Silicon Nitride-From Powder Synthesis to Ceramic Materials

By Horst Lange,” Gerhard Wotting, and Gerhard Winter

Dedicated to Professor Karl Heinz Biichel on the occasion of his 60th birthday
Silicon nitride is a ceramic material of great interest to advanced engine construction and
mechanical engineering owing to an outstanding combination of favorable properties like high
mechanical strength at high temperatures, corrosion and wear resistance, great hardness, and
low density. The material is based on high-quality Si,N, powders, which are shaped and
sintered to the ceramic component. This overview outlines the properties required for Si,N,
powders suitable for advanced ceramics. Processes in commerical use and those under devel-
opment for the production of high quality Si,N, powders are discussed as well as material
manufacturing processes and material properties. By steadily improving powder quality, ma-
terial properties, and the economy of powder and component production, chemistry and
chemical technology play a major role in recent efforts to create a solid fundament for broad
applications of silicon nitride ceramics.

“If one would surrender to geological phantasies, one

could imagine that during the formation of our planet,
when elements combined to the compounds making up its
crust and mountain ranges, silicon reacted with nitrogen,
and the still red-hot nitrogen-silicon, on contact with wa-
ter, may have decomposed to silicic acid and ammonia.
Thus, ammonia may have been formed originally and
nitrogen thereby introduced into the forming organic
compounds when living nature first started to appear.”
H. Sainte-Claire Deville and F. Wohler[**’

1. Introduction material. Silicon nitride ceramics significantly extend the

Following speculations by Deville and Wohler,“’ silicon
nitride attracted attention for the first time as a possible raw
material for the technical synthesis of ammonia. A series of
patents from the period 1909- 1918describes the synthesis of
ammonia by heating Si,N, with solutions or dispersions of
basic oxides, hydroxides, or salts, by treatment with hot
water vapor, or by heating it in hydrogen
Because of the concurrent development of the Haber-Bosch
process, these methods never gained any importance. It is
not surprising, therefore, that this early interest in silicon
nitride soon declined.
However, silicon nitride saw a remarkable renaissance af-
ter the discovery that it can be converted into a ceramic
[‘I Dr. H. Lange
PK-F, Bayer AG
W-4150 Krefeld-Uerdingen (FRG)
Dr. G. Wotting
Cremer Forschungsinstitut
W-8633 Rodental (FRG)
Prof. Dr. G. Winter
Hermann C. Starck Berlin GmbH Co KG +
W-3380 Goslar (FRG)
[*‘I “Ueber die directe Bildung des Stickstoffsiliciums” in: Ann. Chem. Phurm.
34 (1 859) 248: “If one would surrender to geological phantasies, one could
imagine that during the formation of our planet, when elements combined
to the compounds making up its crust and mountain ranges, silicon reacted
with nitrogen, and the still red-hot nitrogen-silicon, on contact with water,
may have decomposed to silicic acid and ammonia. Thus, ammonia may
have been formed originally and nitrogen thereby introduced into the
forming organic compounds when living nature first started to appear.
limits of metallic materials under combined thermal and me-
chanical stress in corrosive environments.
2. Silicon Nitride as Ceramic Material
Silicon nitride is of great interest as a heavy-duty material
for applications in chemical engineering, wear technology,
metal working, energy technology, and especially in engine
and turbine construction.[’ 2-241 This broad interest arises
from a favorable combination of great hardness, wear resis-
tance, chemical stability, low density, and high mechanical
strength at temperatures up to 1300 “C. The application of
Si,N, ceramic parts in combustion engines and gas turbines
promises advantages like higher efiiciency and better fuel use
due to higher combustion temperatures, faster response of
oscillating or rotating engine components (valves, pistons,
turbocharger, and turbine rotors) due to low density, and
longer service intervals due to a generally improved wear
behavior.
Silicon nitride ceramics are produced either by nitriding
silicon powder compacts or by sintering Si,N, powder com-
p a c t ~ . [ ~The
~ *first
~ ~ method
l produces a porous, reaction-
bonded material (RBSN, reaction-bonded silicon nitride)
with almost negligible shrinkage; this material is used either
directly or may be densified by a following sintering step
(SRBSN, sintered RBSN).12’- 301 The second method, which
is covered comprehensively in this article, leads to Si,N,
ceramics of superior quality. These are of special interest to

Angew. Chem. Int. Ed. Engl. 30 (199i) 1579-1597 0 VCH Verlugsgesellschuft mbH. W-6940 Weinheim, 1991 0570-0833/91/1212-iS79S3.50-k ,2510 1519
advanced engine construction and advanced mechanical en- Powder synthesis, specification
gineering.
To demonstrate their technological benefits reliably,
Si,N, components require a perfect and economical control
of the entire manufacturing process, from the synthesis of
the Si,N, powder, its processing, forming, sintering to the
precise finishing of the structural component (Fig. 1).
Nonuniformity of the starting powder-for example, even
just a few extraneous particles, ill-defined particle clusters, or pressure, temperature
particle morphologies such as a mass of disordered, more or
less agglomerated lumps, fibers, or whiskers, as well as extra-
neous particles or impurities dragged in through powder
processing-induce fracture-causing structural defects, J.
which cannot be remedied in the following manufacturing ICeramic Component I testing, application
steps. Products of inferior quality and reliability are the re-
sult. Since powder-inherent sources of defects can hardly be Fig. 1. Manufacturing process from powder to component

eliminated by subsequent ceramic processing, the powder

producer has a special responsibility to supply extremely
well-defined, high-quality powders. To avoid environmental manufacturing touch many problems of solid-state chem-
contamination by, say, dust particles, the transfer of powder istry, surface chemistry, tribochemistry, and chemical engi-
processing, shaping, and sintering into clean rooms has been neering,IZ6* 351 some of which are fundamental.
discussed.[3 321 Repeatedly, this measure has been de-
‘9

scribed to improve fracture strength and reliability.[33,341

Furthermore, defects also arise during shaping, sintering,
and finishing. These nowise trivial problems have to be
solved convincingly to allow an economical, large-scale pro-
duction of silicon nitride components. Here, chemistry plays
an important role, since powder synthesis and component
3. The Structure of Silicon Nitrideorigin
of Hardness, Durability, and Strength
Crystalline silicon nitride exists in two hexagonal modifi-
cations, a and /?,which are built up from a three-dimensional

Horst Lange was born in 19.57 in Enkhausen (Sauerland) and studied chemistry from 1975 to
1981 at the Universitat Dortmund. In 1983 he received his Ph.D. under Prof. Nauman for work
on perfluoroalkylzinc and -cadmium compounds and then worked for one year as a postdoc with
Prof. Shreeve at the University of Idaho. Since 1985 he has worked at Bayer AG (Uerdingen)
and since 1989 he has been leader of the engineering ceramics group.

Gerhard Wotting was born in 19.51 in Markredwitz (Oberfranken) and studied Materials Science
from 1969 to 1977 at the Fachhochschule SelblRegensburg and the Technische Universitat Berlin
with emphasis on glass and ceramics. In 1982 he received his Ph.D. under Prof. Hausnerfor work
on the sintering behavior of silicon nitridepowders. From 1981 to 1987 he worked as a researcher
at the Institut fur Werkstoff-Forschung der Deutschen Forschungs- und Versuchsanstaltfur Luft-
und Raumfahrt in Cologne. Since t987 he has been involved in developmental work in the area
of materials technologylhigh-performance ceramics at the Cremer Forschungsinstitut, Rodental.

Gerhard Winter was born in 1937 in Klein-Mohrau (Sudetenland) and studied chemistry from
1957 to 1963 at the Universitat Tubingen. He earned his doctorate in 1966 with a dissertation on
graphite inclusion compounds under Prof. Riidorff. In 1967 he began work at Bayer AG. Since
1986 he has taught at the Universitat-GesamthochschuleSiegen. He currently heads research and
development at Hermann C. Starck Berlin in Goslar and is the author of the book “Industrielle
Anorganische Chemie ”.

1580 Angew. Chem. Int. Ed. Engl. 30 (1991) 1579-1597

network of SiN, tetrahedrons.136.371 Rigid structure and
strong covalent bonds are the cause of the extraordinary
hardness, durability, and mechanical strength of this ma-
terial.
Figure 2 shows the crystal structure of fi-Si,N,, which is
built from a Si6N, unit Along the crystallographic c
4. The Synthesis of Si,N, Powders
For the technical synthesis of high-quality Si,N, powders
the three following methods are important (see Sections 4.2
to 4.4): nitridation of silicon powder [Eq. (a)],[58-611car-
bothermal reduction of SiO, in the presence of nitrogen
[Eq. (b)] or ammonia,t62-661and ammonolysis of reactive
silicon compounds [Eqs. (c) and (d)] - 7 1 1

-
m

1 100- 1400°C
3 Si + 2N, Si,N, (a)
1450- 1600°C
3Si0, + 2N, + 6C- Si,N, + 6CO (b)
ca. 25-1400°C
+ 4NH, + 12HCI
-
3SiC1, Si,N, (C)
600- 1400°C
3SiH, + 4NH, Si,N, + 12H, (4

In contrast to direct nitridation or carbothermal reduc-

Fig 2 Section of the crystal structure of p-Si,N,, view approximately along c tion, ammonolysis does not yield crystalline Si,N, directly.
The reaction leads initially to extremely moisture-sensitive
axis, channels with a diameter of about 0.15 nm play a cer- silicon diimide [Eq. (e)], which is then transformed by pyrol-
tain role in the diffusion of atoms, even large ones. a-Si,N, ysis, via amorphous Si,N,, to a-Si,N, [Eqs. (f) and
(g)]-t67-69.721
is built from a Si,,N,, unit cell;[241since no channels occur
in this structure, diffusion is much more difficult than in
-
+ 6NH,
ca. 25 "C
+ 4NH,Cl
-
P-Si,N, (Fig. 3). SKI, Si(NH), (e)
900 - 1200°C
+ 2NH,
-
3 Si(NH), Si,N, (amorphous) (f)
1300-1500°C
3 Si,N, (amorphous) a-Si,N,

Several other reactions [Eq. (h),[73-751 (i),[761(j)[77*

781]
have not gained importance for technological or economical
reasons, such as too great expense, too slow reaction kinet-
ics, or the development of undesirable particle morpholo-
gies.

3SiS, + 4NH, - Si,N, + 6H,S

Fig. 3. Section of the crystal structure of a-Si,N,; view approximately along c. 3SiC + 4NH, -+

3Si0, + 4NH, - Si,N, + 3CH,

Si,N, + 6H,O ti)

Early work on the conditions leading to formation
of either the a or P phase indicated that the a phase, assumed
to be an oxygen-stabilized low-temperature modification with
a narrow range of existence, has the empirical formula
Si11.4-11,5N1500.3-0,5 (actually an oxinitride phase).[36,40-421
However, the formation of the a phase required significantly
less oxygen than presumed.t431By chemical vapor deposition
it was possible to produce a-Si,N, single crystals extremely
low in o ~ y g e n . [ ' ~ , Today
~ ~ - ~ a-
~ ]and p-Si,N, are regarded
as polymorphic modifications; a-Si,N, is the stable low-tem-
perature modification, since the a-Si,N, content of a powder
increases as the temperature of synthesis decreases and since
CI -+ transformation occurs only at temperatures exceeding
1650 "C. Probably for kinetic reasons, a p -+ c( transforma-
tion has not yet been observed.
The C I / ratio
~ of commercially available powders is usually
determined by X-ray 491 but also IRtsO-5 2 1 and
29Si MAS NMR spectroscopy may be applied.[53-55]29Si
MAS NMR spectroscopy is particularly useful since it can be
employed to distinguish and quantify not only the crystalline
phases but also amorphous Si3N4.Is41This method is also
suitable for the study of sintering phenomena.[56*5 7 1
Furthermore, there have been numerous attempts to syn-
thesize Si,N, by pyrolysis or carbothermical reduction from
silazanes [Eq. (k)] or ~ i l o x a n e s . [Because
~~] of the compara-
1 800-1400"C, NH,
-[SIR, - NR], Si,N,
-RH, -H2
tively complicated and costly production and handling of
silazanes, this method is less interesting for powder synthesis
than for the manufacturing of Si,N, fibers or coatings. Poly-
meric silazanes of suitable structure may be processed by
spinning to produce fibers or by melt or solution coating;
subsequent pyrolysis usually gives a 60-80 YOceramic yield.
There is also some fundamental interest in the use of sil-
azanes as binders or plasticizers for silicon nitride powder
molding by dry pressing or injection molding, since pyrolysis
leaves nothing but Si,N,.
4.1. Required Powder Properties
A Si,N, powder qualified for applications in advanced
ceramics has to meet numerous demands regarding chemical

Angebi. Chem. Inr. Ed. Engl. 30 (1991) 1579-1597 1581

and physical properties. Important criteria for powder qual-
ity include purity, crystallinity, particle shape, particle size
distribution, degree of particle agglomeration, and cr/P ratio,
as well as technological properties like good processing be-
havior in different powder shaping techniques and good sin-
tering activity.
To minimize shrinkage and to avoid the development of
density gradients during sintering, powder shaping has to
aim at particle packing densities as high and as homoge-
neous as possible. This is achieved by defined particle size
distributions, spherical particle shapes, mean particle sizes
less than 1 pm, and exclusion of coarse or hard agglomerated
particles. These factors, together with defined C and 0 con-
tents, exclusion of extraneous particles, and a high crib ratio,
are important characteristics of powders with good sintering
behavior and favor the development of a homogeneous grain
structure during sintering. The spectrum of all these proper-
ties influences the general sintering activity of a powder.
Roughly, sintering activity increases with decreasing particle
size. However, powder processing becomes increasingly dif-
ficult (dust generation, bad densification behavior in dry
pressing, high sintering shrinkage) as particle sizes decrease.
Therefore, the search for universally applicable powders
often requires a compromise between opposing demands.
These circumstances, in turn, offer possibilities for special
“powder designs”, that is, tailor-made powders with special
advantages in certain manufacturing processes. A free-flow-
ing granulated Si,N, powder, which will not crumble into
dust particles but which is easy to densify, is favorable for
charging automated dry presses and may illustrate this
point.
Some powder properties, like the c r / j ratio, have to be
adjusted during the Si,N4 synthesis; others, like particle size,
particle size distribution, or C and 0 content, may be influ-
enced subsequently by suitable powder processing (e.g.,
milling, screening, or annealing). In order to minimize the
efforts spent on powder processing, it is advantageous to
adjust as many of the required properties as possible during
the synthesis. To what extent this approach is technologically
feasible and economically appropriate depends on the syn-
thetic method chosen.
4.2. Si,N, Synthesis by Direct Nitridation
of Elemental Silicon
Direct nitridation of elemental silicon-the process used
more than 80 years ago to show the correct stoichiometry of
silicon nitride to be Si,N,[801-is still the dominant proce-
dure for the industrial synthesis of silicon nitride pow-
d e r ~ . [ ~The
~ - main
~ ~ ]processing steps are nitridation of sil-
icon powder, milling, and finally purification of the crude
product (Fig. 4).
The selection of silicon powders of different purities
strongly influences the impurity level of Si,N4. Besides com-
mercially available, low-cost, metallurgical-grade silicon of
different levels of purity, it is possible to use semiconductor-
grade silicon as starting material of extremely high purity.[”]
For the actual synthesis, piles of silicon powder are al-
lowed to react with nitrogen either discontinuously in cham-
ber furnaces or continuously in conveyor-type pusher fur-
1582
U Si Powder
NRridation
Drying
E5
a-Si3N4 powder
Fig. 4. Process for Si,N, synthesis by direct nitridation.
naces according to Equation (a) (AH = - 750 kJ mol- ’).
The reaction proceeds at a reasonable rate only above
1100 “C. Reaction rates strongly depend on particle size and
chemical purity of the silicon powder.[60.61, 831 Especially ”3
traces of Fe catalyze the nitridation.[82.841 Ow’ing to its
strong exothermal character the reaction has to be controlled
carefully. Generally, low temperatures and the presence of
hydrogen in the nitriding gas favor the formation of cr-phase
material.[60.61* 851 Too high temperatures cause not only the
formation of undesired P-Si,N4 but also strongly sintered
agglomerates of Si,N, primary particles, which finally re-
quire a more intensive milling process. Careful control of the
exothermic reaction is also necessary to avoid an uncon-
trolled temperature rise exceeding the melting point of sili-
con in the powder bed.[60,61-82] The evolution of heat can be
reduced by lowering the concentration of nitrogen in the
nitriding atmosphere after onset of the reaction (“exother-
mal control”r861).It may also be linited by a suitable, often
empirically determined temperature control depending on
nitridation kinetics, powder packing density, depth of pow-
der bed, charge size, and type of furnace.[60.61, 821
After synthesis the sintered product is crushed and finally
milled to the desired particle size. Depending on the powder
processing, possible metallic impurities due to milling wear
are removed by subsequent acid leaching.
A variation of the direct nitridation described here is the
so-called SHS synthesis (self-propagating high-temperature
synthesis[” - 901). Here the reaction proceeds very fast
(“thermite-like”) after local ignition under increased N,
pressure.t91-”I Und er these conditions the reaction zone
moves with a speed of up to 0.1 msec-’ through the powder
bed with temperatures often exceeding 1700 “C.The product
is a high-/3-phase material (/3 > 95%), which requires the
usual processing by milling and acid leaching.[951So far the
question whether high-P-phase Si,N, powder is suitable for
manufacturing advanced silicon nitride ceramics has been
answered positively only sporadically;[96.971 further investi-
gation is required.[951Other open questions in the further
development of SHS synthesis, which may also be used for
the production of other refractory corn pound^,[^^-^^^ 941
concern the control of the cr/P ratio and the mastery of cost-
efficient, large-scale production. Whether SHS synthesis will
Angew. Chem. h i . Ed. Engl. 30 (1991) 1579-1597
allow direct manufacturing of high-quality sintered compo-
1800
-
11001200
TIOCI
1000 800
nents is another interesting issue. I -,
12- ii
. S I ~ N ~ I+SClsl
) Cl
4.3. Si,N, Synthesis by Carbothermal Reduction 8- dl

This method uses the reaction of SiO, powder with carbon lg PN,
I LI
-
at temperatures of about 1500 "C in a N, atmosphere, pro- 0-
ducing Si3N4via a series of reactions [e.g., Eqs. (a), (I), and
- l - SIClSI + Clsl
(m)]. The overall reaction is given by Equation (b).

SiO, +C
SiO + C
-
- SiO + CO
Si + CO
(1)
(m)
05 06 07
1 0 0 0 ~T-'[K-'I -
08 09

3Si + ZN, --* Si,N, Fig. 5. Stability diagram for the system SiC/Si,N,/SiO,/C under varying CO
partial pressures (1061. All compounds are present as solids. pco: a) 1 atm. b)
3Si0, + 6 C + 2 N 2 - Si,N, + 6CO 0.345 atm, c) 0.1 atm, d) 0.01 atm.

Since cheap and readily available silicate raw materials

may be used, carbothermal reduction attracted early interest
during the first attempts to synthesize Si,N4 as starting ma-
terial for industrial-scale ammonia synthesis.15- l l , "] There
was no concern about chemical purity or particle morpholo-
gy; reaction mixtures of quartz sand, silicates, carbon, and
coke were even compounded with metal oxides to decrease
the reaction temperature. Purification of the product from
metallic impurities and nonreacted carbon was first achieved
by acid leaching and oxidative treatment."
well. Very fine, high-surface carbon powders favor the for-
mation of spheroidal Si,N4 particles; coarse, low-surface
powders favor whisker formation.[99,1021
After synthesis the reaction product is milled to adjust the
desired particle size and the particle size distribution (Fig. 6).
0- S O p Powder

Q
Modern procedures ensure chemical purity by careful con-
Mixing
trol of the purity levels of the starting materials. Besides
high-purity, synthetic materials from pyrolysis[621or sol-gel
reactions,[63299,I'' natural products like quartz sand[981
and clay[1oL1 may also be used, although at the expense of
purity. Though stoichiometry requires a SiO,/C ratio by
I I Carbothermal Reduction
1450 - 1550 "C, Nz

weight of just 1 :0.4 for a complete reaction, a considerable

1
excess of carbon is required in practice. Usually, SiO,/C
ratios of 1 :2 to 1 :I0 are employed.[62-66.1oz,1031Very good
results yield extremely fine SiO, and C powders from, for
example, gas-phase pyrolysis.[62*l o 3 , An intensive ho-
mogenization of the powders is necessary to ensure that the
reaction is homogeneous and proceeds to completion. A very
HCllHF Acid Leaching
good alternative is provided by sol-gel-type methods, in
which polycondensation of silicon halides with alcohols
prone to polymerization (e.g., furfurol) yield easy-to-handle Drying
polymeric granules containing Si, 0, and C in ultradisperse
distribution. Thermal cracking yields an extremely homoge-
neous SiO,/C mixture, which undergoes ready carbothermal I
~~
a-Si3N4 Powder
~
I
reduction.[' 0 5 ]
Fig. 6. Process for Si,N, synthesis by carbothermal reduction.
Because carbothermal reduction may also proceed re-
versibly, CO formed in the course of the reaction has to be
removed. In practice, the reaction is carried out either con- By tempering in air,[661NH,, or chlorine-containing atmo-
tinuously in conveyor-type pusher furnaces or in chamber spheres['". loS1at temperatures in the range of 600-800 "C
kilns, where the CO partial pressure is kept low by flowing excess carbon is removed. If required, incompletely reacted
N, . Though Si,N4 formation generally increases with in- SiO, may be removed by H F leaching.
creasing temperature, increasing amounts of Sic, depending
on CO partial pressure, are formed at temperatures exceed-
ing 1450 "C; the S i c is practically inseparable from the 4.4. Ammonolysis of Reactive Silicon Compounds
Si N C65.99. 1061 (Fig. 5).
3 4
Particle size and particle morphology may be controlled 4.4.1. Si, N4 Synthesis by Liquid-Phase Reaction
by adding either crystalline spheroidal Si,N4 particles or of SiCI, and NH,
Si,N4 whiskers as nuclei to the reaction Since
carbon acts also as a nucleation center for Si,N4 formation, The work on the liquid-phase reaction of SiCI, and NH,
its particle size influences Si3N, powder characteristics as dates back to 1830, when P e r ~ o z [isolated
' ~ ~ ~ a white precip-

Angen. Chem. Int. Ed. Engl. 30 (1991) 1579-1597 1583

itate, which he considered to be silicon tetraamide,
Si(NH,), . Subsequently, however, this precipitate was iden-
- 69* '' -
tified as silicon diimide, Si(NH), Th ough
this reaction may be described in its most simple form by
Equation (e), further investigation showed a very complex
SiCI, + 6NH, --t SI(NH), + 4NH4CI
process, which led to differently polymerized, extremely
moisture-sensitive [Si(NH),], .[' "1 Subsequent high-temper-
ature pyrolysis leads to stable, processable a-Si3N4via sever-
al intermediates and amorphous Si,N, accompanied by
NH, or N,/H, liberation [Eq. (n)].[67-69s112-1171 The
transformation of amorphous silicon nitride to crystalline
a-Si,N, proceeds above 1200 "C in a diffusion-controlled
manner with an activation energy of 306 kJ mol-l.[l 1 8 ]
3
-[Si(NH),], -1200-1400°C
a-Si,N, + N, + 3 H,
It is remarkable that NH,C1 still present from the Sic],/
NH, reaction [Eq. (e)] influences the Si(NH), pyrolysis.[' 15]
In the absence of NH,CI, Si(NH), is stable to 200 "C; it
gradually loses NH, with increasing temperature, until final-
ly amorphous Si,N, is formed. However, thermal decompo-
sition in the presence of NH,CI results in reaction of Si(NH),
and HCI to give a compound of the composition Si,N3H,CI,
which decomposes to amorphous silicon nitride above
800 "C.
Pyrolysis of Si(NH), at temperatures below 1200 K leads
to the formation of an extremely fine, moisture-sensitive,
amorphous Si,N, powder showing primary particle sizes of
about 10-30 nm and BET surfaces greater than 100 mz per
g. Prolonged heating at temperatures of 1200 to 1400 "C
induces crystallization of or-Si,N, accompanied by particle
coarsening. At temperatures exceeding 1500 "C mainly p-
Si,N, is formed.[691Particle morphology, particle size, and
organic solvent
-30 to 0 "C
Filtration
NH4CI
NH,CI Separation
I
t
I Si(NH)Z 1
Amorphous Sb y
i technological point of view the use of cheap SiCl, requires
Crystallization
Fig. 7. Process for Si,N, synthesis by SiCI,/NH, liquid-phase reaction.
1584
a/p ratio are influenced by temperature, retention time, and
impurities.[' '*O]
193
Since SiCI,/NH, liquid-phase reaction allows the synthe-
sis of a very pure and fine Si,N, powder from easily purified
and readily available starting materials, this method (often
referred to as the diimide process) has been developed on a
(e) pilot scale (Fig. 7). The SiCI,/NH, reaction is carried out in
a two-phase system consisting of an organic solvent and
liquid NH3[72* 1 1 6 , 1 1 7 . 1 2 1 1 or by reacting SiCl, vapor with
excess liquid NH, ,I' thus dissolving the by-product
NH,CI. The Si(NH), precipitate is filtered and washed with
liquid ammonia to remove residual NH,Cl and finally cal-
cined and crystallized to give a-Si,N,. In contrast to thermal
NH,CI separation by sublimation, this procedure offers the
technological advantage that no corrosive NH3/HCI vapors
are generated. However, upscaling has to take into consider-
ation the large amount of NH,CI by-product, generated ac-
cording to Equation (0). An economically favorable and
ecologically safe application or disposal has yet to be found
for this by-product.
3SiC1, + 16NH, --t Si,N4 + 12NH4CI (0)
4.4.2. Si,N4 Synthesis by Gas-Phase Reactions of SiC14
or SiH, with NH,
Owing mainly to homogeneous nuclei formation, gas-
phase reactions have a great potential for the production of
extremely tine powders.[' z31 After formation and growth of
nuclei in the reaction zone, particles cluster to aggregates and
agglomerates, which may be separated as fine dust (Fig. 8).
reactants
tube reactor
i. *. ... *.**.
:=::t:.:t*..:::;::::zone of reaction and
j )
...
nuclei formation
:.*.***. **Pi
it* 2.::) nuclei growth
Fig. 8. Particle formation in gas-phase reactions [123].
For economical and technical reasons gas-phase reactions
of SiCI, or SiH, with NH, are of special interest. From a
the separation of the corrosive NH,CI by-product through
either hot-gas filtration, extraction, or sublimation. Because
of spontaneous ignition of SiH, in contact with air, however,
the use of expensive SiH, requires extensive safety precau-
tions. A technological advantage, though, is the formation
Angew. Chem. Int. Ed. Engl. 30 (1991) 1579-1597
of hydrogen as gaseous by-product, which is easily separat-
ed. If SiCI, is used, reaction parameters may be adjusted to
approach the stoichiometry of the reaction [Eq. (p)], thus
SiCl, + 2NH, - Si(NH), + 4HCI
keeping the amount of solid NH,CI by-product low com-
pared to the corresponding liquid-phase reaction. Instead of
using expensive pressure vessels, gas-phase reactions are run
at atmospheric pressure in heated tube reactors (Fig. 9). Sim-
electrical
heaters
Si(NHh,
amorphous Si3N4
filtering system for
separation of solid products
Fig. 9. Setup of a gas-phase reactor for the synthesis of Si,N, from SiCI, and
NH,.
ilar to industrial-scale synthesis of SiO, and TiO, powders,
these reactions represent a good technological basis for a
continuous, large-scale production of fine powders. As
liquid-phase reactions, SiH,/SiCI,-NH, gas-phase reactions
also yield amorphous Si,N, precursors because of the short
retention times of gas and particle streams in the hot reaction
zone. These amorphous precursors have to be crystallized
separately in a subsequent step.
The reaction of SiH, and NH, in the temperature range of
500-900 "C yields amorphous powders with particle sizes of
30-200 nm and BET surfaces up to 26 m2g- .[", '11 Our '
investigations on SiCI,/NH, gas-phase reactions at tempera-
tures of 300-1700 "C showed the formation of extremely
Fig. 10. a-Si,N, powder by crystallization of amorphous Si,N, from SiCl,/
NH, gas-phase reaction.
Angew. Chem. i n t . Ed. Engl. 30 (1991) 1579-1597
fine, spheroidal and amorphous particles with BET surfaces
up to 300 m2g- ' 12'] Crystallization of these precursors
induces particle coarsening; thus, the BET surface may be
(P)
adjusted in the range of 2-20 m2g-1.[70,12']
Strict control of impurities, temperature, and retention
time is important for the generation of very fine, uniform,
high-a-phase Si,N, particles by crystallization of amor-
phous Si,N, (Fig. 10). The powders from SiCl,/NH, gas-
phase reactions require significantly less processing (Fig. 11)
than products from direct nitridation or carbothermal re-
duction because of their inherent fine particle size and weak
agglomeration. They are characterized by high chemical pu-
Gas-phase Reaction
300 - 1600 "C
Sublimation500 - 1000 "C
NHpCl Separation
Amorphous Sit$
~~
Fig. 11. Process for Si,N, synthesis by SiCIJNH, gas-phase reaction.
rity, good manufacturing properties, and high sintering ac-
tivity.
4.5. Si,N, Synthesis by Laser-Induced and
Plasmachemical Reactions
The work on laser-induced" 26- 291 and plasmachemical
reactions" 3 0 - 341 as alternatives to "usual" thermal gas-
phase reactions tries to avoid any heterogeneous nuclei for-
mation due to contact of the reacting gases with hot reactor
walls; thus, an extremely high degree of particle fineness and
uniformity is guaranteed. Characteristic properties of both
processes, which are based on chemical reactions already
described above, are extremely fast heating and cooling rates
of about 10' to lo6 K s-' and fast reaction rates on the order
of about s. Figures 12 and 13 show experimental setups
for laser-induced and plasmachemical Si,N, synthesis from
reactions of SiH, or SiCl, with NH,. Particle size, crys-
tallinity, a / p ratio, and stoichiometric composition of the
reaction product are influenced by mass flow, pressure, stoi-
chiometric ratio of reactants, and laser or plasmagenerator
power output. A major problem of laser-induced synthesis is
the small reaction diameter of the laser beam, which allows
only product formation rates on the order ofjust a few grams
per hour. Because of the extreme temperatures of several
1585
 filter machemical reactions are not yet of importance to large-
n scale synthesis of Si,N, powders, despite intense research.
da
:le
5. Silicon Nitride Whiskers

*-
laser beam After the discovery that crystal whiskers show unusual
mechanical strength!' 351 interest in the properties, produc-
\.window tion, and applications of ceramic whiskers grew."36313']The
use of whiskers to reinforce metallic or ceramic materials
water-cooled
aims at improving fracture toughness or, more generally,
mechanical properties of the matrix material. In spite of the
II "--ilowing gas inlet
strong general interest in ceramic whiskers, there are still
reaction gas
inlet problems in producing pure and uniform whiskers on a large
(SiH, , NH3)
scale in an economical way. The development of whisker
Fig. 12. Reactor for laser-induced Si,N, synthesis from SiH, and NH, [126]. production and processing methods especially has to take
into account health precautions in order to exclude a poten-
tial hazard like that arising from asbestos fibers." 38, 1391
thousand K in plasmachemical reactions, the reactants are Chemically, the same methods as in the synthesis of
broken apart to different radicals, which may recombine in spheroidal Si,N, powder particles are used for the produc-
various ways in the temperature gradients of the reaction tion of Si,N, whiskers. However, additional measures are
zone. Since fluid dynamics is also very important, it is very required in order to apply general techniques like vapor-
difficult to control the reaction precisely. Both laser-induced phase transport or crystallization by vapor-liquid-solid
(VLS) mechanisms to favor whisker formation.

H20
H20 5.1. Whiskers from the Reaction of Si and N,
c plasma gas
=+ stabilization gas In direct nitridation of elemental silicon, Si,N, whiskers
3 + cooling gas
are formed by reaction of silicon vapor and N, . Figure 14
shows a simple experimental setup for this production
coil
.
induction
method. Silicon is evaporated from a crucible at the bottom;

N, inlet

SiCI, n.1n
__c v
gas outlet h
pon for
temperature
measuring
fquenching gas

* '

quenching zone +filter reaction

and
nucleation
zone

ii
sedimentation

Fig. 13. Reactor for plasmachemical synthesis of Si,N, from SiCl, and NH,
[133].

and plasmachemical synthesis allow the generation of ex-
tremely fine powders with particle sizes of just 10-30 nm
and BET surfaces greater than 100 m'g-'. However, the
products often show incorrect stoichiometric composition,
are amorphous, or possess changing, not exactly repro-
ducible a//3 ratios. Furthermore, they may contain free sili-
con as an undesired by-product from decomposition reac-
tions. Because of these difficulties, laser-induced and plas-
carrier gas
Fig. 14. Reactor for Si,N, whisker synthesis from a Si/N, gas-phase reaction
[140].
a stream of inert carrier gas is used to guide the Si vapor into
a reaction zone in the upper part of the apparatus where it
reacts with N, or NH,. The Si,N, whiskers precipitate onto
graphite baffles from where they may be collected.

1586 Angew. Chem. In!. Ed. Engl. 30 (1991) 1579-1597

5.2. Whiskers from Carbothermal Reduction of SiO,

This process, which may be run continuously in conveyor-

type pusher furnaces, yields whiskers from the gas-phase
reaction of SiO and N, or NH, in CO-containing atmo-
~ ~ By adjusting stoichiometry, particle size,
s p h e r e ~ . [-' 1431
homogeneity, and packing density of the reaction mixture of
silica and carbon raw materials, addition of silicon or metal
oxides, and control of the reaction temperature, the amount
of SiO generation and, consequently, Si,N, whisker forma-
tion is optimized. Whisker formation is also favored if Si3N4
whiskers are added to the reaction mixture as growth nu-
clei.['431 Fig. 16. Amorphous Si,N, "spaghetti" from thermal decomposition of
(Si-S-N-H), polymers [74].

5.3. Whiskers from the Reaction of SICI, with NH, Si,N4 ~ h i s k e r s . [ ~ In

~ -the
~ ~first
I step, SiS, is synthesized by
reaction of Si powder with H,S at high temperature [Eq. (q)].
As described above, the reaction of SiCl, with NH, leads
to Si(NH),, which yields amorphous Si,N4 on calcination. If
small amounts of Fe or SiO, are added to this material and
Si + 2H,S -
900 "C
SiS, + 2H, (n)
the resulting mixture is heated to 1200-1500 "C in the
The high vapor pressure of SiS, which forms on dissocia-
absence of oxygen, Si3N4whiskers are formed by a vapor-
tion of SiS,, leads to SiS, whisker growth by a VLS mecha-
liquid-solid mechanism from Fe- or silicate-containing eutec-
nism from eutectic droplets of SiS and sulfur vapor. Reac-
tic melt droplets[72*1431 (Fig. 15).
tion of SiS, with NH, affords a (Si-S-N-H), polymer, which
,
thermally decomposes under NH to amorphous silicon ni-
tride [Eqs. (r) and (s)]. The amorphous silicon nitride is ob-
tained in "spaghetti-like'' morphology (Fig. 16) and may be
crystallized to cr-Si,N, with retention of morphology.

SiS, - NH,
(Si-S-N-H)wiyme,

-
ca. 25-9OO'C
NH,
(Si-S-N-H),,,,,,, Si,N, (amorphous, crystalline) (s)
900 - 1500 "C

5.5. Whiskers from the Reaction of SIC and NH,

The reaction of S i c with NH, is remarkable since it leads

Fig. 15. r-Si,N, whiskers by crystallization of amorphous Si,N, [72].
5.4. Whiskers from the Reaction of SiS, with NH,
Originally intended to produce high-purity Si,N4 powder,
the reaction of SiS, with NH, offers a good way to produce
to Si,N4 particles of unusual morphology. By heating a mix-
ture of S i c and Fe powder in NH, to 1440 "C followed by a
short-term temperature rise to 1480 "C, Glemser und
Horn1761obtained spiral-shaped a-Si,N, whiskers (Fig. 17,
left). Some of these spirals could be seen with the naked eye.
Recently, similar observations have been made in the in-
vestigation of vapor-phase deposition of Si3N4from Si,CI,,

Fig. 17 Left: a-Si,N, spirals from the reaction of Sic and NH, in presence of Fe [76]. Right: a-Si,N, spirals by vapor-phase deposition from a mixture of Si,CI,,
NH,, and H, onto a Fe-coated graphite substrate [144].

Angen. Chem. Inr. Ed. Engl. 30 (1991) 1579-1597 1587

NH,, and H, at 1200 “C onto a graphite substrate coated
with Fe-containing compounds.r144.1451 The spiral-shaped
whiskers (Fig. 17, right) are about 0.5-1.0 pm thick and
consist of a-phase Si,N, slightly contaminated by carbon
and oxygen. They show a quite uniform morphology with a
regular pitch of 3-5 pm, a spiral diameter of 5-10 pm, and
a length of 50- 100 pm. Obviously, spirals are formed only in
a narrow fiber-diameter range of about 0.1 -5 pm.
a-Si,N,. Because of their inherent fine particle size and only
weak particle agglomeration, the extent of subsequent pow-
der processing is considerably reduced compared with direct
nitridation and carbothermal reduction. Direct nitridation
and SiCl,/NH, gas-phase reactions seem to offer the best
chances to furnish economically high-quality powders for
the manufacturing of broadly applicable silicon nitride ce-
ramics.

5.6. Properties of Si,N, Whiskers Table 2. Comparison of high-purity Si,N, powders from different synthetic
methods.

Some properties of commercially available Si,N, whiskers Powder type DN 1 [a] DN 2 [b] GP [c] FP [dl CT [el
are shown in Table 1. The principal problems in whisker
Elemental analysis [wt %]
production are the requirements of high chemical purity and N 38.2 38.2 38.5 138.0 37.5
uniform whisker morphology. Because of technological dif- 0 1.8-2.1 1.7-2.0 1.1-1.6 <2.0 2.0
C <0.2 < 0.2 <0.05 <0.2 0.9
CI <0.001 <O.OOi <0.1 <0.01 [fl
Fe <0.008 < 0.03 <0.01 <0.01 0.007
Table 1. Properties of commercially available Si,N, whiskers. A1 <0.005 <0.06 <0.004 <0.005 0.2
Ca t0.002 tO.O1 <0.002 <0.005 0.01
Product Tateho SNW [a] Ube SN-W [b] a-Si,N, > 92 Yo > 94 Y@ >90% 295% 98 Yo
~~~~~~ ~ ~ ~ - - - ~ ~ ~

Synthetic method carbothermal reduction from amorphous Si,N, Mean particle 0.6 0.8 0.5 0.5 0.9
Crystal phase U U
size d,, [pm]
Diameter d 0.1 - 1.6 pm 0.1-0.4 pm
Length I 5 - 200 pm 5-20 pm [a] DN 1 =direct nitridation (LC 12 - SX, H. C. Starck, Berlin). [b]
Aspect ratio / / d 3 - 2000 10-200 DN 2 = direct nitridation (LC 10, H. C. Starck, Berlin). [c] GP = SiCI,/NH,
Density 3.18 g ~ m - ~ 3.18g~m-~ gas-phase reaction (Grade GP, H. C. Starck, Berlin). [d] FP = SiCI,/NH3 liq-
Fe max. 1000 ppm 4000- 5000 ppm uid-phase reaction (SN E 10, Ube Ind., Tokyo). [el CT = carbothermal nitrida-
A1 rnax. 2000 ppm < 100 ppm tion (A 200, Toshiba Ceramics, Tokyo). [fl Not determined.
Ca max. 5000 ppm < 100 ppm
Mg max. 2000 ppm not specified
0 not specified 2-3%

[a] Tateho Chem. Ind.. Japan [143]. [b] Ube Ind., Japan [72].
ficulties in producing a homogeneous distribution of Si,N,
whiskers in a matrix material, fracture-causing structural
defects are often induced during material processing; in these
cases, the originally intended toughening of the matrix actu-
ally turns out to be a ~ e a k e n i n g . 1 ’ ~ ~ .Fundamental prob-
lems in whisker processing are often connected with shaping
and sintering, since heaps of needlelike particles are much
more difficult to compact by, say, dry pressing than heaps of
spheroidal particles.
6. Remarks on the Procedures for Synthesis
of Si3N4 Powders
The production of Si,N, whiskers is not yet commercially
important, since Si,N, whisker-reinforced materials have
not found broad applications because of high costs and a
lack of large-scale production methods for reliable compo-
nents. For technological and economical reasons, especially
carbothermal reduction and whisker growth from amor-
phous Si,N, should be suited best to meet an eventually
increasing demand.
7. The Manufacture of Sintered Si3N4 Ceramics
7.1. Fundamentals of Sintering and Structure
Development
7.1.1. Physical and Chemical Aspects of Si,N, Sintering

A comparison of chemical and physical characteristics of “Dry” sintering techniques used in densification of oxide
powders from commercially used synthetic methods shows ceramics cannot be applied to the sintering of Si,N, powder
that direct nitridation, carbothermal reduction, and am- compacts. Strong covalent Si-N bonds hinder useful mass
monolysis of reactive silicon compounds are principally able transport through grain-boundary or lattice diffusion, The
to furnish very fine, high-purity Si,N, powders for applica- activation of diffusion by simply raising the sintering tem-
tions in advanced ceramics (Table 2). Often variations of perature is limited by ever-increasing thermal decomposition
particle sizes, particle size distribution, and particle surface [Eq. (91.
properties, which are important to ceramic processing, may
be carried out after Si,N, synthesis by suitable powder pro-
cessing. Direct nitridation and carbothermal reduction use
Si,N, (solid) -- 3 Si (liquid)
3Si (gas)
+ 2N, (gas)

cheap raw materials and yield crystalline Si,N, directly.

However, the reaction products require extensive subsequent Since a N, partial pressure of 1 bar is reached at about
processing. On the other hand, ammonolysis of reactive sili- 1900 “C, several precautions have to be taken in order to
con compounds yields moisture-sensitive products which re- prevent excessive decomposition during sintering of Si,N, at
quire further thermal treatment for crystallization to yield high temperatures. Most important is the addition of com-

1588 Angew. Chem. Ini. Ed. Engl. 30 (1991) 1579-1597

pounds that form molten silicate phases and allow densifica- pN2 Iatml-
tion by liquid-phase sintering mechanisms. Well-suited addi- 1 0 - 4 1 0 - ~ 1 0 - ~ 1 0 -1~ 101 102 l o 3
tives include alkaline-earth oxides and rare-earth oxides ei- 10-2 3

ther alone or in combination with AI,O, or A1N.[148-152]

10-3 2
Above 1300 "C sintering additives react with SiO, or
Si,N,O always present in Si,N, powders to yield molten I 10-4 1
silicate phases. In the case of sufficient wetting and solubility
of Si,N,, these silicate melts allow densification by capillary- 1 0

force-induced particle rearrangements and dissolution/re- PSi [atml lg Psi

10-6 -1
precipitation processes.
The efficiency of these mechanisms is illustrated by a lo-' -2
model experiment using a presynthesized, nitrogen-saturat-
10-8 -3
ed Mg-AI silicate glass as sintering additive (Fig. 18). At

2000
10
10-10 1 2 3 4

lg PN2-
5 6 7 8

I 1800]

I Fig. 19. Silicon vapor pressure in equilibrium with silicon nitride as a function
of N, pressure and temperature (1491.The bold lines show temperature inter-
SXlO [%]
vals of 100 K from 1300 "C to 2200 "C. The hatched region represents the range
dSldt
where sintering of Si,N, takes place. The pressures were measured in Pa.

7.1.2. Structure Development

t [min] - After particle rearrangement at low temperatures, which

Fig. 18. Dilatometric investigation of Si,N, sintering in the absence (1) and
presence ( 2 ) of a nitrogen-saturated glass [153]. Temperature----. dS/df
-shrinkage dS/df in [%min-'].
1300 "C dilatometric monitoring of the process shows densi-
fication by capillary-force-induced particle rearrangement,
since nitrogen saturation of the silicate glass does not allow
further dissolution of N, or Si,N,. With increasing temper-
ature Si,N, solubility increases and densification via dissolu-
tion/reprecipitation is observed. A Si,N, sample without
sintering additives shows a completely unsatisfactory densi-
fication.
Another important precaution is sintering under high N,
pressure to suppress decomposition according to Equa-
tion (t). Figure 19 shows that this technique significantly ex-
tends the temperature range of Si,N, sintering.
increases the packing density almost without influencing
particle shape and particle size distribution, true sintering by
dissolution/reprecipitation occurs at higher temperatures.
At present, structure development is thought to depend on
the kind of Si,N, starting powder. Starting from a-Si,N,,
reprecipitation of dissolved cc-Si,N, from almost saturated
or slightly oversaturated solutions leads to crystallization of
needle- or rodlike P-Si,N4 grains far from the energetic min-
im~m.['~ ~ ] a fine-grained, needlelike structure has a
Since
positive influence on fracture-mechanical properties ("in-
situ whisker reinforcement") for numerous applications, this
grain morphology is desired.[155,15@. If P-Si,N, powder is
used, dissolution/reprecipitation occurs almost in equilibri-
um. The surface energy difference between small and large
particles causes a continuous dissolution of small particles
and their reprecipitation on large grains. This process allows
grain growth with minimization of boundary surface energy

Fig. 20. Structure development in sintering of a Y,O,/Al,O,-doped Si,N, powder [158]. Left: 1800 "C (10 min). Middle: 1800 "C (2 h). then 1820 'C (2 h). Right: SO
sintering cycles (see middle for conditions). Additives: 1 5 w t % Y , O , + 3.4 w t % AI,O,.

Angew. C'hrm. Int. Ed. Engl. 30 (1991) 1579-1597 1589

leading to the development of approximately globular
Prolonged thermal treatment, far beyond the moment
when densification is complete, favors grain growth by min-
imization of boundary energy (“Ostwald ripening”) also in
needle-grained structures and leads to grain coarsening with
growth of spheroidal grains. In this case, structural develop-
ment leads to the formation of globular grains, no matter
whether a- or P-Si,N, has been used as starting material. A
study on structure development on prolonged heat treatment
of a-phase Si,N, is shown in Figure 20.
After sintering, all these materials contain an amorphous
or semicrystalline secondary phase in between grain
boundaries or in grain triple points (Fig. 21). Since especially
Fig. 21. Transmission electron microscopy (TEM) of amorphous secondary
phase along grain boundaries in sintered Si,N, [159]. The black lines show the
directiop (lOTO),, A a grain triple point, B a grain boundary.
material properties at high temperatures are greatly influ-
enced by the secondary phase, the reduction, modification,
or complete elimination of this phenomenon is of major
importance to the optimization of Si,N, ceramic proper-
7.1.3. Influence of Sintering Additives
The amount and chemistry of the molten silicate phase,
which is formed by sintering additives, are of importance to
the course of sintering, since they determine sintering kinet-
ics. For example, the kinetics of MgO-doped systems are
governed by dissolution, whereas the rate of diffusion is
crucial in Y,O,-doped The influence of typi-
cal additives on sintering behavior is shown in Figure 22. For
instance, the densification of Y,O,-doped Si,N,, which sin-
Fig. 23. Left: Globular structure in a F-Si-
AI-0-N material; right: needle-type struc-
ture in a MgO/AI>O,-doped material.
1590
ters at relatively high temperatures, may proceed at the low
+
temperature level of (MgO Al,O,)-doped materials if
AI,O, is added.
20001
r20
1800
s [%.I
{ ] ] ]
20 40
t [min]-
60 80 100
Fig. 22. Influence of type of additives on sintering behavior. - ~ -tempera-
-
ture,-MgO + A1,O,,---YY,O, +
A1,O,,---YY,O,.S = shrinkage.
Different additive systems may form compounds of the
type a‘-Me(Si,AI),(N,O), or /3’-Si6-xAI,01Ns-, with newly
precipitated Si,N, grains.[162.1631 The expectation that
Si,N, ceramics free of secondary grain-boundary phases can
be produced by using this principle has only been fulfilled for
Be-doped 1601
The amount and kind of additives also influence structure
development and thus material properties. Fine-grained
Si,N, structures are favored in systems where the molten
silicate phase shows a relatively high viscosity at sintering
temperatures (e.g., systems doped with rare-earth oxides).
The influence of additives is especially clear in the structure
development of /3’-SiAION materials, where globular grains
are favored. Figure 23 shows a comparison of these materi-
als with a material sintered with MgO/AI,O,, which devel-
oped a needlelike structure. The exact reasons for this behav-
ior are not yet completely understood.
7.1.4. Influence of Powder Characteristics
Besides the kind and amount of additives, the sintering
behavior, structure development, and, finally, material prop-
erties depend strongly on the powder characteristics of the
starting Si,N, powder. Of further importance are the pow-
der properties resulting from processing prior to shaping and
sintering; in particular, it is necessary to break up particle
agglomerates and to produce a homogeneous distribution of
sintering additives. Relevant powder properties can be divid-
Angew. Chem. Int. Ed. Engl. 30 (1991) 1579-1597
ed into physical, chemical, and technical characteristics,
which together determine processing behavior and sintering
activity in a complex way.
The influence of ct/P-Si,N, ratio has already been
mentioned and is still a subject of intensive discus-
~ i 0 n . I1~2 4~* 1.s 5 , 16’] A high a-phase content enhances
sintering activity and favors the development of rodlike P-
Si,N, grains. With respect to sintering activity, amorphous
Si,N, would be of even greater advantage. However, its
large-scale use is complicated owing to its sensitivity towards
hydrolysis and its low powder-packing density, which results
in enormous shrinkage during sintering.
Among chemical powder characteristics, the oxygen con-
tent is of special importance, since it influences the softening
behavior and the amount and viscosity of the silicate phase
formed on reaction with sintering additives. Although a
great amount of low-viscosity silicate melt phase enhances
sintering, it has a negative effect on the high-temperature
properties of the material if the silicate phase remains as an
amorphous, glassy grain-boundary phase. Thus, the oxygen
content has to be adjusted to the amount of sintering addi-
tives required (or vice versa); it is a compromise between
beneficial effects on sintering behavior and detrimental ef-
fects on high-temperature material properties. Usually, com-
mercially available powders possess an oxygen content in the
range of 1 -2 %.
Also the distribution of oxygen in the particle itself is of
importance. If oxygen is concentrated on particle surfaces, it
is directly available for silicate phase formation by reaction
with sintering additives. In this way, surface oxygen im-
proves sintering activity considerably.[’66316’] Therefore,
high-quality Si,N, powders usually possess oxygen-enriched
particle surfaces, which allow fine-tuning of the amount of
sintering additives required for complete densification and
thereby result in improved material properties. The coating
of a Si,N, particle with an amorphous layer rich in oxygen
is shown in Figure 24.[’68’
Fig. 24. TEM picture of the coaling of a Si,N, particle with an amorphous
layer rich in oxygen [168]. Beam direction (T2TO). The arrows indicate Schottky
partial dislocations.
Free carbon has a negative influence on sintering behav-
ior, since it reduces the oxygen content of the powder with
formation of volatile SiO and CO. The resulting ill-defined
variations in silicate phase chemistry may cause incomplete
sintering, undesired structure development, and, finally poor
Angrn. CIwm. l n l . Ed. Engl. 30 (I9911 1579-1597
material properties.[’ 5391 6 9 1 Chemically bonded carbon in
the form of SIC is much less critical. Because of its inherent
stability, this material may be considered as inert
1 4 7 1 The effects of other impurities have to be
filler.t108*
judged by their behavior in sintering; they may dissolve in
the liquid phase with incorporation in the silicate structure
or they may remain as particle inclusions with or without
reaction with the Si,N, matrix. Metal oxides and metal
halides either evaporate during sintering or dissolve in the
liquid phase, lowering its viscosity with the already discussed
effects on sintering behavior, structure development. and
material properties.
Metal particles like Fe, Mn, and Ti react with the Si,N,
matrix to form silicides or nitrides.[’701Compared to origi-
nal particle sizes, inhomogeneities due to chemical reactions
are larger” and thus generally detrimental to mechanical
properties like fracture strength (Fig. 25).
&
y
1 300-
a[MPa] pm
200-
100- scattering range
surtacecrack
I
I I I I I I I I
200 400 600 800
Size of extraneous particles [pm] -
Fig. 25. Dependence of fracture stress u on size of extraneous particles in Si,N,
sintered ceramics (1711.
Granulometric powder properties, which involve particle
size distribution, particle morphology, and particle agglom-
eration, influence processing behavior and the extent of pow-
der processing required to produce an admixture of high
sintering activity. Since sintering activity increases with in-
creasing surface energy, “sub-pm” powders with a high con-
tent of particles less than 1 pm are advantageous. The
amount of “coarse grains” attracts special attention, since
these particles will dissolve in the silicate phase comparative-
ly slowly. Therefore, sintering is slowed down and some par-
ticles may survive more or less unchanged to form structure
inhomogeneities.
Whisker- or fiberlike Si,N, particles cause similar effects,
additionally making powder shaping more difficult. “Coarse
grains” greater than 1 pm, as well as deviant particle mor-
phologies, usually are not destroyed during powder process-
ing to generate the sintering admixture. Powder processing
has to guarantee that agglomerates of primary crystallites,
which are principally present, are broken apart, since their
size and the lack of sintering additives in their cores would
induce very large defects and thus limit strength and reliabil-
ity of the sintered component. Furthermore, the size and
hardness of these agglomerates determine dispersibility and
homogeneity of the sintering admixture; these properties are
very important quality criteria. A qualitative and quantita-
tive description of agglomeration mechanisms and agglom-
1591
erate properties is steadily gaining importance as a goal of
research." 721
The shape-sharp-edged to spheroidal/globular-and the
size distribution of primary crystallites determine also the
limits of densification and the extent of sintering shrinkage.
Green densities (i.e., the densities of the powder-shaped
bodies prior to sintering) must be as high as possible to
reduce the danger of critical tensions due to high shrinkage;
these tensions would otherwise lead to cracks and fissures
during temperature treatment.
Physical, chemical, and technological powder properties
have a complex influence on sintering behavior, structure
development, and final material properties. The relative in-
fluence of a single powder property may be estimated by
means of statistical ~a1culations.l'~~~ 711
7.2. Technological Aspects
7.2.1. Powder Processing
The processing of a Si,N4 powder to a highly sintering
active admixture aims at breaking up particle agglomerates
and distributing homogeneously the sintering additives. Wet
processing in mills of high-energy density is well-suited for
this purpose. However, attention has to be paid to the kind
and amount of wear debris from these machines. Oxygen
contamination due to partial hydrolysis of Si,N4 and carbon
contamination are important if processing is done in either
water- or organic-solvent-containing media. The extent of
processing depends on starting powder quality, the desired
powder shaping and sintering techniques, and the material
property profile of the component to be manufactured. Since
powder characteristics may vary considerably during pro-
cessing, rigorous controls are necessary to ensure the highest
possible uniformity of processing from lot to lot.
Fig. 26. Y distribution in Y,O,-doped Si,N, sinteringpowder admixture. Left:
By mechanical dispersal of Y,O,. Right: By precipitation of Y(OH),.
Extremely homogeneous distribution of sintering addi-
tives may be achieved far better by precipitation from solu-
tion than by intensive mechanical dispersion. Here, codrying
of salt solutions and Si,N, slips['531has been investigated as
well as precipitation of hydroxides from salt solutions[' 731
and precipitation by hydrolysis of metal alcoholates.'' 74, 1751
Figure 26 shows that this approach leads to extremely homo-
geneous additive distributions.
1592
7.2.2, Powder Shaping
Axial or isostatic dry pressing, extrusion, slip casting, or
injection molding is used for powder shaping (Fig. 27).
These procedures are well-known to the ceramic industry.
Selection criteria depend on component complexity, on eco-
nomics and, if required, on the feasibility of large-scale pro-
duction. Dry pressing is used mainly for the production of
Powder shaping methods
I
I I I I
axial molding
powder product
p.
injection
powder
powder
rub&r She,l 'hydraulic liquid
Droduct
gypsum mold
Fig. 27. Ceramic powder shaping methods. p = pressure
components with simple geometry like plates, tubes, or cylin-
ders. Slip casting and injection molding are favored to pro-
duce net-shape components of complex geometry on a large
scale. All shaping techniques require certain, usually organ-
ic, processing additives. Binders ensure the stability of pow-
der compacts in dry pressing, dispersion agents allow the pro-
duction of highly particle-loaded, stable slips for slip casting,
and plasticizers allow injection molding. Since especially in-
jection molding promises an economical, large-scale produc-
tion of complex components, its development has attracted
worldwide attention.r'76-'78]All organic additives have to
be burned out quickly and quantitatively prior to sintering
without inducing defects like pores, cracks, or fissures. Be-
cause of the high amount of plasticizers, usually about 10-
25 weight percent, this step is especially critical in injection
molding. Although shaping is finished in a few seconds, plas-
ticizer burnout requires several hours to several days de-
pending on component thickness and kind of plasticizer. To
improve this situation the development of new organic plas-
ticizer systems, which may be decomposed either chemically
or thermally after powder shaping, is of fundamental impor-
tance.
7.2.3. Sinrering
The sintering techniques used for the manufacture of
Si,N, ceramics are compiled in Figure 28 together with pro-
cess characteristics. Axial hot pressing in graphite matrices is
used almost only for components of relatively simple geome-
try like rods, plates, or cylinders. Hot isostatic pressing
(HIP), however, allows sintering of complex compo-
nent~.["~] Powder compacts are sealed gas-tight in metals or
glasses of high melting point; plastic deformation of the
softening material of the capsule results in uniform applica-
Angew. Chem. Inr. Ed. Engl. 30 (1991) 1579-1597
 Method: Hot Pressing Sintering Hot Isostatic Pressing
normal gas sinter-HIP capsule-HIP
Material pressure pressure
abbreviation HPSN SSN (GP-)SSN HIP-SSN HIP-SN
~ ~~~

starting material S$t$ sintering Si& powder compacts Si& powder compacts

processing
admixtures
+
hot pressing sintering
J. A
presintering encasing
steps

conditions 1 i-7
< 182OOC < 2100°C
+
(to 293% th. D.)

HIP
J.
HIP
T 5 1880°C < 2000°C < 2000°C
t 21 h <5h <5h <2h c4h
p(gas) 2 50 MPa mech.) 0.1 MPa N2 2 10 MPa N1 2 200 MPa (Nt + Ar) 5 200 MPa Ar

product
1
dense body
LJ near nel-shape
component
G near net-shape
component
decasing

process
characteristics
linear shrinkage only height 218% 5 18%

finishing very extensive less extensive less extensive extensive

Fig. 28. Sintering processes for the manufacturing of dense Si,N, components. mech. = mechanical, th. D. = theoretical density.

tion of the external gas pressure on the powder compact.
Densification occurs with very precise retention of shape.
After sintering is complete, the capsule is removed mechani-
cally (sandblasting) or chemically (etching). Thus, this so-
called capsule-hipping is an expensive and slow procedure
not suited for low-cost mass production of ceramic compo-
nents. Usually, it is applied for the production of compo-
nents which are used under extreme conditions and would
otherwise require an even greater effort for
However, "hipping" allows the manufacture of Si,N, sin-
tered materials with very good high-temperature properties
due to the only very small amount-or even absence-of an
amorphous grain-boundary phase.["', '"I These develop-
ments, to date on laboratory scale, may gain importance for
the manufacturing of Si,N, components showing long-term
mechanical strength at high temperatures.
industrially employed.['491In this process a powder compact
is heated to sintering temperature in a powder bed consisting
of Si,N, and BN. The course of temperature and pressure
has to be adjusted to furnace geometry, sintering additives,
and powder compact geometry (characteristic data in
Fig. 28). Sintering under normal pressure limits the maxi-
mum temperature to about 1820 "C owing to the decomposi-
tion of Si,N,. However, sintering at increased N, pressure
allows a further temperature increase and results in a pres-
sure-assisted densification, which is effective only if the stage
of closed porosity above 93 % theoretical density was
reached by normal pressure sintering. This method shortens
the overall time required for complete densification ; it even
has a (limited) ability to increase strength and reliability of
Si,N, sintered components because of some defect healing.
A typical course of temperature/pressure versus time in gas
pressure sintering is shown in Figure 29.t'491

-100
7.2.4. Finishing

-Oo
-60
t
h 2
Since sintered components are rarely used as fired, that is,
without precise finishing, corrections of shape with adjust-
lbarl
-40
ments of tolerances, as well as high-quality surface finishing,
are required, especially for applications as engine or turbine
P
i -20 components. Because of high hardness and comparatively
8.
8. high toughness of Si,N, materials, these steps are time-con-
*.
I I I I I suming and expensive. Mainly cutting, grinding, honing,
20 40 60
t bin1 -
80 100 120
lapping, and ultrasonic erosion are used for finishing. Laser
cutting and spark erosion are under d e v e l ~ p m e n t .1841
~'~~~
Fig. 29. Temperature-pressure-time profile during gas-pressure sintering of
Si,N, 1149). Ultrasonic erosion is of special interest, since it allows the
production of very complex components (e.g., gas turbine
rotors) from simple monolithic shapes (Fig. 30). Generally,
Cost-efficient mass production of near-finished Si,N4 finishing has to be done extremely carefully in order to avoid
components is possible by N, gas-pressure sintering, which strength and reliability deterioration by fracture-causing
was developed during the seventies and which is meanwhile surface defects like cracks, fissures, and pits.

Angew. Chem. I n i . Ed. Engl. 30 (1991) 1579-1597 1593

 Fig. 30. Left: Manufacturing study for ultra-
sonic erosion of a turbine wheel from a hot-
pressed Si,N, monolith [ISS]. Right: Turbine
wheels made of Si,N, for applications in auto-
motive gas turbines [186].

8. Physical and Chemical Properties forts to improve Si,N, powder quality and production meth-
ods. The influence of sintering techniques on material prop-
8.1. Physical Properties erties is reflected in the so-called Weibull modulus (a statisti-
cal parameter to characterize a property distribution over a
Table 3 shows a compilation of important properties of manifold of samples), which is used to characterize the scat-
completely densified Si,N, ceramics. The scattering range of tering of fracture strength and thus the reliability of the
the data is mainly due to structural differences, which are material. The (limited) ability of a particular sintering pro-
influenced by starting powder characteristics, amount and cess to anneal defects like pores, bubbles, internal cracks,
kind of sintering additives, powder shaping, and sintering and fissures is thereby quantified to a certain extent. The
techniques as well as temperature, pressure, and soaking following values are typical for Weibull moduli of commer-
time during sintering. Fracture strength is surely the charac- cial materials: pressureless sintered Si,N, > 10; gas-pres-
sure-sintered Si,N, (GP-SSN) > 15; isostatically hot-pressed
Si,N, (HIP-SSN), > 20.
Table 3. Physical properties of dense Si,N, material. A general comparison of fracture strength is difficult,
Property Value since materials for specialized applications have been devel-
~~~ -
oped. Here, the main criteria of quality include not only
Decomposition temperature 2173 K fracture strength, but also the strength level at temperatures
Theoretical density (th. D.) a-phase: 3.168-3.118 g ~ m - ~
a-phase: 3.19-3.202 gcm-’ greater than 1000 “C, fracture toughness, and hardness or
Material density 95-100% th. D. wear resistance. Today, the state of the art is a strength level
Thermal expansion coefficient (293 -1473K) 2.9-3.6 10-6K-1
Specific heat
~

700J Kg-lK-I
of 800- 1000 MPa at room temperature; however, materials
Electrical resistance [a] Rcm with fracture strengths exceeding 1000 MPa have been de-
Microhardness (Vickers) 1400-1700 MNm-’ scribed.[188.1891
Bending strength [a] [b] 600-1000 MPa
Fracture toughness [a] 5-8 MPam”’ By controlled structure development (in situ whisker rein-
Elasticity modulus [a] 280-320GPa forcement) it is possible to increase the fracture toughness of
Thermal conductivity [a] 15-30 Wm -’K-’ Si,N, materials from a level of about 7 MPam1j2 to almost
Critical temperature difference 600-800 K
in thermal shock 10 MPam1/2;r1901 a conventional material is compared to an
“in situ whisker reinforced” material in Fig. 3I.[l9l1 The
[a] RT = room temperature. [b] Four-point bending toughness level attained here could formerly be achieved
only by reinforcement with extraneous particles (like whiskers
or l9,1
teristic property determined most often; usually it is consid- At temperatures exceeding 1000 “C a decrease of strength
ered as a key criterion of quality. Some years ago, a signifi- in many materials is caused by slowly softening amorphous
cant dependence of material properties on the method of grain-boundary glass phases. The amount and kind of these
producing the starting powder was observed.[1871However, phases determine creep and long-time fracture strength. All
these differences almost vanished as a result of constant ef- modifications of materials or technological processes to im-

Fig. 31. Improving fracture toughness Kjc

by in situ whisker reinforcement (1911. Left:
Structure of a conventional Si,N, material
(K,= = 6.5 MPam”*). Right: Structure of
an in situ whisker-reinforced material
(K,<= 9.5 MPam’’z).

1594 Angew. Chem. Inr. Ed. Engl. 30 (1991) 1579-1597

 prove the dependence of fracture strength on temperature
and to improve the strength level at high temperatures aim
at reducing the amounts of amorphous grain-boundary glass
phases or at generating higher refractory, crystallized grain-
boundary phases together with optimization of structure.
Recently, a successful realization of these concepts has been
reported." 891
An evaluation of a commercially available MgO-doped
material is given in Figure 32.[lg4]Here, the failure probabil-
ity resulting from Weibull analysis in the range of linear
elastic stress up to 900 "C and probable reasons for positive
or negative deviations caused by defect annealing or defect
induction is shown. Figure 32 also shows the life expectancy
of the material below short-time fracture load. To avoid
1200-
,rn,,,,y
1000-
fast fracture
800-
1 600-
0 [MPa]
400-
200-
I
I I I I 1 I I I
200 400 600
7 ["C] -
800 1000 1200 1400 1600
Fig. 32. Fracture strength of hot-pressed, MgO-doped Si,N, as a function of
temperature and time [164]. u = flexural strength.
premature failure at a given temperature, the material should
bear only considerably lower mechanical stresses than short-
time fracture strengths would indicate.
8.2. Chemical Properties
Owing to the broad possible applications of sintered
Si,N,, its chemical properties have been investigated with
special regard to corrosive behavior.['95 - lg8]
Silicon nitride is inert to numerous molten metals (e.g., Al,
Zn, Sn, Pb, Cu, Ag, and Cd); however, in contact with
molten transition metals like Fe, Co, Ni, V, and Cr, it reacts
readily to form metal silicides and N,. In contract with
molten salts, oxidic slags, and glasses, only slow corrosion
occurs. With the exception of hydrofluoric acid, Si,N, ce-
ramics are resistant to mineral acids. Mainly porous Si,N,
materials are attacked by hot strong caustic solutions or
melts with formation of NH,.
In the use of engine components made of Si,N, (e.g.,
valves, turbocharger, gas turbines) the oxidation behavior of
sintered Si,N, is especially important. Since Si,N, is coated
with a thin protective layer of SiO, on heating in air, a good
oxidation resistance is shown up to 1400 "C. In high-temper-
ature oxidation two fundamentally different mechanisms of
damage are observed.['961
The first mechanism is based on the diffusion of sintering
additives and impurities along grain boundaries owing to the
higher oxygen potential at the surface of the material. Reac-
Angew. Chem. Inr. Ed. Engl. 30 (19911 1579-1597
tion with SiO, at the surface results in the formation of
oxidic glass phases of low viscosity, which induce enhanced
corrosion accompanied by N, formation. N, pores and
modification changes of grain-boundary phases leading to
different thermal expansion coefficients between glass phase
and matrix material induce defects which lower the fracture
strength of the material.
A second mechanism will lead to complete destruction
if4epending on sintering additives-crystalline phases are
formed during sintering, which are readily oxidized with con-
comitant volume expansion. Internal stress may build up so
strongly, that the sintered component is completely destroyed
in a short time. This phenomenon has been observed primar-
ily in some ternary Y-Si-0-N and Ce-Si-0-N phases.['991A
suitable selection of sintering additives, the use of high-puri-
ty starting powders, and a reduction of additive and oxygen
content are important in the development of high-tempera-
ture oxidation-resistant sintered Si,N, materials.
9. Summary
Sintered silicon nitride is a promising material for applica-
tions in engine construction, mechanical engineering, wear
and chemical technology, where high mechanical strength at
high temperatures, corrosion and wear resistance, hardness,
and low density are desired. Cutting tools, bearings, mill
cladding, bearing gaskets, and engine components like valves,
valve guides, turbocharger rotors, and gas turbines are promi-
nent examples where this material is already used routinely
or where it is being tested as a basic material.
To date, the required high-quality Si,N, powders are com-
mercially produced mainly by direct nitridation, to a lesser
extent also by SiCI,/NH, liquid-phase reaction (diimide pro-
cess). Among processes under development, the SiCIJNH,
gas-phase reaction seems to offer the best potential to fur-
nish economically high-purity, highly sintering-active Si,N,
powders on a large scale.
Chemical and physical characteristics of the starting mate-
rial, kind and amount of sintering additives, and sintering
technique determine material properties. Their interdepen-
dence influences structure development as well as the kind
and composition of silicate phases formed at grain
boundaries.
Crystallization and reduction of the amount of these sili-
cate phases are important to further improve material prop-
erties like fracture strength, creep, and corrosion resistance
especially at high temperatures.
A flawless manufacturing process from powder synthesis
to finished component is required to produce high-quality,
reliable ceramic components. Injection molding, as a pow-
der-shaping technology using cheap, high-quality, easily
processible Si,N, powders, has a great potential for the
large-scale manufacturing of very complex components.
Pressureless or low-pressure sintering is of great interest for
the low-cost production of near-finished components. The
development of economical methods for finishing sintered
components of this very hard material is still necessary to
decrease the very high finishing costs.
The work on economical methods to produce high-quality
Si,N, powders, to improve steadily powder and material
1595
properties, and to manufacture reliably working ceramic
components of superior quality should be viewed in its en-
tirety as a necessary requirement for a broad application of
silicon nitride advanced ceramics in the future.
Received: May 8, 1991 [A 844 IE]
German version: Angew. Chem. f03 (1991) 1606
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