • • • •• . , . to " ••••••••••
·..............
...., ..................
",
. . ... . .....••·.·
tion of the grain
..... . .. •....
"
.. . . .,···f·· .......................
•.•. _ ...........'.
~
boundary
...... .................... ....

•
•• ~~:". ~ ......._•.
........... _
...•..•.... , .••...•......•
"
.. _ _ _ _ ... _
~-.~~ .!~ ~'.
..... __ ..
.
__________
, '\
... .& _ •
,
::... ~:'~,:.~'!l! .. :.~~': ..:.'~
.... ... .
_ . _ _ _ .... _ _ .Iloo..-
~
structure. 11 The
grain boundary is
constructed to re-
duce the total
energy (i.e. the
number) of dan-
gling bonds. The
arrows indicate
the joining inter-
face, and the
joining surface is
perpendicular to
the photographs.
resulting from formation of grain boundaries in high-purity SiC

particles is extremely small.
Based on Fig. 10.2, it can be predicted that the sintering
behavior of pure SiC powder will approximate curve 7, i.e. the
contraction curve for which Ebl Es is 0·970. Even if sintering is
performed at sufficiently high temperatures for a sufficiently long
period of time, the powder will not density to theoretical levels.
In other words, high-purity SiC powders lack the driving energy
required for densification, making them fundamentally nonsin-
terable. Densification requires the reduction of Eb by addition of
219
Hidehiko Tanaka
Fig. 10.5. Grain

boundary ob-
served in an SiC
sintered body
containing a B-C
system sintering
additive. Thick-
ness of the amor-
phousgrain
boundary second
phase is
approximately
O·5nm. 13
a sintering aid, and according to Fig. 10.2 Ebl Es must be brought

down to less than approximately 0·7.
In this way, the role of the sintering aid is to reduce the energy
present at the grain boundaries. Hence it can be predicted that a
structureless amorphous material would be more effective as a
grain boundary phase. The fact that the grain boundary phases of
SiC and Si3N4 sintered bodies are amorphous or glassy phases
support this conclusion. Figure 10.5 is a TEM image of the grain
boundary of a SiC sintered body. 13 Band C were used as
sintering aids. An amorphous second phase (width: approxim-
ately 0·5 nm) is present between the two particles whose layer
structures can be observed, and it can be seen that the opposing
particles are joined through this second phase. The same
observation has been made by Suzuki & Hase. 14 A comparison of
Figs 10.4 and 10.5 makes it easy to understand the difference in
grain boundary structures between pure SiC and sintered bodies
thereof.
Sintering of SiC
10.4 SINTERING ADDITIVES AND SINTERING

TECHNIQUES FOR SiC POWDER
10.4.1 Sintering of SiC Powders Containing 8-C

System Sintering Additives
A great deal of research has been conducted on sintering
additives and sintering techniques for SiC powders, and a wide
variety of materials has been developed. 15 When sintering effects
and the high-temperature properties16 of the materials obtained
are taken into consideration, however, B-C systems can be seen
to be superior. Although there is some problem with the
brittleness of the materials, this is the central technology for the
manufacture of SiC sintered bodies for application in mechanical
components.
10.4.1.1 Band C Content and Sintered Density 17
When B-C system sintering additives were first discovered, it
was thought that the addition of C removed Si02 from the SiC
powder surface, thereby increasing E., and that B precipitated on
the grain boundaries to reduce Eb. 1 Consequently, C was added
in a small quantity sufficient for deoxygenation, while B was
added in a quantity greater than its soluble volume (0·3 wt%) in
SiC. 18 Recently, however, it has come to be recognized that it is
C which acts also as the main sintering aid, since a certain
amount of C is required regardless of the oxygen concentration
of the sintering powder. As described in the previous section,
C and B are believed to reduce Eb at the grain boundaries. B is
required, but in smaller quantities than C.
Figure 10.617 shows ultimate density when high-purity fJ-SiC
powder was sintered with different carbon raw materials. C was
added using pitch tar, phenol resin, furan resin and carbon black,
and 0·6 wt% B was added as a metal. The first four substances
were mixed in the liquid phase. It can be seen from the figure
that densification requires 1·0-2·0 wt% C; when the added C
content drops below 1 wt% the sintered density drops dramati-
cally. When there is insufficient carbon, the particles in the
powder merge during the initial phase of sintering to cause
plate-like grain growth (see Fig. 10.7), thereby inhibiting later
densification. This is because reduction of Eb by C was not
achieved. In addition, the reason why it is difficult to increase
221
Hidehiko Tanaka
Fig. 10.6. Density

of SiC sintered by
the addition of C
from four sources
(sintering condi- 3.00 >-
\'
tions: O·6wt% B,
2050°C, 15 min). 17
M
stJ 2.80
"-
00
\ \
\
>-
:; \
'"z:
UJ
Q
2.60
\
""
~
-'
:::>
IX> o Pitch tar
A Furan resin
~ Phenol resin
1:1 Carbon black
2.40L
.~I----~I----.~--~----~--~
o 1 2 3 5
CARBON CONTENT (%)
sintered density when C is added in the form of carbon black is

thought to be that, since carbon black is a solid it is not able to
diffuse into the powder as well as the liquid materials. Since B
diffuses well into the SiC surface at high temperatures,14 it is the
technique of addition and mixing of C which should be given
more consideration.
Figure 10.S17 shows the results of sintering with 1-1·7 wt% of
C and varying amounts of B. It can be seen that the minimum
amount of B required for sintering is only about 0·15 wt%.
Ordinarily B is added in concentrations of 0·5-1·0 wt%,18 but
this is more than enough, and in fact the addition of large
quantities could actually be deleterious in the sense that grain
groWth is accelerated.
Regardless of the sintering additive used, control of the
sintering atmosphere and heating rate are important to the
sintering of SiC powders. With the addition of B-C system aids,
C'J
S·
~
~.
Fig. 10.7. Structure of SiC sintered bodies containing B-C system sintering additives (a) and (b) contain 2 wt% C and
O·2wt% B; (c) contains 1·7wt% C and O·4wt% B; and (d) contains O·25wt% C and O·25wt% B. Sintering was ~
C'J
a performed for 15 min at 2050"C. 17 ?5
Hidehiko Tanaka
Fig. 10.8. B con-

tent versus sin-
tered density (sin-
3.20
tering conditions:
1·0-1·7wt% C,
2050°C, 15 min;
21500C for 60 min
..
in the case of M
3.00
+V' !
o Pitch carbon 1. 7'7.

<:>. Phenol carbon 1. 0%
2.40
L.....------'_. _--,-I_--'-_--'-I_----1-_"----'
o 0.2 0.4 0.6
BORON CONTENT (%)
the following reactions are likely to occur during sintering.

SiOz + C-+ SiO + CO (4)
2B + 3CO-+ BZ0 3 + 3C (5)
B+CO-+BO+C (6)
In eqn (4), CO gas is produced by the reaction of SiOz in the
powder surface and the added C. CO gas is also formed from
residual oxygen in the furnace and the carbon refractories. CO
gas in the atmosphere reacts with B according to eqns (5) and
(6), and B is dissipated in the vapor phase. Oxygen and CO gas
in the system are deleterious to sintering. Thus it is necessary to
perform sintering in a reduced-pressure atmosphere and elimin-
ate the CO gas from the system.
The next factor to consider is the heating rate. Rapid increases
in temperature are not favorable. The reaction of eqn (4) starts
at approximately lOOO°C in reducing atmospheres and vacuum.
Since time is required for the reaction of C and SiOz to be
completed and the CO gas to be discharged from the system, the
Sintering of SiC
most effective way to increase sintered density with few additives

is to increase the temperature slowly in the range from l000"C to
1500°C or to maintain a constant temperature for a certain time
period within the same range. 19 In the region of 2000°C an Ar
atmosphere is often used to inhibit decomposition of the SiC.
10.4.1.2 Grain Growth and Strength of the Sintered Body
There are two types of abnormal grain growth which occur in SiC
sintered bodies. The first is that in which particles aggregrate and
grow in a plate-like form during the initial stages of sintering; the
second, the exaggerated grain growth which occurs after
densification.
Figure 10.717 shows the relation of fJ-SiC sintered body
structure to additive content. Figure 1O.7(d) is an example of
plate-like particle growth; this can be observed when the additive
is not present or is present but in insufficient quantity, and is due
to a lack of relaxation by Eb' As can be seen in the figure,
plate-like grain growth significantly inhibits densification. Struc-
tures of sintered bodies produced using appropriate amounts of
additive are shown in Fig. 10.7(a) and (b).
Figure 10.7(c) shows an example of exaggerated grain growth.
This type of growth is accelerated by the addition of B, which
increases the diffusion coefficient of SiC. Figure 10.917 shows the
Fig. 10.9. Density
and exaggerated
.c grain growth as a
0.6 r-
3.13
.!:~
"' ...
....
....
.,
function of Band
C content. Sinter-
\ ~~ ingwasper-
formed for 15 min
H 0.4 r '-\ ' .." /! ~ at 2050°C. 17
ffi
~
~=3.0 3.09
~.-\---.--- -.--_.
: ; ; ) . 1 4 3.07:
z: 2.84 3.05 3.12 3.03

~ 0.2r- 0 ~O ~
g 2J6
o '---___ --.L._._ _ _ . L . . - 1_ _ _....I.

1 ....
1 2 3
CARBON CONTENT <Xl
Hidehiko Tanaka
Fig. 10.10. SiC -,

sintered bodies
600
and bending
strength. The. c
a..
marks indicate :IE:
samples in which
exaggerated grain ::t:
I-
<.!> 400
growth was ob- z:
UJ
0
0::
served. Strength I-
was determined '"<.!>

by a 30-mm span ::;
<=l
z:
three-point bend UJ
200 o Normal grain growth
test (JIS R "" • Exaggerated grain
1601).17 growth
0
2.0 3.0 3.2
DENSITY ( g/cm' )
relation of Band C content to density and exaggerated grain

growth. The sensitivity of ultimate density to B can be seen in
Fig. 10.8, and as the quantity of B increases exaggerated grain
growth becomes more likely to occur.
In the example of Fig. 10.9, exaggerated grain growth occurred
with the addition of 0·3 wt% or more of B. This growth is more
likely to occur with fJ-SiC than with a-SiC powders. At sintering
temperatures the fJ (3C) phase is unstable, but the a (mainly 6H,
15R) phase is stable. In the final stages of sintering, therefore,
the fJ phase is easily transformed into an a phase, and the
resulting change in free energy gives rise to grain growth-related
mass transport. This is why fJ-SiC powders are more difficult to
sinter than a-phase powders. As is clear from Fig. 10.9,
however, this problem can be resolved by reducing the B
content.
Figure 10.1017 shows the relation between strength and density
for fJ-SiC sintered bodies prepared under various conditions. It
can be seen that the strength of the sintered bodies increases
sharply when density exceeds approximately 3·1 g/cm3 (97% of
theoretical). Points marked with a • in the figure indicate
sintered bodies which exhibited exaggerated grain growth.
Despite high densities these specimens had low strength,
indicating the deleterious effect of grain growth on strength. In
this way, SiC sintered bodies having high strength can be
Sintering of SiC
obtained only by the use of materials which can be densified to

theoretical levels and are free from abnormal grain growth. The
key points to sintering from a technological aspect, therefore,
are: (1) to optimize Band C content, and in particular to reduce
the amount of B added; and (2) to control the atmosphere and
the heating rate.
10.4.1.3 Structure of (t'- and {J-type SiC Sintered Bodies
More than 50 polytypes of SiC have been discovered, but those
ordinarily found in sintered bodies include 2H, 3C, 4H, 6H and
15R. Among powders for sintering can be found 6H and 3C
Fig.lO.H.
Structure of a-
and tJ-SiC sin-
tered with 8 and
C. The white line
at the bottom of
each photograph
has a length of
approximately
3·3 Jl.111. (A) a-SiC
sintered body; (8)
tJ-SiC sintered
body. 20
Hidehiko Tanaka
Fig. 10.12.
Comparison of
fracture tough-
ness for (1'- and 51-
!J-SiC sintered
bodies. 20 SENB,
single-edge notch 41-
beam;CVNB, N
"- r-RT
chevron notch r<'I
:E:
beam. "-
z: 31-
~
u
:>.: 2 I-
lI-
D
SENB CVNB
polytypes. There are no differences in sintering mechanisms

between these polytypes, and sintering techniques are virtually
identical for both of them. The structures of the resulting
sintered bodies, however, do differ. Figure 10.1120 shows typical
structures for (l'- and p-type SiC sintered bodies. The former is
composed of spherical particles, while the p-type particles grow
into plate-like shapes and tend to have a larger aspect ratio.
No results obtained thus far have suggested that this structural
difference is significantly reflected in the mechanical properties of
the resulting materials, but it appears that a large particle aspect
ratio is conducive to higher strength. 21 Figure 10 .1220 compares
fracture toughness K IC for (l'- and p-type sintered bodies. At
room temperature there was no appreciable difference in the
values, but at high temperatures K IC was observed to increase
more in the p-type variety.
10.4.2 Sintering of SiC Powders Containing AI System

Sintering Additives
10.4.2.1 AI-C System Sintering Aids
The effectiveness of Al metal as a SiC sintering additive was
discovered by Alliegro et al. 1 and this material appears to be the
Sintering of SiC
next most effective additive after B. The technique of adding Al

and hot-pressing was developed by Norton Inc. 22 and Tanaka et
al.,23 but it was a West German group24 which first succeeded in
pressureless sintering with the addition of AI-C.
Like B-C system sintering additives, those of the Al-C
system can be considered to act on the grain boundaries, but Al
must be added in somewhat greater quantities than B-C system
additives because Al forms a solid solution more than Band
because the A4SiC4 and A14C3 produced during the sintering
process are easily volatilized. Care is also required since sintered
bodies produced by the addition of Al-C system additives easily
lose their strength at high temperatures. 23 Generally speaking,
there is less grain growth with Al system additives than with B
system additives.
10.4.2.2 Al20 3 and AlN System Sintering Additive
Just as with sintering by the addition of Si3N4 oxides, this sytem

involves liquid-phase sintering. 25 ,26 Most of the A120 3 additive
remains on the grain boundaries and the triple points, and there
is a deterioration of high-temperature strength despite the small
mean particle size of the sintered body. The technique of
pressureless sintering by the addition of A120 3 was developed
and commercialized by Asahi Glass of Japan. These sintered
bodies are characterized by control over particle aspect ratio and
a strong correlation between aspect ratio and strength. 27
Naturally, the larger the aspect ratio the higher the strength.
With hot-pressing, SiC powders can be sintered by the addition
of AlN. 28,29 Although the sintering mechanism is not yet fully
understood, ~olid solutions are present in a wide range between
SiC and AlN.3Il--32 Examples of SiC solid solutions are rare, and
they are of interest as ceramic alloys. 32
Much research has also been conducted on systems combining
Al20 3 and other oxides, and pressureless sintering is possible
with the addition of substances like A120 3- Y20333 and Al20 r
Y203-MgO. Even when using an A120 3 system sintering
additive, the oxide is easily volatilized at high temperatures
because sintering is conducted in a reducing atmosphere. In
order to reduce this volatilization, a certain degree of control
over atmosphere and sintering temperature is required.
Hidehiko Tanaka
10.4.2.3 AI-B-C System Sintering Additives

AI-B-C system additives are extremely effective as sintering
aids. Methods of addition include use of an AIB2 compound,34
addition of AI and B from separate elements,23.35.36 and the
formation of an Al solid solution in the SiC powder. 37 In any
case, only a small amount of additive is required for
densification.
Table 10.123 shows strengths of SiC sintered by the addition of
Al and B in the form of A4~ and B metal, respectively. It can
be seen that with this doping system, B content can be reduced
to extremely smail levels. As Al content increases, however,
inter-granular fracture dominates and high-temperature strength
is compromised. Figure 10.1338 shows phase relationships for the
system SiC-AI4C3-B4C at 1800°C. The grain boundary phase of
the sintered body formed by common addition of AI-B-C can be
surmised from the relationships in the figure. AI4SiC4 and
Al8B4~ are present as stable compounds, the latter being a
liquid phase at 18000C. When a liquid phase is formed at high
temperatures sintering is facilitated, but this can also have a
deleterious effect on high-temperature strength.
10.4.2.4 Pressureless Sintering of SiC Powder with Al
Solution37
In order to prevent the reduction of high-temperature strength in
sintered bodies produced by the addition of AI-B-C, the author
and others synthesized a fJ-SiC powder with an Al solid solution
and performed pressureless sintering using B. By forming an Al
solid solution in the particles, it is possible to prevent large
precipitation of excess Al and the formation of a liquid phase on
the grain boundaries. The AI increases the lattice diffusion
constant of the SiC particles and contributes to sintering-induced
densification. Furthermore, it seldom amplifies grain growth,
which is proportional to the rate of grain boundary diffusion.
Consequently, sintered bodies with small mean particle sizes can
be produced.
In an experiment, powders differing only in Al concentration
(AI: 0·018-0·49 wt%; Si02: 0·3-0·4 wt%; Fe:0·03-0·05 wt%;
mean particle size: 0·24-0·28 J.UIl) were synthesized and then
pressureless-sintered according to the method described in this
section. The powders were fJ (3C) phase varieties containing
Table 10.1
Strength of Hot-Pressed SiC with AI, Band C23
Sample Starting Additives (wt%) Atomic Density Bending strength MN/m z (Fracture mode)·
No. Powder weight (g/cm J)
C AI"CJ B ratio Room temperature 13OO"C l5OO"C
AI:B
1 B1 0·5 0 0·2 0:100 3·11 452(TG) 565(TG) 642(TG)

2 B1 0·5 0·24 0·15 33:67 3·10 550(TG) 439(TG) 589(TG,IG)
3 B1 0·5 0·49 0·10 60:40 3·12 457(TG) 497(TG) 538(TG> IG)
4 B1 0·5 0·54 0·08 67:33 3·08 498(TG,IG) 499(TG,IG) 451(TG,IG)
5 B1 0·5 1·07 0 100:0 3·09 469(IG) 555(IG) 363(IG)
6 B2 0·8 3·19 576(TG) 583 (TG) 570(TG>IG)
7 B3 0·8 3·21 711(IG) 530(IG) 301(IG)
B1: Pure ~-SiC powder.

B2 and B3: SiC powders which contain 0·69 and 1·11 wt% AI, respectively.
* TG: Transgranular fracture, IG: Intergranular fracture.
~
...
Hidehiko Tanaka
Fig. 10.13. Phase 4SiC

relationships for
the SiC-B4C-
A14~ system at
18OO"C. The hori-
zontalline is the
region in which a
liquid phase was
formed at
18OO"C. 38
AI4C3 L-_ _ _-=~~=~~--~--

13 14 15
__ -~ B4C
AI6B4C7
trace amounts of the 2H phase. Sintering results are shown in

Figs 10.14-10.16. 37
Figure 10.14 is a comparison of the sinterability of two
powders, one containing 0·018 wt% AI as an impurity and one
containing 0·49 wt% Al as a solid solution. Sintered density is
Fig. 10.14. 3.5

Sinterability of a
SiC powder
-T.D.
containing
.., , .JT'
0·49 wt% Al as a
u 3.0
~ ,,
solid solution (e)
, " ""
.....
and a high-purity I!)
powder (0).0-
-
>-
" '"
, ,,6 "
I-
0·29wt% Band ( I)
2·0 wt% C were z:
'" "
I.JJ
added, with the t=I 2.5
• 0.49 WT% Al
,,
j;)'
density shown
being the value o 0.018 WT% Al
attained after
sintering at
2100°C for 1 h. 37 2.00~-------~~1--------~0~------~
O. .2
BORON ADDITION (WT%)
232
Sintering of SiC
3.5 r-------------------, Fig.IO.lS.

Sinterability of a
SiC powder con-
T.D. taining, 0·018-
~
0·49 wt% Al as a
1:
u
3.0 solid solution.
....... 0·1 wt%Band
c.!I
2·0 wt% C were
added,withthe
density shown
0.1 WT% B being the value
2.0 WT% C attained after
sintering at
2100"C for 1 h. 37
2. 0 ~_-'- _ ___L_ _..L..._....L_ _ _ _ ' L . . _ _........._ ......
o 0.2 0.4 0.6

AL CONTENT (wT%l
shown as a function of B content. The powder in which an AI

solution had been formed reached almost theoretical density with
only 0·1 wt% of B, giving it remarkably better sinterability than
the AI-free powder. The effect of AI begins to be exhibited at a
content of approximately 0·3 wt% (Figure 10.15). Figure 10.16
shows the structures of the resulting sintered bodies, (a) being
produced from a powder containing 0·29 wt% AI as a solution
and (b) from a high-purity powder containing only 0·018 wt% AI.
The former exhibits a finer structure than the latter.
In this way, the formation of an Al solution supplements the
additive effect of B and reduces particle size. Al seems to
accelerate the solid-state diffusion of SiC particles. It was also
found that some of it precipitates on the grain boundaries. 39
The properties of SiC sintered bodies containing Al are
somewhat different from those of bodies produced using B-C
system sintering additives. In particular, the high-temperature
creep rate is much higher than for those not containing AI. 40 This
is because diffusion of the material is accelerated by the AI. The
blunting of crack tips has also been observed in materials of this
system. 40
Hidehiko Tanaka
Fig. 10.16.
Structure of SiC
sintered bodies.
( a) Powder con-
taining O· 29 wt%
AI as a solid solu-
tion; (b) powder
containing
0·018 wt% AI.
Sintering was per-
formed at 2100"C
for 1 h after ad-
ding 0·25 wt% B
and 2 wt% C. 37
10.4.3 Sintering of SiC Powders Containing other

Sintering Additives
No sintering additives for the pressureless sintering of SiC have
been discovered outside the B-C system, the system of Al and
AI-containing compounds, and mixed systems thereof. In the
case of hot-pressing, Alliegro et al. 1 have pointed out that several
Sintering of SiC
metals are effective as sintering additives. In addition, BeO,41

BaO-C,42 and rare earth metal oxide-~3 allow densification of
SiC powders by hot-pressing. These additives have a smaller
solubility in SiC than AI or B, and materials with high thermal
conductivity can be obtained. In particular, sintered bodies
produced by the addition of BeO have high electrical resistance
and are used as IC substrates.
10.5 SUMMARY
SiC sintering and sintering aids were reviewed with an emphasis

on experimental results from the B-C and Al-B-C systems.
First, SiC sintering theory was explained based on the free
energy theory of mass transport. Next, sintering methods and
technologies using a variety of sintering aids were discussed. A
summary follows:
SiC sintering theorf shows that:
(1) Excess free energy present on the powder surfaces and
interfaces directly drives sintering-related mass transport.
(2) When there is little relaxation of surface energy by the
formation of interfaces, complete densification of the
powder cannot be achieved. On the other hand, it was
made clear from consideration of high-purity SiC crystal
interfaces that:
(a) there is extremely little relaxation of surface energy by the
formation of SiC crystal interfaces;
(b) SiC is fundamentally a non-sinterable material; and
(c) sintering additive is required for the densification.
Next, it was explained from the results of sintering SiC
powders using B-C system additives that:
(6) B and C sintering additive reduce Eb on the grain
boundaries;
(7) B is needed only in very small quantities; and
(8) An oxygen-free sintering atmosphere at temperatures
below 1500°C, gradual increase of the temperature are
important.
Finally, in the sintering of SiC powders using Al-B-C system
sintering aids,
235
Hidehiko Tanaka
(9) The formation of an Al solid solution in the SiC particles

will improve sinterability.
REFERENCES
1. Alliegro, R. A., Coffin, L. B. & Tinklepaugh, J. R., Pressure-
sintered silicon carbide. J. Am. Ceram. Soc., 39(11) (1956), 386-9.
2. Prochazka, S., The role of boron and carbon in the sintering of
silicon carbide. In Special Ceramics, Vol. 6, British Ceramic
Research Association, 1975, pp. 171-81.
3. Inomata, Y., Free energy theory of the initial sintering of solids. J.
Ceram. Soc. Japan, 90(9) (1982), 527-31.
4. Inomata, Y., Free energy theory of material transport for sintering
and diffusional creep. In Proc. Int. Symp. on Ceramic Components
for Engine, ed. S. Somiya et al. KTK Scientific Publishers, Tokyo,
1984, pp. 253-61.
5. Inomata, Y., Reconstruction of the theory of sintering. Ceramics
Japan, 22(6) (1987), 467-72.
6. Schober, T. & Balluffi, R. W., Quantitative observation of misfit
dislocation arrays in low and high angle twist grain boundaries. Phil.
Mag., 21 (1973), 109-23.
7. Kimura, S., Yasuda, E., Sakai, M., Kim, H. J. & Moriyoshi, Y.,
Grain boundaries of MgO bicrystals. J. Ceram. Soc. Japan, 94(8)
(1986), 795-800.
8. Fujimoto, M., High resolution transmission electron microscopy of
a coincidence site boundary in BaTi03 ceramics. Jap. J. Appl.
Phys., 26(8) (1987), L1344-47.
9. Inoue, Z., Uemura, Y. & Inomata, Y., A SiC-bicrystal junction on
the (0001) plane. J. Mater. Sci., 16 (1981), 2297-302.
10. Ichinose, H., Inomata, Y. & Ishida, Y., HREM analysis of SiC
grain boundary structure. J. Ceram. Soc. Japan, 94(4) (1987),
415-18.
11. Uemura, Y., Inomata, Y. & Ichinose, H., Boundary structures of
SiC bicrystal. J. Ceram. Soc. Japan, 95(9) (1987), 841-4.
12. Uemura, Y., Inomata, Y. & Inoue, Z., A grain boundary of a-SiC
bicrystals. J. Mater. Sci., 16 (1981), 2333-5.
13. Hannick, R. H. J., Bando, Y., Tanaka, H. & Inomata, Y.,
Microstructural investigation and indentation response of
pressureless-sintered a and fJ-SiC. J. Mater. Sci., 23 (1988),
2093-101.
14. Suzuki, H. & Hase, T., Boron transport and change of lattice
parameter during sintering of fJ-SiC. J. Am. Ceram. Soc., 63(5-6)
(1980), 349-50.
15. Inomata, Y., In Development of sintering additives in SiC ceramics.
Report of 124 Committee of Japan Society for Promotion of
Science, No. 81, 1987.
Sintering of SiC
16. Hase, T., Suzuki, H. & Ueda, H., High temperature strength of
pressureless-sintered SiC. J. Ceram. Soc. Japan, 87(10) (1979),
522-8.
17. Tanaka, H., Inomata, Y., Tsukuda, K. & Hagimura, A., Normal
sintering of fJ-SiC powder. J. Ceram. Soc. Japan, 92(8) (1984),
461-5.
18. Prochazka, S., Japanese Patent Gazette Shou 57-32035, 1982.
19. Tanaka, H., Inomata, Y. & Tsukuda, K., Japanese Patent Gazette
Shou 61-3303, 1986, U.S. Patent 4579704.
20. Orange, G., Tanaka, H. & Fantozzi, G., Fracture toughness of
pressureless sintered silicon carbide: a comparison of K 1c measure-
ment methods. Ceramics International, 13 (1987), 159-65.
21. Suzuki, K., Relation between microstructure and fracture toughness
of ceramics. Ceramics Japan 21(7) (1986), 590-7.
22. Japanese Patent Application 49-7311, 1974.
SiC by the addition of Al and B. J. Ceram. Soc. Japan, 88(9)
(1980), 570-4.
24. BOcker, W., Landfermann, H. & Hausner, H., Sintering of alpha
silicon carbide with additions of aluminum. Powder Met. Int., 11(2)
(1979), 83-5.
25. Ashcroft, W., The tensile and bend strengths of silicon nitride and
hot-pressed silicon carbide. In Special Ceramics 6, ed. P. Popper et
al. The British Ceramic Research Association, 1975, pp. 245-60.
26. Lange, F. F., Hot-pressing behaviour of silicon carbide powders
with additions of aluminium oxide. J. Mater. Sci., 10 (1975),
314-20.
27. Suzuki, K. & Furukawa, K., HIP treatment of SiC. In FC Report,
Japan Fine Ceramics Assocation, 3(4) (1984), 15-20.
28. Tanaka, H. & Yamashita, Y., Japanese Patent Gazette Shou
52-140516, 1977.
29. Ruh, R., Zangvil, A. & Barlowe, J., Elastic properties of SiC, AIN
and their solid solutions and particulate composites. Am. Ceram.
Soc. Bull., 64(10) (1985), 1368-73.
30. Cutler, I. B., Miller, P. D., Rafaniello, W., Park, H. K.,
Thompson, D. P. & Jack, K. H., New materials in the Si-C-AI-
O-N and related systems. Nature, 275 (1978), 434-5.
31. Shimada, M., Sakai, K. & Koizumi, M., Fabrication and charac-
terization of AIN-SiC ceramics. In Proc. Int. Symp. on Ceramic
Components for Engines. KTK Scientific Publishers, Tokyo, 1984,
pp.466-72.
32. Patience, M. M., England, R. J., Thompson, D. P. & Jack, K. H.,
Ceramic alloys of silicon carbide with aluminium nitride and
nitrogen. In Proc. Int. Symp. on Ceramic Components for Engines.
KTK Scientific Publishers, Tokyo, 1984, pp. 473-9.
33. Omori, M. & Takei, H., Pressureless sintering of SiC. J. Am.
Ceram. Soc., 65(6) (1982), C-92.
34. Coppola, J. A. et al. Japanese Patent Application Shou 53-121810,
1978.
237
Hidehiko Tanaka
35. Stutz, D. H., Prochazka, S. & Lorenz, J., Sintering and microstruc-
ture formation of ~-silicon carbide. J. Am. Ceram. Soc., 68(9)
(1985), 479-82.
36. Shinozaki, S., Williams, R. M., Juterbock, B. N., Donlon, W. T.,
Hangas, J. & Peters, C. R., Microstructure developments in
pressureless sintered ~-SiC materials with AI, Band C additions.
Am. Ceram. Soc. Bull., 64(10) (1985), 1389-93.
37. Tanaka, H., Inomata, Y., Hara, K. & Hasegawa, H., Normal
sintering of Al-doped ~-SiC. J. Mater. Sci. Leuers, 4 (1985),
315-17.
38. Inomata, Y., Tanaka, H., Inoue, Z. & Kawabata, H., Phase
relation in SiC-AL.~-B4C system at 1800"C. J. Ceram. Soc. Japan,
88(6) (1980), 353-5.
39. Tanaka, H., Investigation on the sintering of SiC. Report of
National Institute for Research in Inorganic Materials No. 52, 1987,
pp.24-9.
40. Tsunoda, K., Horibe, S. & Maruyama, N., Investigation on high
temperature fatigue. Report on Investigation on Controlling Surface
and Grain Boundary for Development of High Performance
Materials, Research and Development Bureau, Science and Tech-
nology Agency of Japan, 1986.
41. Ura, M. & Asai, 0., Development and application of electrical
insulating SiC sintered material. FC Report, Japan Fine Ceramic
Association, 1(4) (1983) 5-13.
42. Sakai, T. & Hirosaki, N., Hot-pressing of SiC with additions of BaO
and C. J. Am. Ceram. Soc., 68(8) (1985), C191-93.
43. Sakai, T. & Aikawa, T., Influence of rare earths on the sintering of
SiC. Abstracts of 24th Symposium on Basic Science of Ceramics,
the Ceramic Society of Japan, 1986, p. 5.
11 Joining of SiC
Ceramics
TAKAYOSHI ISEKI
ABSTRAC'f
First, in order to understand the joining of SiC, the wettability of

various molten metals to SiC and reactions between various metals
and SiC are reviewed. Second, the state of the art of joining of SiC
ceramics is described using the following classification: inorganic
adhesives, metallizing, active metal brazing, brazing with frit or
glass, solid-state bonding, and reaction bonding. Furthermore,
several methods for the reduction of thermal expansion mismatch
in joining ceramic to metal are described: using an inert layer
having an intermediate thermal expansion coefficient, using a soft
or ductile insert, balancing of thermal stress, and the effect of
phase transformation.
11.1 INTRODUcrION
Together with Si3N4 , SiC ceramics are viewed as promlsmg

structural ceramics because of their excellent heat resistance and
mechanical properties. In order to make use of SiC ceramics as
structural materials, however, adequate processing technologies
must first be developed. In particular, joining techniques are
required for the fabrication of large pieces or pieces with
complicated shapes and for the combined use of different
materials. Conventionally, ceramic joining technology was lim-
ited to joining the edges of SiC resistance heating elements or
using mortar to join refractory bricks or saggers for ceramic
firing, but the promise shown by fine ceramics has led to
extensive research on SiC joining.
Takayoshi Iseki
Techniques for the joining of ceramics, and oxide ceramics in

particular, can be grouped according to the following clas-
sification: mechanical fitting, organic adhesive, inorganic ad-
hesive, metallizing, active metal brazing, brazing with frit,
solid-state bonding, reaction bonding, and fusion welding. 1
Although there are some variations depending on the material,
virtually all of these can be applied in principle to SiC. Because
SiC begins sublimation at temperatures of 20000C and above,
however, fusion welding is difficult unless certain special
conditions are satisfied. Most of the methods used with Si3N4 ,
which has become something of a rival to SiC, will serve as
reference in examination of SiC joining methods. 2
One point which must be taken into consideration in the
joining of SiC is the fact that differences in SiC ceramic
fabrication methods will result in differing minor components,
which may affect joining. The variety of these ceramics is
wide-ranging, from comparatively high-purity substances such as
Fig. 11.1. Factors

influencing joined
bodies.
Joining of SiC Ceramics
CVD (chemical vapor deposition) and recrystallized SiC to

pressureless-sintered and hot-pressed SiC, which may contain
1-2% of B, C, AI, BeO, etc., as sintering additives. Therefore,
knowledge of the fabrication method of the SiC to be joined and
its composition is important.
Factors influencing the joined body are as shown in Fig. 11.1.
This chapter will offer an overview of the joining of SiC sintered
bodies, i.e. SiC ceramics through a discussion of the wettability
and reactions which govern bonding, methods of reducing
thermal stress owing to expansion mismatch in the joining of
metal and SiC, and actual examples of joining.
11.2 WETIABILITY AND REACI10N
11.2.1 Wettability
Wettability is the first problem to be encountered during use of
an organic adhesive. Wettability of bodies by adhesive is
commonly evaluated by the angle of contact, shown in Fig. 11.2.
The contact angle and the energy of each interface are related by
Young's formula:
Ys = YSL + YL cos 8
There is also the Young-Dupre formula:
WA = ydl + cos 8)
Here, WA is adhesive work, indicating the strength of the bond.
Numerous reservations have been expressed concerning contact
angle: the fact that the solid surface is not smooth and is not
single phase, the question of whether a tangent can be drawn to
the tip of a droplet, the presence or absence of air, the question
of whether the angle is stable, etc. 3 Furthermore, during the
FIg. 11.2.
Contact angle and
interface energy.
241
Takayoshi Iseki
Jommg of ceramics, the brazing filler used after joining is

normally a solid, preventing fulfillment of the assumption that
diffusion layers and reaction products are not formed on the
interface. Finally, current measurements of joining strength
measure not so much joining strength itself as the fracture
strength of the joining system, raising doubts as to whether
adhesive work is being accurately measured. On the other hand,
joining does not necessarily require wettability. An extreme
example is solid-phase joining, which completely ignores the
liquid phase. It is said that even when brazing filler, or another
liquid phase is involved, the filler does not require a great deal of
wettability. Nicholas et al. 4 have reported that a contact angle of
less than approximately 100° is sufficient. During contact angle
measurement using the sessile drop method, however, poor
wettability results in round shape, and vibrations cause the
droplet to fall from the specimen table. In other words, the filler
will escape from between the bodies to be joined during joining.
In any case, one guideline for when filler is involved is that
joining is possible if the contact angle is less than 90°.
The wettability of various metal melts with respect to SiC is
summarized in Table 11.1. It should be remembered that the
contact angle will vary depending upon sample type, measured
temperature, atmosphere, surface conditions, and elapsed time
at the measured temperature.
11.2.2 Reaction
The joining mechanisms of ceramics can be broadly divided into
physical bonding and chemical bonding. Chemical bonding
techniques can be further divided into those which form a solid
solution and those which form a reaction product. With chemical
bonding, the diffusion layer or reaction layer is extremely thin, to
the extent that in some cases it may remain undetected. Since
ceramics have grain boundaries, a reaction with the grain
boundary phase may also occur. Pries & Ruge 1S formed an
oxide-free adherent surface on the surface of SiC samples under
an ultra-high vacuum of 1O-9-10- 1o mbar (1O- 7 _1O- 8 Pa) and
reported that it was possible to join them by sandwiching Mg or
AI metal foil between and applying pressure for 20 min at room
temperature. This is an extreme example, and the achieved
joining strength was not indicated. When a reaction product is
242
Table 11.1
Wettability of SiC by Various Metal Melts
Metlll Type 01 Atmos- Temp- Co"tm:t ReI· Metal Type 01 Atmos- Temp- Co"uu:t ReI·
SIC" phere _true angle (? SIC" phere _true angle r)
rc) rc)
AI RB In vacuum 900 145 5 Ge SC In vacuum 1000 135 11
RB Invacuum 1100 65 5 SC In vacuum 1250 105 11
PLS In vacuum 900 135 5 RB In vacuum 1000 95 11
PLS In vacuum 1100 60 5 RB Invacuum 1250 50 11
SC In vacuum 950 102 6 Ag SC In vacuum 1100 128 10
AI-l% Co SC In vacuum 950 120 6 Ag-28% Cu PLS In vacuum 950 135 12
AI-5% Mn SC In vacuum 950 78 6 (72Ag-28Cu) RB In vacuum 950 110 12
AI-2% Ni SC Invacuum 1000 126 6 -2%Ti PLS In vacuum 950 25 12
AI-5% Ce SC In vacuum 950 151 6 In SC In vacuum 800 130 10
AI-6% La SC In vacuum 950 124 6 Sn SC In vacuum 1050 135 10
Si RB In vacuum 1480 30 7 Au SC In vacuum 1150 138 10
HP In vacuum 1480 41 7 Pb CVD H2 600 130 13
Si-l% B RB In vacuum 1480 26 7 TiAl3 SC In vacuum 1450 <40 14
HP In vacuum 1480 40 7 TiSi2 SC In vacuum 1500 <40 14
Si-l0% Fe RB In vacuum 1480 20 7 TiNi SC In vacuum 1500 82 14
HP Invacuum 1480 37 7 TiNi3 SC In vacuum 1500 50 14
Si-l0% Cu RB In vacuum 1480 28 7 TiCr2 SC In vacuum 1500 <40 14
HP In vacuum 1480 45 7 Cr3Si2 SC In vacuum 1460 <40 14
Mn SC Ar 1350 72 8 Fe3AIs SC Invacuum 1300 58 14
Fe SC Ar 1600 82 8 FeSi SC In vacuum 1420 <40 14
Co SC Ar 1550 64 8 F~Sis SC In vacuum 1350 <40 14
Ni SC Ar 1500 45 8 CoSi SC In vacuum 1500 <40 14
Cu SC Ar 1130 136 8 Ni~l SC In vacuum 1550 <40 14
Cu-l0% Ti SC In vacuum 1120 60 9 Ni2Si SC Invacuum 1320 90 14
Cu-18%Sn-l0% Ti SC In vacuum 900 40 9 713LC" SC In vacuum 1350 <40 14
Ga SC Invacuum 800 118 10
"RB, reaction bonding; PLS, pressureless sintering; HP, hot-pressing; SC, single crystal; CVD, chemical vapor deposition.
bANi-base alloy containing Cr, AI and Mo.
~I
Takayoshi Iseki
formed, the formation rate and physical properties of the product

such as thermal expansion coefficient, elastic modulus and
strength determine the quality of the joined body. Depending
upon the operating environment, the chemical properties of the
reaction product may also be important.
Concerning the reaction of SiC and metal, SiC-tiber-reinforced
metal-matrix composite materials have been studied in detail, and
summaries are provided in the Super-Melting Elements and
Compound.s 16 and the Gmelin Handbook. 17 The reaction of SiC
and metal M can be categorized as follows:
SiC + M - MxSiy + C (1)
SiC + M - MxSiy + MmCn (2)
SiC+M-MmCn +Si (3)
Which of these reactions is to occur can be determined using the
Gibbs' free energy of formation /1G, shown in Figs 11.3 and
11.4, as a guideline. When broken down by rate, the smaller the
Fig. 11.3. Free

energy of forma-
tion for various
carbides. 18 E
o
ni
u
'0
.,€
~
c
o
.~
E
...
...o
'0
>. -100
~
~
t
.t -150
-200
~--~----~----~--~
o
Temperature (K)
244
Temperature (K) Fig. 11.4. (a)

298 00 1000 1500 2000 Mg 2Si Free energy of
0
formation for
MoSi2 group II and IV
-50
ZrSi 2
metal silicides; (b)
LaSi
.. free energy of
-100 CaSi2 Th~TISI formation for
ZrSi group V and VI
CaSi
-150 metal silicides; (c)
-200
- TisSi3 Zr2Si
-=Zr5Si3 free energy of
formation for
group VII and
VIII metal
Temperature (K) silicides. 19
298500 1000 1500 2000
0
E
WSi2
~ ~N~Si2
U
-50 C S' TaSI2
=
0 r 12
-
E
-,
~
T~i
c
0 MO]Si
:;; -100
III
E Mass i3 C S'
L. ~r31
....0
....0 Ta4,5Si
-150 VSi2
>.
en
L.
II
c
II
II
II -200
J: Nb!5Si3
Temperature (K)
298500 1000 1500 2000
0
-50
-100
-150
Takayoshi Iseki
value of I1G the easier the formation. A study of much of the

available data shows correspondence of the following elements to
the above reactions:
(1) Fe, Ni, Cu, Pd
(2) Ti, Cr, Mo, Zr, Mo, Ta, W
(3) AI
In addition, ternary compounds such as Ti3Si~ (in the case of
Ti) and MOsShC (in the case of Mo) are possible. The reason for
differing reaction products in the reports is thought to be
different stable products, caused by different reaction tempera-
tures, together with the fact that in reactions (1)-(3) the C and Si
formed undergo a secondary reaction with the excess M. When
considered from the groups of the periodic table, Cr may be an
example of the latter. This could be understood if phase
diagrams were available for the Si-C-M ternary system, but very
few have been prepared as yet.
Thus far discussion of reaction rate has been excluded. In
order to know the reaction rate of various materials a table
drawn up in the course of research on composite materials and
summarizing the reactions of Si fiber and metal is cited in Table
11.2.20 It can be seen that Ni, Co and Ti react easily. With Ti, a
1-2!AJ1l reaction phase is formed upon heating at 900°C for 1 h,
and the reaction is diffusion-controlled. According to Nogi et
al.,21 the reaction rate of Cr and Ti is slow enough to be ignored
when reaction-bonded SiC and a metal were heated at 950°C for
Table 11.2 Mellli HtItIIi"6 ItlmptlrtlIIutI ("C)

Reactivity of SiC
Fibers and 458 5JIJ 6ZtJ 65tI 150 811(1 II5tJ 9tItI !J5tJ 1_ u. utili
Various Pure
Metals20 AI 0 0 0
Ag 0 0 0 0 0
Cu 0 0 0 0 0
Ni 0 0 0 x x
Co 0 0 I::. I::. x
Fe 0 0 0 0 I::.
n I::. I::. I::. I::. I::.
Cr 0 0 I::. I::.
Mo 0 0 0 0 0
Heating for 1 h in ~ (in vacuo for Ti only).
O. no reaction was observed at x 1000 mag.; 1::.. reaction was observed at x 1000 mag;
x. fibers disappeared.
100 h in an inert gas atmosphere. With Co and Ni, on the other

hand, reaction layers of thickness 75 J.Ull and 300 J.Ull, respec-
tively, were formed. Yamada et al. 22 have reported that when
pressureless-sintered SiC and Ni were joined, graphite was
formed parallel to the joining surface, and the resulting joined
body had poor strength. Since reaction-bonded SiC contains free
Si, attention must be paid not only to the reaction of SiC and
metal but also to the reaction of Si and metal.
SiC joined with Ai is one example of a case in which a
reaction product influences the quality of the joined body. 23 By
sandwiching metal Ai foil between two blocks of pressureless-
sintered SiC or reaction-bonded SiC, it is possible to join the two
blocks by heating at l000°C in a vacuum. Here, the pressureless-
sintered SiC produces Ai4C3 as a reaction product, while the
reaction-bonded SiC produces virtually no A~C3' as shown in the
left- and right-hand sides, respectively, of Fig. 11.5. Bending
strength measurements for the two joined bodies after immersion
in boiling water for a fixed period of time are as shown in Fig.
11.6. With the pressureless-sintered SiC, which formed A~C3 on
the interface, the joining portion failed in approximately 1 week;
with the reaction-bonded SiC, which formed little or no A~C3'
no reduction in strength was observed for at least 12 days. These
results are due to the fact that the Al4C3 reaction product reacts
with moisture to decompose; the same results were obtained
when the pieces were exposed to the air in addition to being
immersed in boiling water. The joined body of pressureless-
sintered SiC could easily be broken by hand 20 months after
joining, while the joined body of reaction-bonded SiC remains
unbreakable 4·5 years after its formation. This phenomenon
should be taken into consideration not only in the case of joined
Fig. u.s.
Schematic dia-
gram of SiC/AI
interface (PLS,
pressureless sin-
tering; RB, reac-
tion bonding). 23
247
Takayoshi Iseki
Fig. 11.6.
Bending strength 300 Pressureless-sintered SiC 30
of SiC joined :.
body using Al 5 0
0
(measurement r.
....m
after a fixed period 8 ~
ij '"E
.......
200
-
of immersion in 20
E
boiling water). 23 1ft
m
m
.=
1:J
I:
~
GI
!Xl 100 10
6
Reaction-bonded SiC
o 2 4 6 10 12
Time(days)
bodies but also when fabricating fiber-reinforced AI-base com-

posite materials.
11.3 JOINING MEmODS
One possible overview of ceramic joining is shown in Fig. 11.7.

Joining methods were classified as shown in the lower left portion
of Fig. 11.7. At the end of this section actual examples of SiC
joining will be brought together in a table, but for now each
method will be briefly introduced. Mechanical fitting and organic
adhesives will be omitted from the discussion.
11.3.1 Inorgaaic Adhesives

There are various systems, including alkali silicate, silica sol and
phosphate. Hardening at low temperature allows easy joining,
but strength and airtightness suffer. Although perhaps not
appropriate for this category, there is also the example of joining
by inserting polyborosiloxane or another Si-containing polymer
between SiC sintered bodies and heating to 1500"C. 24
r.~
...,~
r....
...,( ~
c,r.
(,... ~ C01>, 0".0~Ol.
t:,,~ C'o 0 1,0. »O~, O,p;.. r.
.. ",,, $0' 'Ii $c.,
"I"
~I>, c"C'1 "'0c"1)0''c,,/,'01)01) (,''I>, .,.....~C'C!'"
O"»~ c,,"C!' r. "'0"", 0" »c"",~ ,Oc",p~
Oc,,$ O'C!'...C!' ~I,O !:V'I)I"-. I)C!'$$
$1,. C'l, I)) . uO'c., '$~
c"C'Ic":'l)t,,o C'z',;.,~ ~.oC!')
C!') 0'c"C' ~, GI
1"01), .t::
.... >.
.... '0
00
c.o
, 0'0
~I'.;; ~
fII,-
~,2,
'.q,;.l' ' ~
,.~ ~~tl)
C!'t-I>, I!'$$
~I
C'O"" $~OC'+
0$'0 "I!'
1\10 I) "I!o ;s',,st.
I)O'I!' ;s",s ~I)C'
$1" 1~1) C!'
c.,C'z' ' C'I!'
'''I!'
ll!'$l'
'I),p
~
S'
J:'
~
t'l
Fig. 11.7. Joining conditions and evaluation of the joined body, r.;
a~;!
~ Q'
Takayoshi Iseki
11.3.2 MetaUizing
Ceramics cannot be joined by solder or silver brazing filler metal
because of their poor wettability. Therefore, a metal film is first
formed on the ceramic surface, and this metal is then brazed.
This technique, referred to as the Mo-Mn or high-melting-point
metal method, is often used with Ah03 ceramics. Ikegami et al.2S
have used a two-stage firing technique to metallize Mo onto
hot-pressed SiC. In dry air the sintering of Mo proceeds
significantly at 12000C, the temperature at which the reaction of
SiC and Mo begins, and the Mo film is warped. Since the
sintering of Mo is inhibited by the presence of water vapor, SiC
and Mo are first reacted at 1450"C in a wet N2-H2 atmosphere
and then sintered at 1350°C in a dry atmosphere. The Mo is
plated with Nil Au, and an electrical lead is soldered thereon.
Ikegami et al. have also succeeded in metallizing a thin film of
Ag-Pd paste onto a SiC substrate and a thick film of Au paste
onto the same. These techniques could be used with substrates
for LSI packages and hybrid ICs. The Ag-Pd and Au pastes
consisted of a mixture of a metal powder, a low-melting-point
oxide, and an organic binder. Approximate firing temperature
was 600-9OO"C.
11.3.3 Active Metal Bnzing

Both metallizing and active metal brazing are a type of brazing.
The former, however, is a multistage process in which brazing is
performed after metallizing or after metallizing and plating,
while the latter involves only a one-time heating operation. For
the purpose of joining with A120 3, any metal which bonds easily
with 0 can be considered an active metal, and for SiC the
elements shown in Fig. 11.3 that are likely to form carbides, i.e.
Zr, Hf, Ti and Nb, would be likely candidates. These active
metals can be used alone or added in small concentrations to the
brazing filler metal. Pressureless-sintered SiC and silver
brazing filler metal have poor wettability, but this can be
improved by the addition of 1·5% Ti. 12 Joining was made
possible by inserting Ag70oSCu27oSTi200 foil between the two blocks
and heating at 850-950°C in a vacuum.26 Here, it was confirmed
that the active metal Ti concentrates on the SiC surface to form
TiC and TisSi3 (Fig. 11.8).
Fig. u.s.
Structure near the
joining interface
and elemental
concentration dis-
tribution (joining
conditions: 950°C,
30min).26
Si
Ti
CU
I 1 I
o 1 2 3 4 5ILm
11.3.4 Brazing with Frit

In this technique, which might be referred to as ceramic as
opposed to filler metals, the two bodies are joined by molten
glass. Lay et al. 27 have reported that, when joining reaction-
bonded SiC (REFEL) and a mullite ceramic, coating of the SiC
surface with the clay mineral kaolin and heating to 1350°C in
advance will improve the wettability of frit during the joining
process to follow and further will inhibit the formation of
bubbles. Materials such as PbO 19, B20 3 19, Al20 3 5, and Si02
57% are used as frit, and joining is conducted at temperatures of
approximately l000°C.
Ebata et al.28 reported that an adhesive consisting of kaolin
doped with CaF2 was applied to the surfaces to be joined, drying
was performed, and the SiC bodies were joined by heating at
1500°C in air. F contained in the CaF2 chemically reacts with the
251
Takayoshi Iseki
SiC during heating, increasing SiC surface roughness and

oxidizing a portion thereof. As a result, wettability with the
adhesive is improved, and bonding strength is increased.
11.3.5 SoUd-state Joining

Unlike the previous four techniques, which performed joining via
a solution or melt, this method uses pressure at high temperature
to join the two bodies in the solid state. As described in Section
11.2.2, joining is sometimes possible at room temperature given
an ultra-high vacuum and a clean surface. Ordinarily there are
three possible situations: one in which hot-pressing alone is
sufficient to join the bodies; one in which a material of the same
substance as the bodies to be joined is placed between; and one
in which a material of a different substance is placed between the
bodies to be joined. Iseki et al.29 have reported using a mixed
powder consisting of a SiC fine powder to which AI, Band C
have been added in ratios of 6%, 1% and 1%, respectively, and
hot-pressing the hot-pressed or pressureless-sintered SiC bodies
at the low temperature of 16SO"C under a pressure of SO MPa,
with the resulting joined body having a strength approximating
that of the original SiC sintered bodies.
11.3.6 Reaction Bonding

This method joins two ceramic bodies by heating to high
temperature a powder placed on the joining interface and
thereby causing a reaction which yields a dense sintered body.
Iseki et al. 3O have reported obtaining a strong joined body by
kneading a mixed powder (with C and SiC) into a paste using an
organic binder, applying this to the joining interface and
hardening it, and placing it in contact with Si at 14S0°C in a
vacuum, thereby causing the reaction Si + C-+ SiC and trans-
forming the C into SiC.
Thus far, several examples of SiC joining techniques have been
discussed according to the classification of joining methods for
Ai20 3 and other oxide ceramics. Table 11.3 offers a summary of
methods seen in recent academic journals according to this same
classification. In addition to these, various techniques have been
252
presented orally at recent annual meetings and lectures presented

by the Japan Institute of Metals, the Japan Welding Society, and
the Ceramic Society of Japan. Numerous other methods can be
found in a perusal of patents and patent provisional publications.
Of these, the following three examples will be offered as
representative of those not included in Table 11.3.
Ebata et al. 40 have succeeded in metallizing Cu by applying a
mixed paste of CU2S and kaolin to the SiC surface, coating at
1200"C in N2, immersing the heated (to 300°C) sample in
ethanol, and reducing it. Okamura et al. 41 have proposed a
metallizing technique in which a Cr paste is applied to the SiC
surface and fired at 800-1200°C in Ar. Ikuhara et al. 42 have
reported that it is possible to use Al and Cu at high temperatures
by sandwiching Al or Cu foil between pressureless-sintered SiC
bodies and hot-pressing at the high temperature of 18OO"C,
thereby diffusing the Al and Cu to an extent that virtually none
of either remains on the interface.
11.4 METHODS OF RELAXING THERMAL

STRESS43
Ceramics generally have a smaller thermal expansion coefficient

than metals, and when the two are cooled after joining at high
temperatures thermal stress results. In some cases the joined
body may fracture during the cooling process. The impact is
particularly large in the case of components being used under
thermal cycles. Thus the most difficult problem in the joining of
ceramics and metals is the relaxation of this thermal stress. It is
common to use a partner metal with a thermal expansion
coefficient approaching that of the ceramic, such as covar (an
Fe-Ni-Co alloy) for A120 3, or a soft metal with a certain degree
of deformability. Takashio44 reported from his experience with
the joining of Ah03 that a favorable relationship between the
ceramic thermal expansion coefficient and the metal thermal
expansion coefficient is as follows:
-0·5 x 10-6 ~ aM - ac ~ 1·0 x 1O-6°C- 1
Because it is dependent on the temperature difference, thermal
stress is also determined by the joining temperature, but when
this type of relationship cannot be satisfied and direct joining is
253
~
Table 11.3
Examples of Joining SiC
Joining Type 0/ CombllUltion
. Solduor Atmosphere Temp- Pressun SlmIgtil Ref·
metllod SIC Intermediate erature (MPa)
layer ("C) Metllod (MPa)
Adhesive RCb Polyborosiloxane N2 1500 3-point bending 38 24

Metallizing HP Mo N2-H2 1450 >50 25
HP Ag-Pd paste 600 42 25
HP Au paste 900 1 25
Active metal RB Ge Vacuum 1180 4-point bending 200 11
brazing RB AI Vacuum 800 4-point bending 120 5
(one-time PLS AI Vacuum 1000 4-point bending 250 5
heating) HP Cu-C composite Cu-35Mn Ar 870 0·5 Peeling 150 31
RB Cu-Ti Vacuum 1000 Peeling 80 32
RB Cu Cu-Ti Vacuum 1000 Peeling 64 32
RB Ni-Ti Vacuum 1250 Peeling 61 32
PLS Ag-Cu-Ti Vacuum 950 4-point bending 350 26
PLS TiSi2 Ar 1750 51
Brazing RB Mullite Si02-PbO-B20 3 1000 3-point bending 67 27
with frit PLS Kaolin-CaF2 Air 1500 4-point bending 130 28
PLS Si3N.-Y 203-~03-MgO Ar 1700 3-point bending 400 33
Room
Solid-state tempera-
joining MgorAl Ultra-high vacuum lure 15
RB Vacuum 1200 41 4-point bending 270 34
HP SiC-Al-B-C Ar 1650 50 4-point bending 540 29
PLS SiC-Al-B-C Ar 1650 50 4-point bending 400 29
PLS? Nimonic AI Vacuum 610 12·5 Tensile 60 35
&f
PLS WC-6%CO AI-1OSi Vacuum 610 9·8 4-point bending 131 36
PLS Covar AI-1OSi Vacuum 610 9·8 4-point bending 100 36
PLS Ti Vacuum 1500 0·56 3-point bending 300 37
PLS? VorTa Vacuum 5-10 38
PLS Nimonic BOA Ni/W/Cu Vacuum 800 60 22
Reaction RB SiC-C Vacuum 1450 4-point bending 340 30
bonding
Electrical heating RC AI-Si Air 15V- 33 39
(direct) 1000A
• Blank entry indicates SiC-t~SiC joining.

b RC, recrystallized; HP, hot-pressed; RB, reaction-bonded; PLS, pressureiess-sintered .
• A Ni-base alloy containing Cr, Ti, AI and Fe.
9i
Takayoshi Iseki
unsuccessful, the main recourse is to a method employing an

intermediate layer. The following techniques are available:
(1) Insert an intermediate layer with a thermal expansion
coefficient lying midway between that of the two materials
to be joined.
(2) Insert a compliant layer consisting of a material with a
large deformability.
(3) Balance the thermal stress.
(4) Use a shape which inhibits thermal stress.
(5) Use a phase transformation which causes changes in
volume during cooling.
There is no need for these methods to be used alone; several
are often used together. Further possibilities in the case of
anisotropic materials include selection of a direction having the
desired thermal expansion coefficient and elasticity, or, from the
microscopic standpoint of the interface structure, the utilization
of formed amorphous or ultrafine-grain layers and misfit
dislocations on the epitaxial interface. 45
11.4.1 Thermal Expansion Coeftident

Although an intermediate layer is sometimes used, the filler
metal itself may also serve as a kind of cushion layer. There are
many varieties of filler metal and frit, and a wide range available
for choosing a suitable thermal expansion coefficient. When one
intermediate layer is insufficient, a multilayer structure such as a
graded seal in which the thermal expansion coefficient is
gradually changed may be used.
11.4.2 Deformability
AI, Mg and Cu metal foils are among the soft materials available.
When joining SiC with Cu or stainless steel, however, it is
difficult to join large objects with metal foil alone. Okamura et
al. 31 have succeeded in using a Cu-C fiber composite to join
bodies of approximately 50 mm square. The intermediate layer
was prepared by plating C fibers with Cu and pressing. This layer
had a small elastic modulus, and by changing the ratio of C fibers
.it
SiC fracture Joining conditions: Fig. 11.9.
~f
X(W) X Yes 870·C. 1 sec Material selection
0 No for relaxation of
34
thermal stress in
Cu\. Cu-35Mn filler metal
SiC/Cu joining. 31
30 X(Mo) II'!I N. L ' C ·
omphant layer
o· .
16 t>si<::::\
X X X (42 Nil ~ SiC fracture
(36Ni) (Covar)X X X 200mm
12 (36Ni-Cu clad)
8
o 0 0
(Cu-C fiber
SiC composite)
40 2 4 . 6 8 10 12
Thermal expansion coefficient (10-6,·C)
to Cu it was possible to change the thermal expansion coefficient

within the range 5-12 X 1O-6°C- 1 • In the end, a Cu-35 vol.% C
fiber composite was used, and a Cu-35 wt% Mn alloy foil was
used as brazing filler in joining. A high-thermal-conductivity SiC
sintered body was joined to a cooled substrate using this method,
and in tests of channel walls for MHO power generators
extremely good results were obtained. Figure 11.9 shows the
results of material selection for relaxation of thermal stress.
11.4.3 Thermal Stress Equilibrium

Thermal stress equilibrium is a technique used in joining ceramic
and metal in which the metal is sandwiched between ceramics or
the ceramic between metals and the residual stress balanced in
order to reduce residual stress on each side. Suganuma et al. 46
have succeeded in joining Al20 3 and stainless steel through use
of the combination Al2 0 3 /Nb/Mo/stainless steel. The objective
here is to place thermal expansion coefficient tr in the following
relationship:
trAlZ0 3 "'" trNb > trMo < trsus
Yano et have also succeeded in joining SiC and stainless
aI. 47
steel by using an intermediate layer of Ti and Mo, inserting
Ag-Cu foil on each interface, and brazing (Fig. 11.10).
ordinarily, the thermal expansion coefficients of the intermediate
materials gradually move from high to low, or vice versa, as
Takayoshi [seki
Fig. 11.10. Shear 60

strength of
.
SiC/stainless steel Pressureless-
joined body hav-
ing a thermal str-
ess relaxation Ia-
......
1\1
n.
50 si ntered SiC
Ti 0.5mm
,
,I ,1----_ -- -- -",-
.
l: Mo Xmm
yerofTi + Mo.47
I
40 I •
I
....J:01 SUS316
•
c:
~
30 I
""', '\
I '\
ti I
I \
\
L.
1\1
Q) 20 ' \ .
\
J: \
III
-----
\
'\
"-
10 ........
0
o 0.2 0.4 0.6 O.B 1.0
Thickness of Mo layer (mm)
shown in the left-hand side of Fig. 11.11. When joining is

impossible with this arrangement, however, an arrangement like
the one shown in the right-hand side of the figure is selected to
balance out the thermal stress. An experiment was conducted
based upon the hypothesis that any materials would be
acceptable as long as their thermal expansion coefficients were
arranged as shown in the right-hand side of Fig. 11.11. The
experiment, in which the intermediate layer consisted not of
different metals but of the ceramic and metal to be joined
themselves, was successful. Specifically, in the joining of
pressureless-sintered SiC and type 316 stainless steel, 0·5-1·5 mm
of SiC and stainless steel were inserted between the bodies to be
joined, resulting in the arrangement SiC/stainless steel/
SiC/stainless steel, and Ti-containing silver brazing filler metal
Fig. 11.11.
Methods of inter- Ceramic ac PLS-SiC aSIC
mediate layer ar- /\ /\
rangement, where aMI Ti aT!
MI
a is the thermal /\ V
expansion M2 ~2 Mo ~o
coefficient. /\ /\
Metal ~ SUS316 asus
foil was placed on each interface and brazed to produce a joined

body with a shear strength of 33 MPa. 48 This method of using
intermediate layers is simple in that it does not require the
complexities involved in determining optimal thermal expansion
coefficient, brazing properties, reactivity, etc., during the selec-
tion of an intermediate layer.
11.4.4 Shape
This technique uses shape to reli~ve stress generated by thermal
expansion mismatch, and involves reducing metal thickness and
preventing tensile stress from being applied to the ceramic.
11.4.5 J)eforotabDi~
When ceramic and metal are joined at high temperature and then
cooled, generally the metal contracts more than the ceramic,
resulting in residual stress. Here, not only does the difference in
thermal expansion coefficient result in tension on the metal and
compressive stress on the ceramic, as would be expected from a
consideration of the stress distribution near the joining interface;
in addition, a large tensile stress is generated in the ceramic near
the outer peripheral of the joining interface, and it is often from
this stress that fracture occurs. If thermal expansion mismatch
could be reduced, residual stress would also decrease. When the
metal has a larger thermal expansion coefficient, all that is
needed is a phase transformation in which the metal expands, or
in which the ceramic contracts, during cooling. Although not
directly related to SiC, Kouno et al. 49 have applied this concept.
to the joining of a WC-Co alloy and tool steel. In addition,
Sakurai et al. so have prepared a sialon with a Cu-AI alloy and
joined it. In any case, a martensitic transformation is caused by
rapid cooling after joining.
11.5 SUMMARY
Concerning the joining of SiC, a knowledge of fabrication

methods and the structure of SiC sintered bodies is necessary.
159
Takayoshi Iseki
Wettability and reaction, which are required for any investigation

of joining methods, were discussed, and actual examples of
joining methods were introduced. Finally, methods of overcom-
ing the thermal expansion mismatch that is problematic in the
joining of metals and ceramics were examined. The joining of
ceramics remains far from a matter of systematization. At
present, trial-and-error studies are being conducted for each
material to be joined and each service environment. In Fig. 11.1
bonding and stress distribution were given as the major factors
influencing the joined body. Concerning bonding, progress in
transmission electron microscopy is helping to clarify interface
microstructures, while the finite element method and other types
of analysis are making headway in the area of stress distribution.
In addition, techniques for the evaluation of joined bodies and
non-destructive testing methods for the joining interface are
important and have yet to reach a mature stage of development.
Research concerning non-destructive testing in particular has
only just begun. Further progress in joining technology is
awaited for the expansion of ceramic applications.
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(1985), 287-92.
2. Iwamoto, N., Joining of Si3N4. In Silicon Nitride Ceramics, ed. S.
Somiya, M. Yoshimura & M. Mitomo, Uchida Rokakuho Publ-
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3. Imoto, T., Adhesion-Science and Technology. Nikkan Kogyo
Shin bun Ltd, Tokyo, 1984, pp. 100-4.
4. Nicholas, M., Forgan, R. R. D. & Poole, D. M., The adhesion of
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5. Iseki, T., Yamashita, K. & Suzuki, H., Joining of dense silicon
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6. Kohler, W., Untersuchungen zur Benetzung von AlzOr und
SiC-Kristallen durch Aluminium und Aluminiumlegierungen.
Aluminium, 51(7) (1975), 443-7.
7. Whalen, T. J. & Anderson, A. T., Wetting of SiC, Si3N4 and carbon
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8. Samsonov, G. V., Panasyuk, A. D. & Kozina, G. K., Contact
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260
9. Yupko, V. L., Wetting of silicon carbide by Cu-Ti and Cu-Sn-Ti

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11. Iseki, T., Yamashita, K. & Suzuki, H., Joining of self-bonded SiC
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17. Grnelin Handbook of Inorganic Chemistry. Springer-Verlag, Berlin,
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18. Negita, K., Effective sintering aids for silicon carbide ceramics:
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20. Kasai, Y., Saito, M. & Asada, C., Application of new substrateless
continuous SiC filament to metal matrix composite materials, Part
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56-61.
21. Nogi, K., Kato, T. & Hagino, K., Wettability of silicon carbide by
molten metals. J. Iron Steel Inst. Japan, 71(13) (1985), 414.
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60-7.
23. Iseki, T., Kameda, T. & Maruyama, T., Interfacial reactions
between SiC and aluminium during joining. J. Mater. Sci., 19(5)
(1984), 1692-8; Iseki, T., Maruyama, T. & Kameda, T .. Brit.
Ceram. Proc., No. 34 (1984), 241-8.
24. Yajima, S., Okamura, K., Shishido, T., Hasegawa, Y. & Mat-
suzawa, T., Joining of SiC to SiC using polyborosiloxane. Am.
Ceram. Soc. Bull., 60(2) (1981), 253.
25. Ikegami, A., Asai, T. & Suzuki, H., Metallization on SiC ceramics
with high thermal conductivity and high electrical resistivity.
Ceramics Japan, 21(3) (1986), 207-14.
261
Takayoshi Iseki
26. Boadi, J. K., Yano, T. & Iseki, T., Brazing of pressureless-sintered

SiC using Ag-Cu-Ti alloy. J. Mater. Sci., 12(7) (1987),2431-4.
27. Lay, L. A., Morrell, R. & Wallis, R., Joining 'REFEL' silicon
carbide to porcelain. Brit. Ceram. Proc., No. 34 (1984), 231-9.
28. Ebata, Y., Fujii, Y. & Hayami, R., Development and applications
of inorganic adhesive for non-oxide ceramics. Engng Mater.
(Japan), 31(1) (1983), 101-5.
29. Iseki, T., Arakawa, K., Matsuzaki, H. & Suzuki, H., Joining of
dense silicon carbide by hot-pressing. Yogyo-Kyokai-Shi, 91(8)
(1983), 349-54.
30. lseki, T., Imai, M. & Suzuki, H., Joining of dense silicon carbide
containing free silicon by reaction-sintering. Yogyo-Kyokai-Shi,
91(6) (1983), 259-64.
31. Okamura, H., Miyazaki, K., Matsuzaka, T., Shida, T., Ura, M. &
Okuo, T., Bonding of SiC ceramics to copper and thermal
characteristics of bonding elements (Report 1). Quart. J. Japan.
Weld. Soc., 4(2) (1986), 476-83.
32. Naka, M., Tanaka, T. & Okamoto, I., Joining of SiC using
amorphous Ti base filler metal. J. High Temp. Soc. (Japan), 12(2)
(1986), 81-9.
33. Tamari, N., Honda, M., Ebata, Y. & Kinoshita, M., Joining of
silicon carbide ceramics with Si3N4-Y203-La203-MgO mixture.
Yogyo-Kyokai-Shi, 94(10) (1986), 1087-91.
34. Rottenbacher, R. & Willmann, G., Diffusionsschweissen von
Siliziumcarbid. Z. Werkstofftech., 12(1981),227-9.
35. Wicker, A., Darbon, Ph. & Grivon, F., Solid state bonding of metal
to ceramic. Proc. of Int. Symp. on Ceram. Components for Engines,
1983, Hakone, Japan, 1984, pp. 716-20.
36. Kohno, A., Yamada, T. & Yokoi, K., Bonding of ceramics to
metals with interlayers of AI-Si clad aluminium. J. Japan Inst.
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37. Morozumi, S., Endo, M., Kikuchi, M. & Hamajima, K., Bonding
mechanism between silicon carbide and thin foils of reactive metals.
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38. Maliszewski, J., Gyarmati, E., Griibmeier, H., Lison, R. &
Naoumidis, A., Ein Beitrag zur Verbindung von SiC-Keramiken.
Forschrittsberichete der Deut. Keram. Ges., 1(2) (1985), 188-98.
39. Goryainov, K. E., Bazhbeuk-Melikova, I. G. & Antropov, V. I.,
Welding silicon cabide heating rods. Refractories, No. 12 (1967),
728-31.
40. Ebata, Y., Tamari, N., Kinoshita, M. & Hayami, R., Metallizing
technique for silicon nitride ceramics. Yogyo-Kyokai-Shi, 92(5)
(1984), 294-5.
41. Okamura, H., Sakamoto, M., Shida, T. & lseki, T., Silver brazing
of SiC ceramics by using chromium metallization (Report 1). Quart.
J. Japan. Weld. Soc., 6(2) (1988), 226-32.
42. Ikuhara, Y., Miyazaki, H., Kobayashi, M. & Yoshinaga, H.,
Joining of sintered SiC by AI and Cu, Ann. Meet. Ceram. Soc.
Japan, No. 31(10) (1987).
43. Iseki, T., Joining technology for ceramics. Sci. Machine (Japan),
39(11) (1987), 1203-8.
44. Takashio, H., Joining techniques and their applications to fine-
ceramics. Engng Mater. (Japan), 34(8) (1986), 26-74.
45. Ishida, Y. & Ichinose, H., Microstructures of interface in joining
and adhesion. J. Mater. Sci. Soc. Japan., 22(4) (1986), 172-6.
46. Suganuma, K., Okamoto, T. & Koizumi, M., Effect of interlayers in
ceramic-metal joints with thermal expansion mismatches. J. Am.
Ceram. Soc., 67(12) (1984), C-256-C-257.
47. Yano, T., Takada, N. & Iseki, T., Joining of pressureless-sintered
SiC to stainless steel using Ag-Cu alloy and insert metals.
Yogyo-Kyokai-Shi, 95(3) (1987), 357-62.
48. Iseki, T. & Yano, T., Brazing of SiC ceramics with active metal.
Mater. Sci. Forum, 34-36 (1988), 421-5.
49. Kouno, A., Hioki, S., Taguchi, K. & Nakae, H., Diffusion bonding
of WC-CO hardmetal to tool steel. Quart. J. Japan. Weld. Soc.,
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12 •
Multiple Toughening m
A12 0 3 /SiC
Whisker/Zr02
Composites
TETSUO UCHIYAMA, SIGEO
INOUE & KOICHI NUHARA
ABSTRACT
AI20 3 /SiC whisker/Zr02 composites were fabricated by hot-

pressing to full density. Significant toughening and strengthening
were achieved in AI20 3 /25 vol. % SiC whisker/IS vol. % Zr02'
The whisker bridging/pullout mechanism rather than crack deflec-
tion was believed responsible for whisker toughening in the
composites studied. Multiplicative and interactive effects between
whiskers and transformation toughening are discussed.
12.1 INTRODUCTION
Attempts to fabricate composites are attracting attention as a

means of improving fracture toughness in ceramics and other
brittle materials.
The toughening mechanism involves relaxation of the mechan-
ical environment of the crack tip and has been relatively well
explained using fracture mechanics; in the case of a Zr02
composite, for example, there is a stress-induced transformation
from tetragonal to monoclinic in the vicinity of the crack tip, and
a residual strain is introduced in order to shield the propagating
crack from the applied loading. 1
Recently there have been attempts to incorporate SiC whiskers
into a variety of ceramic matrices,2-5 and these efforts are often
Tetsuo Uchiyama, Sigeo Inoue, Koichi Niihara
treated together with the concept of fiber-reinforced metals

(FRM),t in which whiskers take on and support a portion of the
load on the metal. There are two main proposed mechanisms:6-7
pullout from the matrix induced by bridging of the whisker
behind the crack tip;8 and crack deflection by whiskers as
microscopic heterogeneous bodies in the microstructure. 9
In the present work, SiC whiskers and Zr02 were incorporated
into an Ah03 matrix. This chapter will examine multiple
toughening that combines several toughening mechanisms.
12.2 EXPERIMENTAL PROCEDURE
The following raw material powders were used: high-purity

AI20 3 (y-type, BET specific surface area: 200 m2/g) from Asahi
Chemical Industry, SiC whiskers (diameter: 0·05-0·2 IUD; length:
10-40 IUD) from Tateho Chemical Industries, and Zr02 (contain-
ing 2 mol. % Y203; BET specific surface area: 18 m2/ g) from
Toyo Soda Mfg.
The powders were blended at prescribed ratios, 0·3 wt% MgO
was added as a sintering additive, and the powders were
wet-mixed for 24 h in an alumina container with alumina balls
using ethyl alcohol as a mixing fluid. The resulting mixed powder
was then dried. Sintering was conducted by hot-pressing at
1500"C and 30·6 MPa for 1 h to prepare disk-shaped samples
approximately 65 mm in diameter X 6 mm. 3 X 4 X 38 rom speci-
mens were then cut out from these samples, and a three-point
bend test with a span of 30 rom was conducted in room-
temperature air using a crosshead speed of 0·5 mm/min. Here,
the tensile surface of the specimen was polished to a mirror
surface in order to eliminate any influence from the Zr02
transformation, and this was carried out parallel to the direction
t Even the incorporation of long fibers into a ceramic matrixlO falls into
the category of fiber reinforcement in the sense that the fibers support a
portion of the load if the fracture strain of the fibers is larger than that of
the matrix and there is no chemical bond on the fiber-matrix interface.
In the case of whiskers (short fibers), there must be a strong bond on the
whisker-matrix interface in order to transfer the load, and it becomes
impossible to expect improvements in toughness.
of hot-pressing. (The tensile surface is parallel to the direction of
hot-pressing, while the tensile direction is perpendicular thereto.)
After measuring bending strength, the indentation method
(load, 196 N) was used with Niihara's formula l l (Kc = 0·203
(c/a)-312 Ha lfJ., where 2a is the indentation diameter, 2c is the
crack length, and H is Vicker's hardness) to measure fracture
toughness Kc. A fracture surface of the specimen was also
observed by scanning electron microscope.
12.3 RESULTS AND DISCUSSION
The sintered single-phase Al20 3 had a fracture toughness Kc of

3·5 MPaYm and a bending strength Of of 470 MPa. Addition of
SiC whiskers at a volume fraction of 25% and of Zr02 at a
volume fraction of 15% resulted in improvement in these values
to 5·3MPaYm and 590MPa and 5·2MPaYm and SOOMPa,
respectively. Addition of both 25% SiC whiskers and 15% Zr02
resulted in a Kc of 8 MPaYm and a Of of 1128 MPa, indicating
that the toughening mechanisms of both materials could operate
without any degradation.
Figure 12.1 shows strength and fracture toughness for when
1400,...-----------------. Fig. 12.1. Frac-

ture toughness Kc
1200 and bending
strength Of as a
function of Zr02
1000 9 volume fraction in
an Al20 3 /SiC
:. 800 8 whisker/Zr02
l: ~ ceramic composite
7
:. containing
l: 25 vol. % SiC
• whiskers.
u
400 • 6 ~
~
200 5
oo~--~~--~~--~~---J
0.05 0.10 0.15
FIg. 12.1. Frac- 1400,---------------------.

ture toughness Kc
and bending
1200
strength Of as a
function of SiC
whisker volume 9
fraction in an
Al20 3 /SIC r2. 8
whisker/Zr02 ce- ~
ramic composite
containing 15 0- 7
vol.% Zro2 •
6
°o~----~~--~~--~~--~
0.15 0.25 0.35
the volume fraction of SiC whiskers was kept constant at 25%

and that of Zr02 varied from 0% to 15%; Fig. 12.2, the same for
when the volume fraction of Zr02 was fixed at 15% and that of
SiC whiskers varied from 0% to 35%. Within the scope of Fig.
12.1, both fracture toughness and strength increased together
with increases in Zro2 content. In the case of SiC whiskers (Fig.
12.2), on the other hand, fracture toughness and strength peaked
at 25 vol. %. Composites containing a greater volume of SiC
whiskers exhibited reduced fracture toughness and strength,
indicating the difficulty of mixing large-aspect-ratio whiskers.
It has been confirmed from observation of the relatively large
steps along the whisker, as shown in the fracture surface of Fig.
12.3 (crack deflection), and the numerous holes resulting from
whisker pullout and the relatively long whisker-matrix interface
(crack deflection) in Figs 12.3 and 12.4 that there are two
contributing toughening mechanisms in SiC whiskers: crack
deflection and whisker bridging/pullout.
In the crack deflection mechanism,9 the presence of the
residual strain-inducing whisker causes the crack tip to deflect
from the state in which it forms an ideal plane at right angles to
the direction of the applied load. In the bridging/pullout
Fig. 12.3. Frac-
ture surface of an
A120 3 /25 vol. %
SiC whisker/lO
vol. % Zr02 cera-
mic composite. A
relatively large
step is observed
along the SiC
whisker, indicat-
ing the presence
of the crack
deflection
mechanism.
Fig. 12.4. Frac-

ture surface of an
A120 3 /25 vol. %
SiC whisker/lO
vol. % Zr02cera-
mic composite.
Numerous holes,
the remains of
whisker pullout,
are observed,
indicating the
presence of the
whisker pullout
mechanism.
FIg. U.S. Residual stress

Residual stress resulting from the difference in
generated near thermal expansion coefficients
between the whisker and matrix
the whisker by
mismatch of ther- . '-.........t~
mal expansion "'~
=:=====--./'"
coefficient. The
crack is attracted
to the whisker.
Crack
mechanism,7 the whisker forms a bridge behind the crack tip,

causing the whisker to be extracted from the matrix a distance
equal to the crack opening displacement. In the latter mechanism
the improvement in toughness is due to energy consumption,
which is dependent on the shear resistance caused by interlace
friction. Since the priority of the mechanisms depends on the
spatial relationship of the whisker with respect to the propagating
crack, this problem is closely related to such techniques as
control of whisker orientation and random dispersion processing.
Because the composites used in work on the present chapter
were prepared by hot-pressing, the whiskers tended to be
arranged in a plane perpendicular to the direction of hot-pressing
rather than having a completely random distribution. In addition,
since the thermal expansion coefficient of the whiskers is smaller
than that of the matrix (4·5 x 1O-6 rC for the SiC whiskers in
contrast to 8·5 x 1O-6 rC for the Al2 0 3 matrix), in the region of
the matrix near the whisker, as shown in Fig. 12.5, there is a
residual tensile stress in the circumferential and longitudinal
directions of the whisker and a compressive stress in the radial
direction. Thus the mechanical environment is such that the
crack is attracted to the whisker.
When the relationship between the piece used in the bending
strength test and the hot-pressing orientation, i.e. the fact that
the whisker is arranged at nearly right angles to the tip of the
propagating crack (Fig. 12.6), and the relationship with the
residual stress caused by the above-described thermal expansion
coefficient mismatch are taken into consideration, it can be
predicted that the contribution of the bridging/pullout mechan-
ism will increase. From the standpoint of the crack deflection
mechanism,9 it can be predicted that of the tilt and twist
components (analysis of the crack deflection mechanism in
270
Alz03/SiC Whisker/ ZrOz Composites
Fig. U.6.
Relationship of
whisker alignment
Tensile axis due to hot-
~ pressing and crack
which caused a
fracture during
Defect causing-"'-- the bending test.
fracture
whisker (rod-shaped second-phase particles) composites9 has

shown that the twist component makes a larger contribution to
toughness improvement) the latter will have a reduced probabil-
ity and that, considering the size «100 !J.m) of the crack causing
the fracture, there is not a sufficient number of whiskers
contributing to an interactive effect. Consequently, the toughness
improvement brought about by the crack deflection mechanism is
thought to be smaller than that resulting from the bridging/
pullout mechanism.
Toughening by Zr02 occurs together with the stress-induced
martensitic transformation from tetragonal to monoclinic Zr02
within limited stress concentration regions near the crack tip.
This mechanism contributes to toughness improvement by the
behavior of the so-called 'R-curve', in which the transformation
zone is increased along the crack surface together with stable
crack growth to shield the crack tip from the applied loading. 1
Toughness improvement AKc when R-curve behavior is in a
steady state can be expressed as follows:
AKc= yEeTl'tVW (1)
Here, eT is transformation strain, E is Young's modulus, l't is the
volume fraction of transformable Zr02, and W is the width of the
transformation zone; y is a constant.
As a result of combining with SiC whiskers, the increase in
load required to bring the stress field of the crack tip to a critical
level increases width W of the Zr02 transformation zone of eqn
(1) and brings about an additional improvement in toughness
171
Fig. U.7.
Fracture surface
of an Ah03/30
vol.% SiC
whisker ceramic
composite. With-
out Zr02' a high
sintering tem-
perature (1800°C)
is required, re-
sulting in a large
grain size for the
matrix. There-
fore, intragranu-
lar fracture, which
forms a relatively
smooth surface, is
dominant.
because of the whisker bridging/pullout and crack deflection

mechanisms. In Ah03-SiC whisker materials (sintered at
18OO"C) into which Zr02 has not been incorporated, there was
exaggerated grain growth, and intragranular fracture, which
forms a relatively smooth surface, was dominant (Fig. 12.7).
Addition of zr02 allowed reduction of the sintering temperature
to 1500-1600°C, the grain size of the Al20 3 matrix was reduced
(0·5-1 r.tm), and the fracture morphology became intergranular,
thereby introducing the benefits of the crack deflection mechan-
ism (Fig. 12.3). Here, a comparison of the size of the crack
causing the fracture «100 r.tm) and grain size (0·5-1 r.tm) also
indicates that there is a high probability of contributing to
improved toughness, unlike in the case of whisker-induced crack
deflection. Furthermore, as shown in Fig. 12.8, the existence of
an additional mechanism by which Zr02 transformed within the
process zone applies a compressive strain to the whisker,
increases the shear resistance from interface friction, and
increases the energy necessary for whisker pullout can also be
postulated.
rTl
Al20 31SiC Whisker I Zr02 Composites
Residual stress on the whisker Fig. U.8.

Zr02 transformation-induced Additional tough-
crack Shielding stress ening by zr02
with respect to
SiC whisker
bridging/pullout
mechanism.
/
Whisker Remains of whisker pullout
12.4 SUMMARY
SiC whiskers and Zr02 were incorporated into alumina in an

attempt to achieve multiple toughening. The toughening mecha-
nisms of both materials operated without any degradation, and
the existence of an additional mechanism resulting from their
combination was also inferred from investigation of the toughen-
ing mechanisms. Within the scope of the present work, the
bridging/pullout mechanism of SiC whiskers was found to have
priority over the crack deflection mechanism, and Zr02, in
addition to the martensitic transformation-induced crack shield-
ing mechanism, made possible remarkable reductions in sintering
temperature, thereby allowing finer grain in the matrix.
ACKNOWLEDGEMENTS
Permission was received to include this work in the current
volume despite the fact that it deals with alumina-matrix
composite materials. We would like to express our deepest
appreciation to Mr Uchida of Uchida Rokakuho.
REFERENCES
1. Evans, A. G. & Cannon, R. M., Toughening of brittle solids by
martensitic transformations. Acta Metall, 34(5) (1986), 761-800.
2. Veno, K. & Toibana, Y., Mechanical properties of silicon nitride
ceramic composite reinforced with silicon carbide whisker. J.

Ceram. Soc. Japan, 91(11) (1983), 491-7.
3. Becher, P. F. & Wei, G. C., Toughening behavior in SiC-whisker-
reinforced alumina. J. Am. Ceram. Soc., 67(12) (1984), C-267-C-
269.
4. Claussen, N. & Petzow, G., Whisker-reinforced oxide ceramics. J.
de Phys., 47(2) (1986), CI-693-CI-702.
5. Buljan, S. T., Baldoni, J. G. & Huckabee, M. L., Si~4-SiC
composites. Am. Ceram. Soc. Bull., 66(2) (1987), 347-52.
6. Wiederhom, S. M., Brittle fracture and toughening mechanisms in
ceramics. Ann. Rev. Mater. Sci., 14 (1984), 373-403.
7. Faber, K. T., Toughening mechanisms for ceramics in automotive
applications. Ceram. Engng Sci. Proc., 5(5/6) (1984), 408-39.
8. Lange, F. F., Fracture toughness of Si3N4 as a function of the initial
a-phase content. J. Am. Ceram. Soc., 62(7-8) (1979), 428-30.
9. Faber, K. T. & Evans, A. G., Crack deflection processes-I. Theory.
Acta Metall., 31(4) (1983), 565-576.
10. Marshall, D. B., Cox, B. N. & Evans, A. G., The mechanics of
matrix cracking in brittle-matrix fiber composites. Acta Metall.,
33(11) (1985) 2013-21.
11. Koichi Niihara, Indentation microfracture of ceramics-its applica-
tion and problems. Bull. Ceram. Soc. Japan, 20(1) (1985) 12-18.
274
13 Sintering Aids and
Thermal Conductivity
of PolycrystaUine SiC
TOSIKAZU SAKAI
NAOTO mROSAKI &
TosmmKO AIKAWA
ABSTRACf
Silicon carbide powder is usually sintered with additives. These

sintering aids affect not only densijication but also certain pro-
perties of the sintered compact. Effects of the addition of boron
together with carbon; alumina, beryllium, barium oxide with
carbon; and rare earth oxides with carbon on the sintering of SiC
and the thermal conductivity of SiC ceramics are described.
13.1 INTRODUCflON
SiC is a covalent compound and a typical non-sinterable
substance, and it is common to add some kind of sintering aid
during sintering. The sintering aids both promote densification
and have a major impact on the properties of the sintered
compact. These properties are important not only as basic
references for study of the composition and structure of a
substance but also when considering the effective mechanisms of
sintering aids.
In this chapter, the effects of several sintering aids on the
sintering characteristics and thermal conductivity of SiC sintered
compacts will be discussed.
SiC itself is a good conductor of heat, with single crystal
(a-type) SiC being reported to have a thermal conductivity of
275
TosiktJzu SaktJi, Naoto Hirosaki, Toshihiko Aikawa
Table 13.1
Properties of Chemical Analysis SiC >98wt%
fJ-type Silicon Free Si02 0·22
Carbide Powder Free C 0·24
Al 0·03
Fe 0·04
Mean particle size 0·28 J.Ull
Specific surface area (BET) 17.1 m2 /g
65-460 W mK at room temperature. 1 This is one of the special

characteristics of SiC that make it suitable for use as a
mechanical or heat-resistant high-temperature material. Accord-
ing to the same reports, the thermal conductivity of polycry-
stalline SiC varies widely in the range 0·19-205 W1m K (at 70"C),
but most of the· values were approximately one order of
magnitude lower than those shown by the single crystal (variety).
Polycrystalline SiC can be extremely sensitive to influence from
the fabrication method, purity and particle size of the raw
material SiC powder used, grain boundary composition (which in
turn depends on the sintering aid used), and the microstructure
of the sintered compact. The properties and sinterability of the
raw material powder as well as their relationship with the
properties of the sintered compact are not yet fully understood.
For the current work, the (J-Sie shown in Table 13.1 was mainly
used. As sintering aids, several conventional materials as well as
some relatively new substances were selected, and the effect of
sintering aid type and sintering conditions on thermal conduc-
tivity is discussed.
13.2 BORON-CARBON SYSTEM SINTERING

AIDS
13.2.1 Sintering
The technique, discovered in 1975 by Prochazka, of simul-
taneously adding boron and carbon as SiC sintering aids2 is
widely used and considered to be the most effective. According
to patent specifications, 3 a boron-containing compound equiv-
alent to 0·3-3·0 wt% boron with respect to (J-SiC and a carbon
rT6
Properties of Polycrystalline SiC
source equivalent to 0·1-1·0 wt% elemental carbon after thermal

decomposition were added to P-SiC, the resulting mixed powder
was formed into a green compact, and by sintering in an
atmosphere that was chemically inert with respect to silicon
carbide a high-density (at least 85% of theoretical) sintered
compact was produced. This method is extremely effective with
respect to SiC sintering, and numerous later studies have
reported that a high-density sintered compact can be obtained
with even smaller amounts of sintering aid. For example, Tanaka
et al. 4 have used an amorphous metal boron powder as a boron
source and pitch tar or an organic resin solution as a carbon
source with pressureless sintering. Heating at 2150°C for 60 min
with addition of 0·15 wt% boron and 1·0 wt% carbon produced a
highly-densified sintered compact with density of 3·12 (relative
density: 97%). Here, addition of 0·3 wt% or more boron results
in abnormal grain growth during sintering and facilitates the
coarsening of particles.
Opinions differ concerning the effects of boron and carbon as
sintering aids. Prochazka thought that the reason for the
non-sinterability of unaided SiC was the extremely large ratio
rgb/rSY of SiC interlace energy (rgb) to surlace energy (rSY). The
added boron collects on the grain boundaries, with a portion
entering the SiC as a solid solution to reduce grain boundary
energy, while the carbon increases the effective surlace energy by
removing SiC surlace impurities such as Si02 and Si. He
explained this as follows: 'When the mechanisms of both operate
simultaneously, sintering is made possible by reduction of the
energy ratio rgb/rsY'.
Greskovich & Rosolowski5 concluded that boron inhibits SiC
surlace diffusion in the region below 1500°C at which grain
growth does not occur and acts as a sintering aid when the
powder reaches the high-temperature region at which densifica-
tion proceeds in a state of fine powder without grain growth.
13.2.2 Thermal Conductivity of Sintered COlDpacts

Promotion of densification by the simultaneous addition of boron
and carbon is thought to be related to the solution of boron into
SiC. 5 One of the properties heavily influenced by the formation
of a solid solution is thermal conductivity.
Tosikazu Sakai, Naoto Hirosaki, Toshihiko Aikawa
Fig. 13.1. Effect 3.5~--------------.- 2

of boron content 150 E
on SiC sintered ~
.~
..,~
compact density E .~
and thermal con- ~ 3.0 ti
ductivity (1 wt% ~ 100 -6
c
carbon). l:
'OJ
8
c ii
~ 2.5 .....- - -__..... ...
E
"
.c
~
; I I
o 0.01 0.1 10
B concentration (wt .,.)
Figure 13.1 shows density and real thermal conductivity for a

sintered compact formed by adding 1 wt% carbon and 0-10 wt%
boron as sintering aids and hot-pressing at 20S0°C under 20 MPa
for 0·S-2 h. Sintering time was O·S h for boron concentrations of
0·2 wt% or more and longer at lower concentrations. Thermal
conductivity was determined from thermal diffusivity, measured
at room temperature with the laser flash method, and specific
heat. As boron content increased from 0-02 wt% to 0·2 wt%
densification progressed, and an ultimate density of at least
3·0 g/cm3 was attained. Together with this densification, thermal
conductivity decreased suddenly.
The amount of boron contained in the SiC as a solid solution
was approximately 0·1 wt% at 2100°C. 6 The decrease in thermal
conductivity corresponding to the increase in boron content
shown in Fig. 13.1 suggests the formation of a solid solution of
boron and SiC.
13.3 ALUMINA SYSTEM SINTERING AIDS
13.3.1 Sintering
The additive effect of aluminum, alumina and other AI-
containing substances on SiC has long been studied and utilized.
AI is more sensitive to sintering temperature, atmosphere and
heating method than the boron-carbon system described in the
previous section, and as a result density, volatile weight loss, and
phase transformations of SiC polytype are also strongly affected

by these conditions.
Concerning this system, Alliegro et al. 7 reported in 1956 that
SiC prepared from pure carbon and silicon did not sinter, but
that SiC using silicon containing up to 1% Al achieved high
densification by hot-pressing. They also experimented with
various metal additives and confirmed the effect of adding Al
alone as well as AI together with Fe, Band Zr.
The effectiveness of AI2 0 3 as a sintering aid stems from the
fact that it forms an aluminosilicate liquid phase between Si02
and other impurities contained within the SiC, thereby promot-
ing the densification of SiC. 8 The simultaneous addition of Ah03
and carbon has a multiplicative effect, and the densification can
be observed with only a small amount of A120 3.9
When using alumina system sintering aids, various reactions
may occur within the system depending on the conditions, and
the generation of Si vapor and the formation of AhOC are
inferred. 1O Numerous problems, such as the volatile weight loss
accompanying the reactions and abnormal grain growth, must be
taken into consideration when establishing the conditions of
sintering, and strict control over these conditions is required.
Sintered compacts of this system have higher mechanical
strength than those produced from the boron-carbon system
described earlier or the beryllium system to be discussed in the
following section. 11
13.3.2 Thermal Conductivity of Sintered Compacts

The effect of sintering aid content on ultimate density, crystal
phase and thermal conductivity was investigated for hot-pressing
with 1-3 wt% alumina and 0-5 wt% carbon. 9 Hot-pressing was
conducted at a temperature of 1800-2050"C under 20 MPa for
30 min.
As described earlier, alumina has a large effect on densifica-
tion, and addition at a weight fraction of 2% or more will
produce a sintered body with near-theoretical density at
temperatures of 1950°C and above regardless of the presence or
absence of carbon. An interaction of alumina content and carbon
content was observed in the transformation of a polytype of SiC.
As the respective contents of these two materials increased from
Fig. 13.2. EtIect 50 100

of carbon on sin-
tered compact
thermal conduc-
tivity and fJ -+ a 40
.. .
..
80
-
transition (3 wt% ~
A120 3 , 2050"C, E
30 min). i ..!
!.
30 I 60
~ c
I
•
0
...
:~ :;;
....."
u I u
:3
"0 I
c 20 I 40 II
0
u I-=--- E
!I
.. I
ii '0
E I >
II
10 I 20 x
c ~
~
I
I
~
0 0
0
Carbon content (wt .,.)
1 wt% to 2 wt% and from 0 wt% to 1 wt%, there was a marked

change from a 3C to a 4H structure. Increasing the hot-pressing
temperature from 18OO"C to 1900°C also resulted in a rapid phase
transformation (2 wt% each of Ah03 and carbon).
Figure 13.2 shows change in thermal conductivity of the
sintered compact as a function of carbon content. 9 As carbon
content increased from 0 wt% to 1 wt%, thermal conductivity
dropped rapidly from 48 W1m K to 30 W1m K. Here, unlike the
case of the boron-carbon system, density achieved near-
theoretical levels and did not exhibit any fluctuation. The same
rapid decrease in thermal conductivity could be observed when
the hot-pressing temperature was increased from 1800°C to
1850°C (2 wt% each of Ah03 and carbon). In both cases, the
decrease in thermal conductivity occurred simultaneously with
the transformation in the crystal structure.
One possible explanation for the decrease in thermal conduc-
tivity during sintering at high temperatures is the solid solution of
AI in SiC. The solution of AI is heavily dependent on
temperature and increases together with it. 6 It is also well known
that the solution of AIN in SiC causes a remarkable reduction in
thermal conductivityY The addition of carbon, by forming an
aluminum oxycarbide having a structure similar to that of AIN, 10

promotes solution in the SiC. This is believed to have the same
effect on thermal conductivity as an increase in hot-pressing
temperature.
13.4 BERYLLIUM SYSTEM SINTERING AIDS
13.4.1 Sintering
Beryllium itself or a compound thereof is effective as a sintering
aid in the hot-pressing of SiC. When 1-2 wt% Be or BeO was
added to a-SiC with a mean particle size of 2 JA.m, in-vacuo
hot-pressing at 2040°C under 20 MPa for 1 h produced a black,
glossy sintered compact with relative density of 98% and above. 13
BeQ added to the SiC exhibited grain growth during
hot-pressing and ultimately remained on the grain boundaries as
single-crystal particles, virtually none of it entering into the SiC
crystalS. 14 It is also reported that polytype modifications in SiC
near the grain boundaries accompany the BeQ grain growth,
resulting in grain growth in the direction of the C-axis
accompanied by rapid densification. 14 The sintering promotion
mechanism of BeQ remains, however, not yet fully understood.
The bending strength of hot-pressed sintered compacts con-
taining beryllium system sintering aids is approximately 450 MPa,
roughly the same as for the boron-carbon system.

SiC sintered compacts using beryllium alone or an oxide or
carbide thereof as sintering aids are characterized by an
extremely large thermal conductivity of 260 W1m K or more. 13
These compacts also have an extremely large electrical resistance
of 1013 g cm or more. Takeda et al. 13 suggested that the solubility
of Be with respect to SiC crystallites is much smaller than that of
B or AI. In sintered compacts containing BeQ, therefore, BeQ
gathers on a portion of the grain boundaries as crystals. In
addition, no heterogeneous phase could be observed on the grain
boundary portions by high-magnification transmission electron
microscopy of the sintered compact. Given these results, they
concluded that the sintered compact possessed a large thermal
281
Tosikazu SaIcai, Naoto Hirosaki, Toshihiko Aikawa
conductivity and a high electrical resistivity because of the small

impurity concentration in the SiC crystallites.
13.5 BARIUM-CARBON SYSTEM SINTERING

AIDS
13.5.1 Sintering
Numerous studies have been made on the effect of sintering aids
on the promotion of SiC sintering, and there are several reports
in the literature. According to these results, it was thought that
the addition of alkaline earth compounds inhibited SiC
sintering. 7 When an alkaline earth compound and carbon are
simultaneously added and hot-pressed, however, an acceleration
of sintering of SiC is observed.
Concerning the alkaline earth compounds, the results of
studies on BaO, which has a remarkable sintering promotion
effect, will be discussed. 15 fJ-SiC was doped with reagent grade
BaO and, as a carbon source, an ethanol solution of phenol resin
to produce a raw material powder. Hot-pressing was performed
at 2050"C for 30 min under 20 MPa in a reduced-pressure
atmosphere of 10-2 Pa.
BaO (0-30 wt% ) and carbon (0-6 wt% ) were added as
sintering aids. Densification was exhibited at BaO concentrations
of 3 wt% and above. High-density sintered compacts were
produced with BaOIC weight ratios of 3-5 and molar ratios of
1 :4·2-2·5. At approximately 1200°C, BaO and C form a carbide
by the reaction
BaO + 3C = Ba~ + COj.
The above molar ratio approximates the 1: 3 equivalence of the
Ba~ formation reaction. Ultimate density also drops when there
is an excess of carbon, but when there is insufficient carbon with
respect to BaO sintering is strongly inhibited.
A fluid phase is formed at above 15000C between SiC and
Ba~ which is produced by a reaction of BaO on C. This fluid
phase is formed mostly at an equal ratio of Ba~ and SiC.
Densification of SiC is enhanced through the low viscous phase
formed as a result of a reaction between SiC and Ba~, the latter
being produced by a reaction between sintering aids, BaO and C.

Figure 13.3 shows density and real thermal conductivity at room
temperature of a hot-pressed fJ-SiC sintered body containing
0-10wt% BaO and 0-2 wt% carbon. When BaO concentration
increased from 0 wt% to 5 wt% with respect to a steady carbon
content of 1 wt%, thermal conductivity dropped remarkably
from 121 W1m K to 20 W1M K. This change in thermal conduc-
tivity corresponds to the change in density shown in the same
figure.
Figure 13.4 shows a transmission electron microscope
microphotograph of a sintered compact containing BaO and
carbon. A second phase with a thickness of approximately
0·01 J.Ull was observed to be distributed on the grain boundaries
between the SiC particles with almost uniform thickness. This
phase is a reaction product of Ba~ and SiC, and at high
temperatures it wets the SiC particles as a fluid phase to promote
sintering. The relationship between thermal conductivity and
ultimate density also supports this conclusion, and formation of
this grain boundary phase reduced thermal conductivity.
13.6 RARE EARTH OXIDE WITH CARBON

SYSTEM SINTERING AIDS
13.6.1 Sintering
Figure 13.5 shows the relative density of a sintered compact
prepared by hot-pressing at 2050"C for 2 h under 20 MPa in a
reduced-pressure atmosphere an SiC powder shown in Table 13.1
to which 5 wt% of the various rare earth oxides and 5 wt% each
of an oxide and carbon were added. Some increase in density was
observed with the addition of a rare earth oxide alone, but the
effect was minimal. When the rare earth oxide and carbon were
added together, all cases showed a higher density than when
carbon was not added. Addition of holmium oxide alone, for
example, produced an ultimate relative density of only 71 %, with
no observed sintering promotion effect, while addition together
with carbon produced an extremely high-density (98% and
above) sintered body.
Shrinkage during hot-pressing of an SiC green compact
Fig. 13.3. Effect (a) (")

ofBaO and C
content on ultim- 120 120 ~
ate density and
thermal conduc-
tivity. (a) 1 wt%
.
E
100
3.0
100
..
~
>.
:~
Cadded; (b) u 80 80 t:
;:)
\
~ 2.5
5wt%BaO
q
'0
2.5 C
added. 60 60 8
\ i1
\
\
\-
40 40 ttI
2 .0 \ ~
t-
0------0 20 20
L -____- - '_ _ _ _-"-----' 0
~----~~----~~o
o 5 10 o 2
BaO concentration (wt .,.) C concentration (wt .,.)
Fig. 13.4. TEM

photograph of SiC
sintered compact
(lOwt% BaO,
2wt%C). The
arrow indicates a
grain boundary
phase.
O.Spm
~--=-~---- ....
I :Carbon not added

Fig. 13.S.
II Ultimate density
II : Carbon add ed
of SiC to which
Y20 3 various rare earth
oxides were
L~03 added (oxide,
5 wt%; carbon,
5 wt%, 2050°C;
Ce 02 20MPa;2h).
Pr6011
Nd2~
SrTl2D.3
EU20:3
Gd203
Tb40 7
DY203
Ho20 3
Er203
Yb203
50 60 70 80 90 100
Relative density (%)
Oxide type HOzO:J DyzO:J GdzO:J Tb4 0 7 NdzO:J ErzO:J

Table 13.2
Density and
Oxide Thermal Conduc-
concentration tivity of SiC Sin-
(wt%) 0·5 5·0 5·0 5·0 5·0 5·0 tered Compacts to
Carbon which Rare Earth
concentration Oxides and Car-
(wt%) 0·9 5·0 5·0 5·0 5·0 5·0 bon were Simul-
Density (g/ cm 3) 3-19 3-17 3·06 3-13 3·01 3-13 taneously Added
Thermal
conductivity
(W/mK) 170 136 130 127 122 121
285
containing both a rare earth oxide and carbon occurred at

temperatures of 1800°C and above, more than 200°C higher than
when boron-carbon or alumina system sintering aids were used.
Shrinkage gradually continued up to high temperatures.
To take the example of carbon and holmium oxide (HoO t _s),
which had the most remarkable densification promotion effect of
the substances in Fig. 13.5, HoO t _s is effective when added at a
molecular fraction of 0·02 (approximately 0·1 wt%). In this case,
at least 3 mol% (0·9 wt%) of carbon is required. Generally,
increased sintering aid content tends to an increase in the
sintering promotion effect as well. When the carbon is
insufficient, however, further increases in holmium oxide content
bring about a reduction in ultimate density.
When HoO t _s is mixed with carbon and heated, it passes
through an intermediate phase at 1800°C and above and becomes
Ho~ at temperatures of 1900°C and above. Because HoO t _s
reacts more strongly with respect to SiC, however, the above-
described reaction occurs at a temperature approximately
50-100°C lower than in the case of carbon. Here, SiC
decomposes, and Si vapor formation is inferred. The formation
Fig. 13.6. TEM

microphotograph
of SiC sintered
compact
(0·1 mol%
HoO t _s; 3 mol%
C).
,. 1 JJ m
of Si acts to inhibit SiC sintering. The additive effect of carbon is

believed to reduce the effect of Si. However, the sintering
promotion mechanism of rare earth oxide-carbon system
sintering aids is not yet fully understood.
13.6.2 Thermal Conductivity of Siotered Compacts

Table 13.2 shows the thermal conductivity of densified SiC
sintered compacts formed by adding both a rare earth oxide and
carbon and then hot-pressing. The values for thermal conduc-
tivity are between 120 and 170 W1m K, second only to the figures
exhibited by sintered compacts using beryllium system sintering
aids. As with the beryllium system, this is thought to be due to a
lack of solid solution in the SiC crystals and the lack of an
inclusion phase on the grain boundary. Figure 13.6 is a TEM
microphotograph of a sintered compact structure. There is less
grain boundary phase than wth the BaO-C system sintering aids
shown in Fig. 13.4. A portion of the added rare earth remains in
the sintered compact as a carbide. However, there was no
particular correlation between thermal conductivity and sintering
aid content, and it is deduced that these residual products exist
locally at triple points between the particles, with no solution
into the SiC.
REFERENCES
1. Thermal conductivity of SiC. In The TPRC Data Series, vol. 2, ed.

Y. S. Touloukian. Plenum Press, New York, 1970, pp. 585-8.
2. Prochazka, S., The role of boron and carbon in the sintering of
silicon carbide. In Special Ceramic 6, ed. P. Popper. British
Ceramic Research Association, Stoke-on-Trent, 1975, pp. 171-81.
3. Prochazka, S., Manufacture methods of dense silicon carbide
ceramics. J. Pat. Gazette Sho., 57-32035.
4. Tanaka, B., Inomata, Y., Tsukuda, K. & Bagimura, A., Normal
sintering of tJ-SiC powder-amounts of boron and carbon additions.
Yogyo-Kyokai-Shi, 92 (1984), 461-5.
5. Greskovich, C. & Rosolowski, J. B., Sintering of covalent solids. J.
Am. Ceram. Soc., S9 (1976), 336-43.
6. Tajima, Y. & Kingery, W. D., Solid solubility of aluminum and
boron in silicon carbide. J. Am. Ceram. Soc., 6S (1982) C-27-29.
7. Alliegro, R. A., Coffin, L. B. & Tinklepaugh, J. R., Pressure-
sintered silicon carbide. J. Am. Ceram. Soc., 39 (1956) 386-9.
8. Lange, F. F., Hot-pressing behaviour of silicon carbide powders

with additions of aluminium oxide. J. Mater. Sci., 10 (1975),
314-20.
9. Sakai, T. & Aikawa, T., Phase transformation and thermal
conductivity of hot-pressed silicon carbide containing alumina and
carbon. J. Am. Ceram. Soc., 71(1) (1988), C-7-C-9.
10. Stutz, D. H., Prochazka, S. & Lorenz, J., Sintering and microstruc-
ture formation of p-silicon carbide. J. Am. Ceram. Soc., 68 (1985),
479-82.
11. Takeda, Y., Nakamura, K., Maeda, K. & Matsushita, Y., Etlects of
elemental additives on electrical resistivity of silicon carbide
ceramics. J. Am. Ceram. Soc., 70 (1987), C-266-67.
12. Rafaniello, W., Cho, K. & Virkar, A. V., Fabrication and
characterization of SiC-AlN alloys. J. Mater. Sci., 16 (1981)
3479-88.
13. Takeda, Y., Nakamura, K., Maeda, K. & Matushita, Y., Etlects of
additives on thermal conductivity and electrical resistivity of SiC
ceramics. Yogyo-Kyokai-Shi, 9S (1987), 860-3.
14. Soeda, A. & Maeda, K., Study on sintering process of SiC ceramics
with BeO or AlN addition by analytical electron microscopy. Yogya
Kyokai-Shi, 93 (1985), 636-48.
15. Sakai, T. & Hirosaki, N., Hot-pressing of SiC with additions of BaO
and C. J. Am. Ceram. Soc., 68 (1985) CI91-93.
Index
ABC notation, 4, 7 Black SiC, 3

Abrasion resistance, 33 Bonding strength, 187
components, 37-9 Boron
liners, 39 concentration, 138-9
Acheson method, 1,2,17,49,54,55, etlect of vapor phase addition,
120,121 . 159-60
Adhesive bonding, 248 impurities, 3
AI-B-C sintering aids, 230 optimal content and sintering
Al-C sintering aids, 229-30 mechanism, 142-5, 156-7
AlN sintering aids, 187-201, 229 role in sintering, 19
A120 3 , sintering aids, 229, 278-9 sintering aids, 187-201, 220-8,
Al2 0 3 /SiC whisker/Zr02 composites, 276-8
265-74 sintering promotion mechanism,
multiple toughening in, 265-74 158-9
Aluminium surface analysis, 35
additives, 228-33 Brazing
impurities, 2-3 active metal, 250
joining with, 247 with frit, 251-2
stabilization, 8 Bridging/pullout mechanism, 268-73
Amorphous SiC, 3
Applications, 87-92
Atomic arrangement, 175 Carbon
Auger electron spectroscopy (AES), etlect of uniform addition, 157
68 etlect of vapor phase addition,
159-60
etlect on sinterability, 161-2
Bandgap, 8 optimal content and sintering
Barium-carbon sintering aids, 282-4 mechanism, 142-5, 156-7
Basal plane epitaxial interface, 175-9 role in sintering, 19
Bending strength, 84 sintering aids, 187-201, 220-8,
Beryllium sintering aids, 281-2 276-8
Index
Carbon-contd. Debye temperature, 8

sintering promotion mechanism, Defect structures, 63-9
158-9 Deformability, 256-7, 259
chemical bonding techniques, 242 Densification, 165, 219
Chemical composition, etJect on Density
densification and grain growth, and B content, 221-5, 232-3, 278
161-2 and C content, 221-5
Chemicat stability, 16 and grain growth, 225
Chemical vapor deposition (CVD), 2, and grain size, 161
5,50,77-98,121-2,200 and particle size, 162-4
fibers, 100 DitJusion coefficients, 20-1
heteroepitaxial growth, 54-71 Dimethyldichlorosilane, 101
high temperatures, 87 Disordered layer regions, 5
homoepitaxial growth, 53-4 Dry pressing, 24
fJ-SiC crystal growth, 54-8
SiC-matrix in-situ composites,
91-2
Elastic properties, 27
structure and properties, 82-7
Electrical properties, 49
synthesis conditions, 80-1
Electron microscopy, 170, 177
synthesis device, 78-80
Electron spin resonance (ESR), 70-1
Chemical vapor infiltration (CVI),
Electronic device crystals, 49
88
Electronics materials, 70
Coincidence-site lattice analysis, 174 Electropolishing, 171
Coincidence-site lattice theory, 179, Epitaxial growth of single crystal
181 films, 45-75
Compacts methods used, 50-4
app6cationsof,37-41 Extrusion, 24
characteristics of, 34-6
manufacture of, 22-6
properties of, 26-34
thermal conductivity, 277-84, 287 Facet structure, 82
Compressive strength, 27 Fans, 40-1
Conductivity, 16 Fiber-reinforced composite materials,
Corrosion resistance, 32 88
coatings, 87-8 Fiber-reinforced metals, 266
components, 37-9 Fibers, 99-118
[C-O]/Si molar ratio, 161-2 chemical vapor deposition, 100
Crack deflection mechanism, 268, preparation method, 100-4
270-3 reactivity with pure metals, 246
Crystal chemistry, 1-11 synthesis of, 103, 114-16
Crystal grain boundaries. See Grain see also Polycarbosilanes
boundaries Finishing, 26
Crystal properties, 47-9 Flexural strength, 27
Crystal structure, 14, 47-9 Forming, 24
Crystallinity, evaluation of, 58-71 Fracture strength, 84, 187
Crystallization process, 92 Fracture toughness, 28-9,44,84,87,
Crystallographic properties, 8-9 228,265-74
C/Si molar ratio, 135, 138, 161 Functionally gradient materials; 93-4
and sinterability, 139-42 Future developments, 92-5
Index
Gas turbines, 39-40, 89 High-melting-point metal method,

Grain boundaries, 83, 169-83 250
amorphous or ultrafine-grain layers High-purity single crystals, 2
on, 170 High-purity varieties, 3
and high-temperature strength, High-resolution TEM (HRTEM),
185-212 66-8
bonding, 186-7 High-temperature strength, 29-30
coincidence-site type, 174 and grain boundaries, 185-212
conditions for identification, 172 of pressureless sintered SiC,
cross-sectional observation, 170-2 187-95
high-energy, 186 Holmium oxide, 284-6
impurity effects, 182-3 Homoepitaxial growth, 53-4
influence of surface damage layer, Hot-pressing, 18, 78, 150, 213, 270,
170-1 284
low-energy, 186 H-system, 151, 155-61
observation of, 173-81 Hydrogen, 3
pressureless sintered SiC, 196-201
regular, 173
thickness, 169 Impurity atoms, 70
validity of extended model, 202-9 Impurity levels, 15
Grain boundary diffusion, 21,158 Impurity solid solutions, 2-3
Grain boundary dislocation analysis, and polytypes, 7-8
Injection molding, 25
181
Inspection, 26
Grain boundary energy, 19
and sinterability, 204-6 Ion polishing, 171
Grain boundary layers, structural Iron impurities, 2
Isostatic pressing, 24
change under electron
irradiation, 202-4
Grain boundary phase, 220 Joining technology, 239-63
Grain boundary strength, orientation classification of techniques, 240
dependence of, 206-9 effect of fabrication methods,
Grain growth, 139,216-17,221 240-1
and strength of sintered body, factors influencing joined bodies,
225-7 240-1
Grain growth rate, 216 methods, 248-53
Grain size, 161 shape effect, 259
Green SiC, 3 solid-state, 252
Griffith's fracture theory, 27 thermal stress relaxation, 253-9
Halogen elements, 3 Lattice constant, 8

Hardness, 15,27 Lattice image observation, 171-2
Heat exchangers, 40-1 Lattice spacing, 8
Heat resistance, 15,45 Layer spacing, 8
coatings, 87-8 Lely method, 49, 55
components, 39-41 Liquid phase epitaxy (LPE), 50
Heteroepitaxial growth, 50 a-SiC, 50-1
chemical vapor deposition, 54-71 Long-period polytypes, formation
Hexagonality,7 and stability of, 6-7
291
Index
Maderlung energy, 7 Polycarbosilane&-Contd.

Manufacture of compacts, 22-6 nuclear magnetic resonance
Mechanical properties, 27-31, 84-7, spectra,107-10
190-5 preparation of, 100-3
Mechanical seals, 37 properties and molecular structure
Metallizing, 250 of, 103-10
Methyltrichlorosilane, 121, 123 thermal decomposition of, 112-14
Microstructures, 33, 85 unfusing mechanism of, 110-12
Mirrors, 90-1 Polycrystalline SiC, 275-88
Mo-Mn method, 250 Polydimethylsilane (PDMS), 101, 106
Molding technologies, 77 Polymethylpolysilanes, 133
Molecular beam epitaxy (MBE), 50, Polymorphs, 3
52-3 Polysilastyrene, 99
Polysilazane, 99
Polysiloxane, 99
Nanocomposites, 92 Polytitanocarbosilane, 99,100
Nicalon, 100 Polytypes, 1-8, 47, 49
Nitrogen, 2-3, 8 and impurity solid solutions, 7-8
Non-destructive testing, 43-4 stability of, 5-8
Non-stoichiometry, 2 structural analysis of interfaces,
Normalski ditlerential interference 179-81
microscope, 58 Powders, 2, 91-2,119-47
Nuclear magnetic resonance spectra, blanding ratios, 164
polycarbosilanes, 107-10 formation by vapor phase method,
122-6
formation mechanisms of ultrafine,
Organometallic polymers, 99 133-4
Orientation relationship with Si macroscopic and microscopic
substrate, 59-63 control, 131-3
O/Si molar ratio, 161 sintering. See Sintering
O/Si ratio, 136 structure of, 126-9
synthesis. See Synthesis
Particle size Precursor method, 99, 100
and density, 162-4 Pressureless sintering, 14, 18-22, n,
and sinterability, 162-4 135, 150, 213
blending, 164-5 and grain boundaries, 196-201
Particle size distribution, 154,217 and high-temperature strength,
Particle size function, 216 187-95
Pebble structure, 82 and joining technology, 247
Physical properties, 13-14 with Al solution, 230-3
Plasma thermal decomposition P-system, 151, 153, 155-61
method,126 Pump components, 39
Pnjunction,91
Polyborosiloxane, 248
Polycarbosilanes, 99,188,197 Ramsdell notation, 4
conversion to SiC, 112-16 Rare earth oxide/carbon sintering
infrared absorption spectra, 105-7 aids, 284-6
molecular weight and intrinsic Raw material preparation, 23-4
viscosity, 104-5 R-curve, 271
Index
Reaction bonding, 252-3 Single crystal ingots, method of

Reaction products, 246-7 growing,49-50
Reaction rate, 246 Sinterability
Reaction sintering, 78, 150 and C/Si molar ratio, 139-42
Reaction with metals, 244-6 and grain boundary energy, 204-6
Recrystallization, 2, 78 and non-sinterability, 217-20
Reflection high energy electron effect of carbon, 161-2
diffraction (RHEED), 58-60 effect of particle size, 162-4
Reliability, 34 S, H and P systems, 159
Residual impurities, 70-1 Sintering, 18-21, 25, 213-38
Rhombohedral crystal system, 4 ruds, 213,217-28,234-5,275-88
and structure, 227-8
behavior of ultrafine powder,
Sample fabrication, 187-90 149-68
Scanning electron microscopy (SEM), free energy theory, 214-17
58, 136, 138, 141, 143 powder properties for, 135-45
Screw dislocations, 7 techniques, 221-35
Secondary ion mass spectroscopy temperature, 135-8
(SIMS), 70-1 Slip casting, 24
Semiconductor substrates, 83 Sol-gel method, 2
Semiconductors, 77, 91 Solid-phase reaction, 150
Shape effect in joining, 259 Solid-phase sintering, 19
Short-period polytypes, 5-6 Solid-state joining, 252
Si-B-C system, 20 Specific heat, 32, 87
Si-C-B system, 93 Sputtering, 50-2
Si-C-M system, 246 S-system, 151, 155-61
Si-C-Ti system, 93 Stacking faults, 2, 85
Si-Ti-C-O fibers, 100 Strength, 84
Sialon, 203 and grrun growth, 225-7
a-SiC, 2,14,25,47,153,173,227-8, see also High-temperature strength
275 Strength properties, 27
bicrystals, 20 Stress concentration, 28, 186
liquid phase epitaxy (LPE), 50-1 Stress expansion coefficient, 44
synthesis, 17 Structural applications, 14
P-SiC, 2, 4,14,25,47,83,127,139, Structural materials, 13,77
142,143,153,221,225,226, Sublimation deposition, 179
227-8,276-7,282 Surface energy, 19
crystal growth, chemical vapor Surface morphology, 58-9
deposition (CVD), 54-8 Surface structures, 82
powder, 77 Susceptors, 88
synthesis, 17-18 Synthesis, 1-2, 159
SiC-A4C3-B4C system, 230 conditions and properties of
SiC-AIN-AI2CO, 3, 8 powders, 151
SiC-C system, 93 methods, 151-5
SiC-matrix in-situ composites, 91-2 a-SiC, 17
Silicon nitride, 13 P-SiC, 17-18
Single crystal films
epitaxial growth of, 45-75 Tetramethyldisilane (TMDS), 121,
methods used, 50-4 123, 127, 129, 131-3, 138, 145
293
Index
Thermal conductivity, 16,31-2, Vapor phase methods----contd.

275-88 see also Chemical vapor deposition
of sintered compacts, 277-84, 287 (CVD); Chemical vapor
Thermal expansion coefficient, 16, infiltration
32,253,256 Vapor phase reaction, 2, 3,150,159
Thermal properites, 31-2
Thermal shock resistance, 30-1
Thermal stability, 5-6 Weibull coefficient, 34
long-period polytypes, 6-7 Weibull distribution, 34
Thermal stress equilibrium, 257-9 Wettability, 241-2, 250
Thermal stress relaxation, 94, 253-9 Whisker fibers, 49
Translational lattices, 176, 180 Wide-range solid solution, 3
Transmission electron microscopy
(rE~),63-9, 127, 131, 132, 143,
151,186,196,199,200,208,220,
287 X-ray diffraction patterns, 151
Tyranno, 100
Young's modulus, 8
Uniform functionality, 93
Zhdanov notation, 4
Vapor phase methods, 17, 120-34, Zr02, See AI20 3 /SiC whisker/Zr02
151 composites

Yoshizo Inomata (Auth.), Shigeyuki Sömiya, Yoshizo Inomata (Eds.) - Silicon Carbide Ceramics-1 - Fundamental and Solid Reaction-Springer Netherlands (1991)

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Yoshizo Inomata (Auth.), Shigeyuki Sömiya, Yoshizo Inomata (Eds.) - Silicon Carbide Ceramics-1 - Fundamental and Solid Reaction-Springer Netherlands (1991)

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Silicon Carbide Ceramics-l

Fundamental and Solid Reaction

Ceramic Research and Development in Japan Series

ELSEVIER APPLIED SCIENCE

Silicon carbide ceramics-l/edited by Shigeyuki SOmiya and Yoshizo Inomata.

All rights reserved. No part of this publication may be reproduced, stored in a

Discovered by Edward G. Acheson about 1890, silicon carbide

One of the characteristics of the study of silicon carbide in

They encouraged us to study silicon carbide.

1 Crystal Chemistry of Silieon Carbide 1

2 Properties and App6cations of Silieon Carbide

3 Epituial Growth of SiC Single Crystal Films 45

4 Silieon Carbide Prepared by Chemical Vapor

5 Continuous Silieon Carbide Fibers 99

6 Preparation and Sintering Properties of Ultrafine

7 Sintering Behavior of Ultrafine Silicon Carbide Powder 149

8 Gnin Boundaries in High-Purity Silicon Carbide 169

9 Gnin Boundary and High-Temperature Strength in

10 Sintering of Silicon Carbide 213

11 Joining of SiC Ceramics 239

12 Multiple Toughening in A120 3 /SiC Whisker/Zr02

13 Sintering Aids and Thermal Conductivity of Polycry-

Recent data on crystal chemistry and polytypes on silicon carbide

SiC is well known as a substance having numerous polytypes.

Most silicon carbide is manufactured by the Acheson process, in

reacted at high temperatures. In this method, the core tempera-

1.3 IMPURITY SOLID SOLUTIONS

Concerning high-purity SiC crystals obtained under relatively

this method has a purity of approximately 98-99·9%. Compara-

Numerous polytypes9 have been discovered for SiC. Polytypes

customary to provide the Zhdanov description together with the

1.5 STABILITY OF POLYTYPES

1.5.1 Thermal Stability of Short-period Polytypes

temperatures above 2000°C. Compared with 6H, however,

I.S.2 Formation and Stability of Long-period Polytypes

Formation of long-period polytypes using screw dislocations as

1.5.3 Impurity So6d Solutions and Polytypes

1.6 CRYSTALLOGRAPHIC PROPERTIES

SiC has a high covalency, with the ionicity of SiC bonds

2830°C and under pressurized atmosphere it decomposes into a

1. Suzuki, A., Furukawa, K., Higashigaki, Y., Harada, S., Nakajima,

20. Mardix, S., Kalman, Z. H. & Steinberger, I. T., Periodic slip

Silicon carbide is a promzslng candidate for high-temperature

In the past, the list of ceramics used as industrial materials

excellent resistance to oxidation make it promising as the main

2.2 PROPERTIES OF SILICON CARBIDE1 ,3

2.2.1 Crystal Structure

sintered bodies produced using the pressureless sintering method

2.2.4 Heat Resistance

2.2.5 Thermal Conductivity

2.2.6 Thermal Expansion Coemdent

2.2.8 Chemical Stability

2.3 SYNTHESIS AND SINTERING OF SILICON

2.3.1 Synthesis of SiC

discharge in a mixed gas (consisting of an inert gas and H2 or N2)

2.3.2 Sintering of SiC

Following is a brief discussion of currently proposed sintering

T (K) Fig.2.2. Self-

at which SiC sintering proceeds, however, this diffusion

2.4 MANUFACTURE OF SILICON CARBIDE

In the pressureless sintering technique, a submicron SiC powder

Fig. 2.4. SiC cer-

the basic process resembles the conventional manufacturing