J. Am. Ceram. Soc.
, 93 [6] 1501–1522 (2010)
Journal
Silicon Nitride for High-Temperature Applications
Fraunhofer Institute Ceramic Technologies and Systems (IKTS), Winterbergstr. 28, Dresden 01277, Germany
In this paper, a summary of the development of high-tempera-
ture silicon nitride (T412001C) is provided. The high-temper-
ature capacity of various advanced commercial silicon nitrides
and materials under development was analyzed in comparison
with a silicon nitride without sintering additives produced by hot
isostatic pressing. Based on this model Si3N4 composed of only
crystalline Si3N4 grains and amorphous silica in the grain
boundaries the influence of various sintering additive systems
will be evaluated with focus on the high-temperature potential of
the resulting materials. The specific design of the amorphous
grain-boundary films is the key factor determining the properties
at elevated temperatures. Advanced Si3N4 with Lu2O3 or Sc2O3
as sintering additive are characterized by a superior elevated
temperature resistance caused by effective crystallization of the
grain-boundary phase. Nearly clean amorphous films between
the Si3N4 grains comparable to that of Si3N4 without sintering
additives were found to be the reason of this behavior. Benefit in
the long-term stability of Si3N4 at elevated temperatures was
observed in composites with SiC and MoSi2 caused by a mod-
ified oxidation mechanism. The insufficient corrosion stability in
hot gas environments at elevated temperatures was found to be
the main problem of Si3N4 for application in advanced gas tur-
bines. Progress has been achieved in the development of potential
material systems for environmental barrier coatings (EBC) for
Si3N4; however, the long-term stability of the whole system EBC-
base Si3N4 has to be subject of comprehensive future studies.
Besides the superior high-temperature properties, the whole appli-
cation process from cost-effective industrial production, reliability
and failure probability, industrial handling up to specific conditions
during the application have to be focused in order to bring ad-
vanced Si3N4 currently available to industrial application.
I. Introduction
V ARIOUS high-temperature processes in several industries like
power generation, mechanical engineering and plant con-
struction, or traffic engineering require materials that are able to
serve in structural applications at elevated temperatures and in
different environments. Most of the materials used in high-tem-
perature processes are metallic materials characterized by a pur-
D. J. Green—contributing editor
Manuscript No. 27314. Received December 30, 2009; approved April 3, 2010.
*Member, The American Ceramic Society.
w
Author to whom correspondence should be addressed. e-mail: hagen.klemm@ikts.
fraunhofer.de
DOI: 10.1111/j.1551-2916.2010.03839.x
r 2010 The American Ceramic Society
Hagen Klemm*,w
poseful evaluated knowledge of their mechanical, thermo-
physical, and chemical properties.
Nickel-based super alloys applied in the hot gas path of in-
dustrial gas turbines for energy production are one example for
such kind of well-optimized material systems. With advanced
cooling concepts (thermal barrier coatings, film cooling) it is
possible to apply these metallic materials in hot gas tempera-
tures up to 14001C although these metals are limited with a real
material temperature potential of about 10001C caused by their
inherent physical properties.
The improvement of the efficiency as one main strategic goal
in the development of advanced gas turbines necessitates an
increase of the gas temperature in the turbine. However, higher
turbine temperatures cannot be compensated by additional cool-
ing. This would be in contrast to the environmental requirements
as the second main strategic goal. It is the aim to reduce the
emissions during the process because additional cooling results
in an increase of the emissions of the gas turbine (e.g., NOx). For
that reason new high-temperature engineering strategies are re-
quired to reduce cooling demands for high-temperature gas tur-
bines. Such strategies cannot be solved with metallic alloys.
On the lines of this example similar significant amount of re-
search needs to be carried out for applications in several other
industrial processes at elevated temperatures.
In this context ceramic materials are promising alternative
candidate especially in combination with corrosion processes.
The main advantage of ceramics was found to be the consider-
able higher potential for material temperatures above 10001C, in
particular their mechanical and chemical stability at elevated
temperatures. However, there are still disadvantageous proper-
ties limiting the application of ceramic materials at elevated
temperatures. At first, the typical ‘‘ceramic’’ properties such as
high brittleness, negligible ductility, and lack of damage toler-
ance as well as high costs in fabrication have to be considered in
the development process. Recently, another critical factor of
high-temperature ceramics for applications in hot gas environ-
ments of industrial gas turbines has been in the focus. Material
loss was observed for nearly all structural ceramics in such en-
vironments as the consequence of corrosion processes at the
surface of the materials.
A comparison of the high-temperature potential of various
oxide and nonoxide ceramic materials for structural applications
is given in Sidebar 1. Oxide ceramics are limited up to temper-
atures of maximal 12001C. Nonoxide silicon-based materials
with the typical examples SiC and Si3N4 exhibit a potential up to
temperatures of 15001C.
Among nonoxide ceramic materials Si3N4 has been most
widely studied. With variation of the sintering additive compo-
Feature
1502 Journal of the American Ceramic Society—Klemm Vol. 93, No. 6

Sidebar 1. High-Temperature Potential of Ceramic Materials

Various ceramics have been subject of comprehensive scientific studies in order to develop materials for use in long-term
applications at elevated temperatures. A summary of potential candidates of oxide and nonoxide ceramics in comparison with
graphite known as the material with the highest potential in structural applications at elevated temperatures is summarized in
Table A1. First comparisons were made on a rough assessment of the coefficient of volume diffusion of these materials at
14001C.1–10 A clear tendency can be seen indicating the highest potential in case of the graphite materials as known. The
difference between the oxide ceramics and the silicon-based nonoxides can be explained by the bonding type. Whereas the
nonoxides are characterized by a dominantly covalent bonding, the oxide ceramics exhibit a major degree of ionic bonding,
which results in much higher coefficients of diffusion. A logic consequence of this behavior is the approximate value of the
maximal temperature of sintering without sintering additives necessary to obtain dense materials in the second line of the table.
Lower sintering temperatures are required for oxide materials caused by the higher diffusion ability as compared with the
nonoxides. This behavior is continued by the evaluation of the mechanical properties of the materials. Both the long-term
strength potential at 14001C and the creep rate at 15001C, 100 MPa (four-point bending) illustrate a high suitability of Si3N4 and
SiC for structural applications at temperatures between 14001 and 15001C, whereas the oxides are limited up to temperatures
of maximal 11001C and can be used only in low-stress applications at higher temperatures. A high potential in the field of
oxide ceramics could be opened with ceramic matrix composites with single crystalline fibers,10 which exhibit a considerably
improved creep behavior. Such kind of fibers with thin diameter (o20 mm), however, are currently not available.

Table A1. Comparison of Elevated-Temperature Potential of Various Oxide and Nonoxide Ceramic Materials
Material Oxides (YAG, Al2O3, mullite, ZrO2) Si3N4 SiC Graphite

D/cm2/s 1013–1015 1017–1018 1018–1019 1019–1020

Tfabrication/1C 1500–1700 2000 2200 42300
s/MPa o50 200 150 120
e/h1 103 105 106 —
Ox stability/1C Without limitation 1500 1600 400
Long-term potential No limit in non-structural applications 14001C, 200 MPa 15001C, 150 MPa Inert 420001C
D, diffusion coefficient at 14001C; Tfabrication, value of maximal sintering temperature; s, long-term stress potential at 14001C; e, creep rate at 15001C, 100 MPa; Ox
Stability, limit of oxidation stability in air.

On the other hand, an additional main requirement to be evaluated is the stability of the ceramic materials at application
temperature in air. Oxides have already reacted with oxygen and offer consequently a potentially good high-temperature
thermodynamic and surface stability under oxidizing conditions. Nonoxides are thermodynamically instable. For that reason a
long-term stabilization of these materials can only be achieved with a protective oxygen diffusion barrier. In case of the silicon-
based nonoxides an effective diffusion barrier of silica is formed during operation at elevated temperatures as oxidation
product. Other nonoxide high-temperature ceramics, e.g. ultra high-temperature ceramics based on HfB2/TiC, ZrB2/SiC, or
ZrB2/C/SiC, are very refractory up to temperatures of 20001C. Because of the lack of effective oxygen protection layer systems
their oxidation rates were found to be several orders of magnitude higher and consequently not applicable for long-term use
in oxidative environments.11,12
Besides oxidation additional attention has to be drawn to corrosion processes as the consequence of surface interaction with
the environment, e.g. hot gas corrosion in gas turbine environments.
In summary of this assessment of currently available ceramic materials it can be followed that only nonoxide silicon-based
ceramics are able to serve in long-term structural applications at temperatures 412001C. Main future research requirements for
nonoxides have to be focused to oxidation and corrosion processes and the microstructural and compositional stability during
long-term service at elevated temperatures. A broad field in low-stress applications exists for oxide ceramics as result of their
oxidation stability. With respect to corrosion processes in more reactive environments (e.g., water vapor), however,
comprehensive studies are also required for these materials.

sition a broad range of different kinds of Si3N4 has been fab-
ricated with special property combinations. This was found to
be one main advantage in comparison with other ceramic
materials as the microstructure can be designed by liquid-phase
sintering to achieve elongated grains providing benefits in frac-
ture toughness.
Silicon nitride for high-temperature applications have been
the subject of numerous scientific studies performed in univer-
sities, scientific institutes, and industries. In principle, three main
requirements for high-temperature materials were in the focus of
these studies:
1. Depending on the application desired, the materials have
to be characterized by a combination of mechanical properties
(e.g., reliable strength level, KIc, subcritical crack growth [SCG],
creep), chemical resistance (e.g., oxidation and corrosion) and
thermophysical properties (e.g., thermal shock resistance) in a
sufficient level. This includes the whole temperature range from
ambient, intermediate, and elevated temperatures during oper-
ation.
2. Most of the applications at elevated temperatures are
long-term applications. For that reason, the materials must ex-
hibit superior long-term stability; i.e. the high level of properties
required must be maintained as much as possible throughout the
entire duration of operation.
3. The manufacturing process to obtain ceramic compo-
nents is the third crucial factor for a successful application of
silicon nitride in all kind of industries. In addition to simple and
cost-efficient manufacturing methods (powder processing, shap-
ing, sintering, and finish) high reproducibility, reliability, and
dimensional stability of the ceramic components in industrial
scale have to be assured.
The following paper provides a summary of the development
of high-temperature silicon nitride. The main focus is placed on
materials for applications at temperatures 412001C. Based on the
evaluation of typical Si3N4 systems presented in literature (com-
mercial grades and silicon nitride in laboratory scale), the poten-
tial and limits of these materials are provided. By means of the
appendices in the side bars supplementary issues are discussed.
II. Hot Isostatic Pressing (HIP) Silicon Nitride Without
Sintering Additives
Several different kinds of Si3N4 have been the result of substan-
tial studies in the scientific community. The intergranular phase
June 2010 Silicon Nitride for High-Temperature Applications
was outlined as the main influencing factor for the behavior of
these materials at elevated temperatures in the majority of these
investigations. The mass transport of the intergranular phase is
several orders of magnitude faster than that in the silicon nitride
crystals. Besides the interactions with the environment (oxidation
or corrosion) the high-temperature processes in Si3N4 conse-
quently have their seeds in the processes in intergranular glassy
films and triple junctions. From this point of view, a tailored
intergranular phase with a minimal impurity level and sintering
additives forming high-refractory silicates with a high degree of
crystallization was found to be the overall guide of these studies
for the development of high-temperature silicon nitride.
Based on this understanding it makes sense to start from
Si3N4 without sintering additives as a base model material. This
material, densified by encapsulation HIP, is characterized by a
clean grain-boundary phase containing only amorphous silica.
In all cases, when other components were added to the Si3N4
(impurities or doping in ppm range, sintering additives or com-
posite additions) a change of amount, composition, or condition
of grain-boundary phase was observed consequently leading to
different materials with changed microstructures and properties.
First systematic studies of the mechanical properties at ele-
vated temperatures on Si3N4 without sintering additives were
Fig. 1. SEM microstructure of polished and chemically etched cross-
section Si3N4 sintered without additives (A), TEM micrograph of
the intergranular glassy phase in the same material (B). Courtesy Isao
Tanaka.16
1503
performed by Tanaka and Pezzotti.13–15 The materials fabri-
cated by encapsulation HIP were characterized by a micro-
structure with mostly globular grains (Fig. 1)16 surrounded by
the amorphous grain-boundary phase of silica. As the conse-
quence of this microstructure in combination with a strong in-
terface between the Si3N4 grains and the intergranulary phase
the mechanical properties at ambient temperatures were ob-
served rather poor with a four-point bending strength level of
about 500 MPa and fracture toughness of 2.5 MPa  m1/2.13 The
high-temperature properties, however, were found to be excel-
lent, in case of a high-purity Si3N4 raw material powder (E10,
UBE Industries, Tokyo, Japan) a constant strength level with-
out degradation up to temperatures of 15001C (Fig. 2) as well a
superior creep and SCG resistance was reported.16
Property degradation at elevated temperatures was obtained
by adding only a small amount of other ions to the pure silica
grain-boundary phase. Significant reduction of the strength has
already been observed in case of using a raw material powder
with higher impurities content in parts per million (ppm) scale
(LC-12, H.C. Starck, Goslar, Germany) (Fig. 2). Based on in-
ternal friction measurements up to elevated temperatures an
impurity enhanced cavity formation consequently leading to
slow crack growth processes was proposed as the dominant
strength degradation mechanism.16
More systematic studies with defined impurity amounts have
been performed by Tanaka and colleagues by purposeful doping
Ca21 and F impurities.17–21 Already the presence of a small
amount of these impurities was found to cause a significant de-
gradation of the SCG and creep resistance as well. Changes in
thickness and chemistry of the grain boundaries were observed
by doping pure Si3N4 with 80, 220, and 450 ppm Ca21.18 The
influence of the thickness of the intergranular film was found to
be inconsistent and less important for the interpretation of the
mechanical properties behavior. It decreased with increasing
Ca21 up to 80 ppm, with higher Ca21 content an increased film
thickness was observed. This phenomenon can be qualitatively
understood by a model proposed by Clarke et al.22,23 It suggests
the determination of the film thickness by a competition between
the structural (steric) and EDL repulsive forces and the attrac-
tive van der Waals force.
Much higher importance, however, was attached to the chem-
istry of the grain-boundary film. Based by internal friction
experiments, indicating the presence of a clear grain-boundary
relaxation peak, a decreased viscosity of the chemically modified
grain-boundary phase was suggested to be the consequence of
the presence of the Ca21 impurities in the intergranular film
between two grain junctions.
The weakening of the materials with increasing the amount of
dopants is illustrated by their SCG susceptibility (Fig. 3) and the
Fig. 2. Temperature dependence of flexural strength (four-point bend-
ing) of two HIPed Si3N4 materials based on raw material powders with
different impurities, DE10, Ube Industries, J LC-12, H.C. Starck.
Courtesy Isao Tanaka.16
1504 Journal of the American Ceramic Society—Klemm
Fig. 3. Intergranular subcritical crack growth (SCG) length at fracture
surface after bending test of precracked bars of undoped and Ca21-
doped Si3N4 materials without additives as the function of outer fiber
strain rate at 14001C. Courtesy Isao Tanaka.18
creep behavior (Fig. 4).18 Based on the high-temperature exper-
iments on materials with variation of the Ca21 doping a changed
fracture mechanism from brittle fracture to SCG controlled to
creep failure was proposed and summarized in a fracture mech-
anism map demonstrated in Fig. 5.
The use of the viscosity to model the high-temperature
behavior like creep is also supported by the studies of internal
friction of pure Si3N4 by Pezzotti et al.24
In summary of these studies on model Si3N4 systems, the
strong influence of the composition and condition of the inter-
granular film on the elevated temperature behavior of Si3N4 was
demonstrated. Changes in the chemistry of the pure SiO2 glass in
the grain boundaries always caused a decrease in its viscosity
consequently leading to the reduction of the activation energy of
typical high-temperature processes like viscous sliding or for-
Fig. 4. Comparison of steady-state creep strain rate as a function of
applied stress of undoped and 80 ppm Ca21-doped Si3N4 without sinte-
ring additives. Courtesy Isao Tanaka.18
Vol. 93, No. 6
Fig. 5. Fracture mechanism map of low Ca-doped Si3N4 at 14001C.
Open circles: fractured at ambient temperature, time-dependent fracture
process. Closed circles: fractured by SCG. Closed box: fractured by ap-
preciable creep strain due to primary creep mechanism. X, measured
steady creep rate at 200 MPa. Courtesy Isao Tanaka.18
mation of cavities. As the result of these processes a degraded
SCG and creep resistance of the materials was obtained.
III. Silicon Nitride with Sintering Additives
The main reason for using additives in Si3N4 is sintering. From
application point of view a fabrication via encapsulation HIP
would be complex in technical efforts and costs. By using
sintering additives a liquid phase is formed during sintering at
elevated temperatures by the sintering additives and the silica
always present as an impurity in the Si3N4 powder. The liquid
phase promotes the densification accelerating the mass transport
by solution and reprecipitation processes with the result of sta-
ble b-Si3N4 grains embedded in a silicate phase in the grain
boundaries and triple junctions after cooling. With the growth
of large acicular grains during sintering and the weakening of
the grain boundary a significantly higher amount of intergran-
ular fracture mode was observed consequently leading to an in-
crease of fracture toughness and flaw tolerance of the Si3N4.25,26
Additionally, some benefit can be obtained at high temperatures
by a reduction in size of the inherent defects and crack blunting
and healing effects. On the other hand, however, these materials
are usually characterized by degraded high-temperature behav-
ior caused by enhanced SCG or creep damages (cavity forma-
tion) as a consequence of the weaker grain boundary.27 This fact
reflects a principle dilemma in the development of ceramics for
high-temperature structural applications. The parameters that
enhance densification by liquid-phase sintering or cause an in-
crease in flaw tolerance and fracture resistance at room as well
elevated temperatures are the same ones that promote property
degradation at high temperatures (decrease in the SCG and
deformation resistance).
During the development of silicon nitride various sintering
additive systems have been studied. From the high-temperature
application point of view, however, only additives forming high
refractory silicate glasses with high melting point and low vis-
cosity are useful. Several studies investigated the dependency of
the glass composition on transition temperature and viscosity of
oxynitride glasses in the YSiAlON system.28–33 A shift to higher
transition temperatures and viscosities was found for higher ra-
tios of N/O and Y/Al. Furthermore, high refractory glasses were
observed without low eutectica forming components like Al or
Mg. In this way, standard sintering additive systems with com-
ponents like MgO or Al2O3 are less beneficial for the develop-
ment of high-temperature Si3N4.
The presence of additives forming low eutectics (Al2O3, AlN)
was found to be the main problem of SiAlON materials as well.
June 2010 Silicon Nitride for High-Temperature Applications 1505

Actually, the tailoring of Si3N4 for high-temperature applica- with a comprehensive mechanical characterization is represented
tions should be possible due to their ability to incorporate some by various HIP qualities with only a small amount of Y2O3 (4–6
of the grain-boundary constituents into their crystal lattice (sub- wt%). Typical materials described in the literature39–55 are
stitution of Al–O for Si–N in b0 -SiAlON). By adding metal ions 1. NT 154 (Norton, Norton Advanced Ceramics, North-
into the two large interstices in the unit cell of the a-Si3N4 the boro, MA) 4 wt% Y2O3, a/d Y2Si2O7 and some apatite phase
a0 -SiAlON is formed and stabilized. This feature makes it pos- Y5(SiO4)N,39–44
sible to tailor the grain-boundary phase by the resorption of the 2. NT 164 (Norton) 4 wt% Y2O3 (higher SiO2 amount
metal ions, which are primarily used as sintering additive in the forming Si2ON2, 30–40% residual a-Si3N4,45,46
first stage of the densification process. In this way a high content 3. NCX-5102 (Norton) 4 wt% Y2O3, higher amount of
of a0 -SiAlON was found to be beneficial in terms of creep a-Si3N4, only g-Y2Si2O7,47,48
behavior of such materials. The same materials, however, were 4. PY6 (GTE Laboratories, Inc., Waltham, MA) 6 wt%
characterized by a considerably degraded fracture behavior at Y2O3, Y2Si2O7.48–52
elevated temperatures and a poor oxidation resistance. The There were two purposes in using these compositions. The
presence of Al31 ions will always cause a soft oxidation layer first was to obtain better high-temperature mechanical proper-
with high ability for oxygen diffusion into the Si3N4.34 ties with a minimal amount of sintering additives similar to
studies in other groups.56,57 The second was to realize a stable
(1) Silicon Nitride with Silica as Sintering Additive grain-boundary phase composition near the Si3N4–Y2Si2O7–
Si2ON2 compatibility triangle with high oxidation resistance52,53
The first basic sintering additive to be considered is silica. If
in order to avoid yttrium silicon oxinitride phases that can un-
additional contaminations were avoided only the amount of the
dergo large volume expansion when oxidized.58–60 In principle,
sintering additive was changed in the system. Systematic studies
these materials exhibited comparable microstructures and com-
about pure silicon nitride with SiO2 additions have been per-
positions with the small differences described above.
formed by Zeng et al.35–37 Focusing the ambient temperatures
The calculated SiO2/Y2O3 ratio of these materials was
properties like fracture toughness and flaw tolerance only min-
between 2.3 and 1.7 (with assumption of 1.2 wt% oxygen
imal improvement was observed. This was the consequence of
contamination in Si3N4 powder, UbE E10, possible additions
only small changes in microstructure and the unchanged strong
of SiO2 were not considered).
interaction between Si3N4 grains and grain-boundary phase.
The mechanical behavior of these materials were character-
Sintering was performed by HIP although in case of a higher
ized by a change from a SCG mechanism at lower temperatures
amount of SiO2 a lower sintering temperature was required to
(o12001C) and high stresses or high strain rates to a creep-con-
obtain dense materials. The high-temperature properties were
trolled damage mechanism in accordance to the Monkman–
not significantly altered up to SiO2 additions of 10 wt%. The
Grant relation at higher temperatures and lower stresses or
additional SiO2 was found to be localized in the triple pockets
strain rates similar to that reported by Tanaka for the Si3N4
without reflecting the grain-boundary films between two Si3N4
without additive.18
grains significantly. With higher additions, however, a critical
A comprehensive study about the mechanical behavior of
value between 10 and 20 wt% was reached, where the structure
these materials was provided by Menon et al.40–42 for NT 154.
was changed such that localized glass pockets became intercon-
The nucleation of cavities within the intergranular phase at
nected by a thicker glass layer between the Si3N4 grains. Similar
both two grain and three grain boundaries and the flow of that
results with only marginal high-temperature degradation of
phase away from the side of cavitation were found to be the
SiO2-doped Si3N4 were observed in Klemm and Pezzotti38 study
predominant mechanism for the creep-damage controlled be-
as well. The main conclusion of the studies was that the addition
havior at temperatures 413001C. This has been confirmed by
of pure SiO2 alters only the amount of glassy phase at the grain
Luecke and colleagues in more detailed studies on the creep
boundary without reducing its viscosity or the threshold stress
mechanisms of various Si3N4 for elevated temperature applica-
for cavity formation. In this way, the amount of the sintering
tions.61,62 During tensile creep cavities were formed and grew in
additive was found to have only a slight influence on the high-
the silicate filled multigrain pockets. They allowed the flow of
temperature properties since the two grain boundaries were not
the silicate phase from the cavities to surrounding silicate pock-
affected in composition and shape.
ets with the consequence of dilatation processes in the micro-
A strong influence, however, was found in the case with the
structure and the deformation of the Si3N4.
low-doped Si3N4 with only a small amount of sintering additives
The differences in the mechanical behavior of these materials
reported in the same study. In contrast to the SiO2 doping the
are rather small and should be the consequence of a shift of
addition of only 0.7 vol% of Y2O3 or Yb2O3 and their incor-
SiO2/Y2O3 ratio in the raw materials resulting in variations of
poration to the two grain boundaries led to a general weakening
the crystalline grain-boundary phase composition or differences
of the grain boundary. The reduction of its viscosity and the
in the a-Si3N4 content of the materials.
threshold stress for cavity formation led to degradation of the
As mentioned, the composition of the grain-boundary phase
mechanical properties. In the case of a higher amount of Yb2O3
was fixed mainly to be in the Si3N4–Y2Si2O7–Si2ON2 compat-
doping (1.7 vol%), however, an improvement of the mechanical
ibility triangle with high oxidation resistance. However, despite
behavior at 14001C was found with increasing testing time. This
the high oxidation resistance of these materials the mechanical
was the consequence of crystallization processes in the grain
properties of the Si3N4 were found to be strongly influenced by
boundary during the test. With the crystallization of the
oxidation processes, especially during long-term oxidation treat-
Yb2Si2O7 in the triple junctions the stoichiometric composition
ment. The oxidation of the materials occurred on both the sur-
of the residual glassy grain-boundary phase was strongly influ-
face and in the upper bulk of the materials consequently leading
enced, in other words a significant amount of the Yb31 ions
to changes in the microstructure of the upper region of the bulk
were removed from the glassy two grain boundaries conse-
material. Wereszczak et al.52–55 described a clear evidence of
quently leading to cleaner intergranular films with higher
such oxidation effects in these materials in combination with
viscosity and finally an improved property level at elevated tem-
tensile stress at temperatures 413001C resulting in a stress cor-
peratures. It is important to mention that the crystallization
rosion cracking zone influencing the mechanical behavior of
process was strongly influenced by the stoichiometric composi-
these materials.
tion of the grain-boundary phase. In case of the 0.7 vol% Yb2O3
With increasing amount of the Rare Earth content as sinte-
doped material no crystallization could be found.
ring additives, e.g. Y2O3, the composition of the grain-boundary
phase moves out of the Si3N4–Y2Si2O7–Si2ON2 compatibility
(2) Silicon Nitride with Y2O3 as Sintering Additive triangle to Y2O3-rich silicate and oxynitride phases. There are
The most studies in the field of sintering additives for high-tem- studies on Si3N4 containing a higher amount of Y2O3 or other
perature Si3N4 have been performed with Y2O3. A first group Rare Earth (Yb2O3) describing an excellent mechanical property
1506 Journal of the American Ceramic Society—Klemm
behavior at temperatures 413001C.63–68 The problem of volume
expansion during the oxidation of Y- or Yb-oxynitride grain-
boundary phases like YSiO2N or Y2O3  Si3N4 in case of Y2O3 as
sintering additive58–60 was still present. However, the reported
catastrophic failure as consequence of this volume expansion
and the formation of internal stresses during oxidation was only
found at lower (intermediate) temperatures (o11001C).69 At
higher oxidation temperature these processes were prevented by
the rapid formation of a dense oxidation layer mainly consisting
of silica, which allows only small oxygen diffusion into the ma-
terial.70–73
The high level of mechanical properties at temperatures be-
tween 14001 and 15001C was found to be the consequence of a
higher eutectic by moving from the SiO2-rich corner to the
Y2O3-rich one of the phase diagram. A second point was the
degree of crystallization and the composition of the residual
amorphous grain-boundary phase as reported in a study about
the influence of SiO2/Y2O3 ratio in the raw material composition
on creep, SCG, and oxidation at elevated temperatures.73 The
SiO2/Y2O3 ratio was varied in the raw material composition by
adding different amounts of SiO2 to a base material with 8 wt%
Y2O3. In this way, Si3N4 with different SiO2/Y2O3 ratio from
2.87 to 0.6 were produced by hot pressing. The amount of
grain-boundary phase increased with increasing SiO2 content,
however, it was proposed that the different creep and SCG re-
sistance observed was mainly the consequence of the different
amount and composition of crystalline and residual amorphous
grain-boundary phase, with, e.g., mainly Y2Si2O7 (SiO2-rich) or
Y2O3  Si3N4 (Y2O3-rich). The smallest creep rate (200 MPa,
14001C, four-point bending) was obtained for Y2O3-rich grain-
boundary phases with Y-oxynitrides like YSiO2N and
Y2O3  Si3N4 as crystalline phases. With increasing SiO2 amount
the creep rate was found to be higher up to a SiO2/Y2O3 ratio of
2.36. From this value an improved creep resistance was obtained
(mainly Y2Si2O7 as crystalline grain-boundary phase). A similar
tendency was found for the SCG behavior of these materials.
The different behavior is demonstrated in Fig. 6 with typical
fracture surfaces after dynamic fatigue experiments (15001C,
Fig. 6. Fracture surfaces of two Si3N4 materials with different SiO2/
Y2O3 ratio after dynamic fatigue experiments at 15001C, 0,05 MPa/s.
Bending bars precracked by razor blade prior testing, radius at the tip
about 15 mm, (A) SiO2-rich, (B) Y2O3-rich. H. Klemm.153
Vol. 93, No. 6
0.05 MPa/s on precracked bars (razor blade notch). High SCG
susceptibility was found in case of the SiO2-rich materials dem-
onstrated with a SiO2/Y2O3 ratio 5 2.12 illustrated by the large
SCG region of 1670 mm and a strength of 132 MPa (Fig. 6(A)).
The Y2O3-rich material (SiO2/Y2O3 ratio 5 1.0), however, was
found to be much more stable with only a small SCG region of
350 mm and a consequently higher strength to failure of 207
MPa (Fig. 6(B)). A clear interpretation of these results should be
difficult due to the different volume amount of the grain-bound-
ary phase; however, there are similarities of the SiO2-rich
materials (e.g., 2.12 SiO2/Y2O3 ratio) to the above-described
materials NT 154 and 164 with 4 wt% Y2O3. The materials
showed comparable creep properties in the same order of mag-
nitude.74 Furthermore, the SCG behavior of the SiO2-rich
material (SiO2/Y2O3 ratio of 2.12) seems to be comparable to
the stress oxidation zone reported by Wereszczak et al.52–55
Whereas the amount of the grain-boundary phase was different
(5–6 vol% in NT 154 and 164, 10.5 vol% in the hot pressed
material) the grain-boundary phase composition with a SiO2/
Y2O3 ratio of 42 in both materials was nearly similar. In this
way, the composition of crystalline and residual amorphous
grain-boundary phase seems to be more important than their
overall amount in the sintering additive containing Si3N4, sim-
ilar to the tendency described above for Si3N4 without sintering
additives.
(3) Other Refractory Silicates Forming Sintering Additives
Several studies have been performed in order to replace the
Y2O3 as sintering additive by other oxide systems forming high
refractory silicates like Sc2O3 or the lanthanide Rare Earth
within the group from La31 to Lu31.75–82 Similar properties in
comparison with the Y2O3 system were expected for the lan-
thanide oxides since they have a similar electronic configuration
and form isostructural lanthanide silicates and oxynitrides.83–85
With increasing atomic number the ionic radii decrease from
0.114 nm La31 to 0.086 nm Yb3185 and Lu31 0.085 nm.
An overview about the influence of the different Rare Earth
instead of Y2O3 has been provided by Cinibulk et al.80–82 with
materials using Sm2O3, Gd2O3, Dy2O3, Y2O3, Er2O3, and
Yb2O3 as sintering additive. The materials were fabricated di-
rectly in the Si3N4–RE2Si2O7 tie line of the Si3N4–Si2ON2–
RE2Si2O7 compatibility triangle (12.3 vol% grain-boundary
phase, RE2O3 content between 9 and 10 wt%, SiO2/RE2O3 ra-
tio 5 2). In general, the elevated properties of these materials
were found to be in the same order of magnitude. The oxidation
rates were roughly inversely related to the eutectic temperatures
in the SiO2–RE2O3 system.81 This was the consequence of higher
oxygen diffusion caused by a lower viscosity of the amorphous
silicate phase. A similar effect was reported regarding the creep
results with the lowest steady state creep rate of the most re-
fractory materials.82 Additionally, the creep behavior was found
to be strongly dependent on the impurity content of the residual
grain-boundary phase. A purification effect was observed in the
residual amorphous grain boundaries due to impurity diffusion
to the surface during creep testing. With exception of the Sm2O3
containing material a steady-state creep rate for tests at 14001C
and 200 MPa was found in the range between 2  105 and
5  105 h1. Cavity formation was observed to be the main
deformation mechanism, indicating a similar potential as com-
pared with the HIPed materials with Y2O3 as sintering additive
(e.g., NT 154, NT 164). Results with a similar tendency have
been reported in other studies with focus on fracture toughness,
oxidation resistance, and creep.74–79 Only small differences in
the high-temperature behavior of the materials were obtained
which have been interpreted to be the consequence of higher
eutectic temperatures of the silicate system with the decrease of
the cationic radii of the Rare Earth ion used as sintering additive
(La31-Yb31).
Comparisons of high-temperature properties of oxinitride
systems (Si3N4–RE4Si2O7N2, 2.4 mol%) with Sc31, Yb31,
La31, and Lu31 have been shown by Nishimura et al.79 These
June 2010 Silicon Nitride for High-Temperature Applications 1507

materials exhibited a similar high-temperature behavior too,

however, in case of the Lu13-doped material a considerably
higher level in elevated temperature strength was observed. Es-
pecially with SiO2-rich grain-boundary phase compositions
(crystallization of Lu2SiO5) a superior high-temperature behav-
ior (strength, oxidation, and creep) was reported.
More detailed investigations among the Rare Earth have
mainly been performed with Yb2O3 as sintering additive.86–93
A typical representative for this kind of material is the commer-
cial Si3N4 SN 88 (NGK Insulators Ltd., Nagoya, Japan) with a
mixture of Yb2O3 and Y2O3 as sintering additives. Yb2O3 is one
of the heaviest Rare Earth promising a high refractory behavior
of phases in the system Si3N4–SiO2–Yb2O3. Furthermore, a
superior crystallization behavior of Yb2O3-doped materials
(Yb2Si2O7, Yb4Si2O7N2) has been reported89 finally leading to
a high level of properties at elevated temperatures (strength,
creep, and oxidation resistance). The high-temperature stability
was found to be dependent on the SiO2/Yb2O3 ratio determining
the composition and amount of the crystalline phases and the
residual amorphous grain-boundary phase formed. However, at
high-temperature creep testing all materials in this system showed
cavity formation as the main mechanism during high-temperature
creep testing for all materials indicating a comparable behavior to
that of the materials in the Y2O3 system in principal.

IV. Silicon Nitride-Based Composites

Various studies to improve the high-temperature properties of
silicon nitride have been performed by the formation of com-
posite materials (e.g., SiC, TiN/TiC, silicides (Mo, W), BN,
ZrO2, HfO2). Among these ceramic materials the addition of
SiC and MoSi2 has been turned out as the most promising can-
didates.

(1) Si3N4–SiC Composites
Several studies reported high values for the mechanical proper-
ties (strength, creep) of the Si3N4–SiC composites at elevated
temperatures, which resulted in a significant improvement of the
time-to-failure behavior up to temperatures of 14001C.94–96
Originally, these results were assumed to be the consequence
of a new design concept introduced by Niihara and colleagues
describing structural synergisms between the matrix Si3N4 and
the nano-SiC dispersoid situated at the grain boundaries be-
tween the Si3N4 grains.97–101 Typical microstructures of such
kind of materials are shown in Fig. 7. However, the influence of
the mechanical interaction (i.e. grain-boundary interlocking) be-
tween the dispersed particles and the matrix Si3N4 on mechan-
ical properties such as fracture toughness or creep has not been
demonstrated convincingly. Furthermore, in a study comparing
a pure Si3N4 and a Si3N4–SiC composite densified by encapsu-
lation HIP with no addition of sintering additives,102 there was
found to be no beneficial influence of the nano- or microsized
SiC additions on the mechanical properties at ambient and el-
evated temperatures. The improvement (by several orders of
magnitude) in the creep resistance of the Si3N4–SiC nanocom-
posite reported by Hirano et al.101 was actually the consequence
of making the comparison with a Si3N4 containing a signifi-
cantly higher amount of chlorine impurities.103
Other studies reported only a slight improvement of the prop-
erties at elevated temperatures (strength, creep) of the Si3N4–SiC
nanocomposites in comparison with Si3N4.104–108 This improve-
ment, however, could have been the result of a chemical
modification of the grain-boundary phase caused by the SiC
particles.73 Most of the SiC in the composites was found to be
situated in the grain boundaries between the Si3N4 grains. Espe-
cially, when SiC powders produced by chemical or plasma meth-
ods were used, the oxygen balance of the materials was affected
by the reaction of the finely dispersed SiC or residual free carbon
with the silica during sintering. In case of Y2O3 as sintering ad-
ditive a shift of the grain-boundary phase composition to a lower
SiO2/Y2O3 ratio (larger amount of Y2O3) with the consequence
Fig. 7. Typical microstructure of Si3N4/SiC composite with fine dis-
persed SiC in the grain boundaries between the Si3N4 grains. H. Klemm,
High Temperatures–High Pressure, 27/28 449–56 (1995).
of a higher refractory grain-boundary phase as described above
should be the reason for the property improvement.
Nevertheless, the time-to-failure behavior of the Si3N4–SiC
composites was found to be superior to monolithic Si3N4, al-
though any significant change in creep or SCG resistance was
not observed in the as-sintered materials. A beneficial feature of
the composites was found to be a reduced grain growth during
sintering leading to a narrow grain size distribution preventing
the formation of large Si3N4 grains that can serve as fracture
origins. However, the main factor responsible for the improved
time-to-failure behavior was the considerably improved high-
temperature oxidation resistance of the composites caused by a
changed oxidation mechanism in the Si3N4–SiC composites.
The different oxidation mechanism of the Si3N4 and the
Si3N4–SiC composite materials has been the subject of several
recent studies.109–114 Oxygen penetrates through the protective
oxidation layer (consisting of SiO2 and silicates from the sinte-
ring additive, e.g., Y2Si2O7) during operation at elevated tem-
peratures in air. A part of this diffusing oxygen which did not
react at the interface between the oxidation layer and the bulk
consequently reaches the bulk of the Si3N4. The oxidation pro-
cesses finally occurring in the upper region of the bulk material
are the main reason for the different microstructural develop-
ment of the Si3N4 and the Si3N4–SiC composite. The important
feature of the composite materials was the increased formation
of Si2ON2 instead of SiO2, producing an additional layer be-
tween the oxidation surface and the bulk of the silicon nitride
composite materials. The formation of a SiO2-rich grain bound-
ary in the upper region of the bulk was prevented; thus, there
was no driving force for diffusion and evaporation processes
and no subsequent change in the microstructure of the material
(Sidebar 2). Figure 8 illustrates the result of the oxidation on the
microstructure of a Si3N4 and a Si3N4–SiC composite with the
same sintering additive (8 wt% Y2O3) as observed by SEM on
1508 Journal of the American Ceramic Society—Klemm Vol. 93, No. 6

Sidebar 2. Oxidation of Silicon-Based Nonoxide Ceramic Materials

Oxidation of silicon nitride in ambient air has been subject of several scientific studies. Fundamental research was performed on
pure Si3N4 (produced by chemical vapor deposition (CVD)).115–118 During the oxidation of silicon nitride
Si3 N4 þ 3O2 ! 3SiO2 þ 2N2
gaseous nitrogen and silica were formed as oxidation products resulting in a weight gain of 28.6 wt%. A layer of pure silica
characterized by a small coefficient of oxygen diffusion119 was formed at the surface of the Si3N4. The diffusion of oxygen through
the SiO2 layer was suggested to be the rate-controlling step finally leading to parabolic oxidation kinetic, which was usually found
by measurement of the weight gain as a function of time.
In case of Si3N4 with sintering additive systems crystalline and amorphous silicates were formed additionally in the oxidation
surface layer. In advanced high-temperature silicon nitride the weight gain is still small; however, these silicate contaminations
weaken the pure silica oxidation layer in comparison to the additive-free materials, with the consequence of higher oxygen
diffusion into the ceramic material. Especially during long-term exposure at elevated temperatures, compositional and
microstructural changes in the upper surface and bulk region of these materials were observed.119–126 These processes generate a
new defect population in the materials consequently leading to degradation of the properties of the ceramics in spite of the optimal
combination of properties originally designed during fabrication. Additionally, significant evidence to the consequences of the
oxidation processes were provided in studies dealing with life-time behavior of Si3N4 at elevated temperatures49,54,125
The influence of these processes on microstructure and the mechanical properties was described in127 which compares the
oxidation behavior of a HIPed Si3N4 without sintering additives with a silicon nitride with typical additives (Y2O3 and Y2O3/
Al2O3) as sintering additive. The oxidation behavior of the materials was found to be strongly dependent on the chemical
composition of the oxidation surface layer formed by the oxidation products of the Si3N4 and the sintering additives. The different
behavior of the oxidation is demonstrated by comparison of polished cross sections of the additive-free (2500 h) and the Y2O3/
Al2O3 containing materials (1000 h) after oxidation at 15001C in Fig. A1.

Fig. A1. Comparison of surface region of Si3N4 materials after oxidation at 15001C, (A) HIP Si3N4 without sintering additives, 2500 h, minimal
oxidation observed only at the interface between oxidation layer and bulk Si3N4 material, (B) Si3N4 with 10 wt% Y2O3, 0.6 wt% Al2O3 as sintering
additive, heavy oxidation up to inside the bulk material leading to inhomogeneous distribution of the grain boundary phase caused by strong
diffusion processes. H. Klemm.127

The HIPed material exhibited a very low weight gain with 0.7 mg/cm2 after 2500 h as a clean protective layer of pure SiO2 with
the low-diffusion coefficient of oxygen119 was formed. In the case of the additive containing materials a significant higher
oxidation rate (Si3N4/Y2O3/Al2O3 with weight gain 3.57 mg/cm2 after only 1000 h) was observed. This behavior was the
consequence of increased oxygen diffusion into the material. The upper oxidation layer of these materials consisted of crystalline
Y2Si2O7 and cristobalite in a glassy layer of SiO2 containing ions of the sintering additives used (Y31, Al31). The presence of these
ions of the sintering additives resulted in a change in chemistry and structure of the protective oxidation layer in comparison to the
pure SiO2 layer in the HIP Si3N4 without additives. Because of the lower eutectic and viscosity of the oxidation layer, the oxygen
diffusion into the material was found to be considerably higher.119
June 2010 Silicon Nitride for High-Temperature Applications 1509

Sidebar 2. Continued
A second main difference of the oxidation process was the condition of the upper region of the bulk silicon nitride. Whereas the
bulk microstructure was not affected in case of the HIPed additive-free material (all of the oxygen diffusing through the oxidation
surface layer reacted at the interface between the SiO2 layer and the bulk material), the microstructure of sintering additives
containing materials was found to be considerably changed. Typical oxidation damages like surface cracks, regions with
grain-boundary phase inhomogeneously distributed and pores extending to the middle of the specimen were observed.
In contrast to the additive-free materials, in which the diffusion of the oxygen proceeded only to the interface between the surface
oxidation layer and the bulk, some oxygen diffusion into the bulk of the materials with Y2O3/Al2O3 as sintering additive was
observed. This was the consequence of the higher oxygen diffusion in principle and the enlarged dimension of the grain
boundaries serving as oxygen diffusion paths in comparison to the additive-free material.
The reaction of this diffusing oxygen in the grain boundaries of the bulk beneath the upper oxidation layer was responsible for
the microstructural alterations and damage observed in the additive containing materials. As result of oxidation processes in the
bulk material a SiO2 enriched grain-boundary phase was formed in this area. This SiO2-rich grain-boundary phase at the upper
region of the material created a chemical gradient to the grain-boundary composition in the deeper bulk of the Si3N4. The
relaxation of this chemical gradient was considered to be the reason for the changed microstructure in these Si3N4 (diffusion of
yttria to the surface, enrichment of gaseous reaction products with bubble formation at the surface layer).127
In this context the oxidation behavior of the nonoxide silicon nitride ceramics should be considered as one key factor in the
development of high-temperature silicon nitride and other nonoxide ceramic materials as well. Minimal oxygen diffusion with a
consequent minimal weight gain is the first requirement of the development of Si3N4 with superior oxidation stability. A second
important factor, however, was found to be the control of the oxidation processes inside the ceramic material usually leading to
compositional and microstructural changes in the Si3N4.

polished and etched cross sections of the surface regions of the
materials after 2500 h oxidation at 15001C. An increased SiO2
formation took place in the upper region of the bulk of the
Si3N4, which was responsible for the microstructural degrada-
tion (pores, cracks, grain-boundary inhomogenities, Figs. 8(A)
and (C)) of the materials during oxidation and the resulting de-
graded time-to-failure behavior at elevated temperatures. In case
of the Si3N4–SiC composite, the formation of crystalline Si2ON2
instead of SiO2 during oxidation was observed, which led to a
significantly reduced defect size in these composite materials
after oxidation (Fig. 8(B)). The Si2ON2 crystallites exhibited a
typical partial-fiber, twin-like appearance as shown in Fig. 8(D).
The effects of the different microstructural changes during
oxidation on the mechanical properties were demonstrated eas-
ily by measuring the residual bending strength of the materials
after oxidation at 15001C for 2500 h. Whereas a strong degra-
dation of 465% (970-340 MPa) of the strength of the as-
sintered material was obtained for the monolithic Si3N4, the
Si3N4–SiC composite exhibited a considerably lower strength
recession of about 25% (860-640 MPa) of the strength in the
as-hot-pressed condition.
From these results it was concluded that the higher oxidation
stability of the Si3N4–SiC composite materials was the main
reason for the improved behavior in time to failure at elevated
temperatures. Particular benefit was found after long-term high-
temperature treatment in oxidizing environments on account of
an improved SCG resistance as a result of the considerably
reduced defect size.

Fig. 8. Microstructure of a Si3N4 and Si3N4–SiC (10 wt%) microcomposite (8 wt% Y2O3) after 2500 h of oxidation at 15001C in air. Comparison of
polished cross section of surface region of Si3N4 material (A) with oxidation damages (pores) and Si3N4–SiC microcomposite (B) with homogeneous
microstructure, (C) Pores in the bulk microstructure after oxidation of the Si3N4 materials. (D) Crystalline Si2ON2 as the consequence of changed
oxidation mechanism just beneath the oxidation layer in the Si3N4–SiC microcomposite. H. Klemm.73
1510 Journal of the American Ceramic Society—Klemm
(2) Si3N4–MoSi2 Composites
Similar effects have been found during long-term oxidation of
Si3N4–MoSi2 composite materials.127–131 With a partial oxida-
tion of the MoSi2 according to
5MoSi2 þ 7O2 ! Mo5 Si3 þ 7 SiO2 (1)
an increased formation of crystallization nuclei was assumed to
be the reason of the formation of Si2ON2 crystallites in the
upper region of the bulk material comparable to that of the
Si3N4–SiC composites. As consequence of this microstructural
development to form a composite material a significantly lower
degree of damage was observed in the composite during oxida-
tion that was observed in the silicon nitride structure.
The damage processes described for the monolithic Si3N4 did
not occur even at long-term oxidation treatment of 10 000 h
(relevant test duration for gas turbine applications) at 15001C,
as shown in Fig. 9 by the comparison of polished cross sections
of a Si3N4 (A; with heavy damages) and a Si3N4-10 wt% MoSi2
composite (B; with homogeneous nearly undamaged micro-
structure) (both materials with 8 wt% Y2O3 as sintering addi-
tive).131 The beneficial behavior of the Si3N4–MoSi2 composite
was demonstrated by comparing the residual flexural strength of
the materials after oxidation of 10 000 h at 15001C. Because of
severe microstructural damage observed in the Si3N4, a strong
degradation in strength was measured, with a value of about
260 MPa after 10 000 h (32% of the hot-pressed condition). After
the same oxidation time the composite material exhibited a re-
sidual strength of 4500 MPa (65% of the hot-pressed condition).
The superior high-temperature stability of the composite
materials with SiC or MoSi2 addition (i.e., after cyclic thermal
Fig. 9. Comparison of the surface regions of polished and etched cross-
sections of a Si3N4 material with heavy oxidation damages up to the
middle of the sample (A) and a Si3N4–MoSi2 composite with homoge-
neous microstructure nearly without oxidation damage (B) after 10 000 h
of oxidation at 15001C in air, both materials with 8 wt% Y2O3 as sinte-
ring additive. H. Klemm.131
Vol. 93, No. 6
treatment at 15001C for 41 year in case of the Si3N4–MoSi2
composite) demonstrates the high potential of these composite
materials in comparison with other grades of Si3N4. As conse-
quence of the different oxidation mechanism both material sys-
tems that are worth being considered to solve the problems from
the inner oxidation processes usually observed in nonoxide ce-
ramic materials.
The stability of composition and microstructure is an essen-
tial requirement for successful long-term application of ceramic
materials at elevated temperatures. Both, composition and mi-
crostructure specifically designed during processing and sinte-
ring of the material, used to be the main factors determining the
properties of the Si3N4. Any changes in a ceramic material dur-
ing long-term service at elevated temperatures, such as those
observed in Si3N4, will cause property degradation.
V. Advanced High-Temperature Silicon Nitride
There are several Si3N4 grades in commercial and laboratory
state available that are worth to be considered as advanced high-
temperature silicon nitride. However, it is not possible to specify
all these materials. For that reason the focus in this study is
placed on three materials:
1. AS 800, Honeywell Engines, Systems & Services, well-
optimized material with focus on application temperature in the
range of 10001–13001C,
2. Si3N4 with Lu2O3 as sintering additive, commercial ma-
terials SN 281/282 (Kyocera) characterized by an outstanding
high-temperature stability in comparison with other Si3N4
grades and
3. Si3N4 with Sc2O3 as sintering additive, laboratory scale,
comparable to SN 281/282, studied intensively by the author.
(1) AS 800
One of the most highly developed commercial grades of Si3N4 is
AS 800.132–136 The focus of the development was directed to-
wards applications such as structural parts in the hot gas section
of advanced microturbines (up to 500 kW) with a maximum
temperature of 13001C. Components with a diameter of about
400 mm have been produced by gas pressure sintering using
shaping technologies like slip and gel casting or green machining
as shown in Fig. 10. Besides the high-temperature stability re-
quired for long-term service at temperatures between 12001 and
13001C, the main direction of development was focused on frac-
ture toughness and Weibull parameters in order to improve the
reliability of the structural parts (Sidebar 3).137
A combination of La2O3, Y2O3, and SrO was used as sinte-
ring additive. Additionally, a small amount of SiC was added to
the final composition of the Si3N4. In contrast to the HIPed
materials with Y2O3 as sintering additive as described above the
formation of oxynitride grain-boundary phases with a high crys-
talline amount in apatite structure (H-phase) was intended. The
resulting SiO2/R2O3 ratio should be in the range of 1.2 and 1.5;
outside of the compatibility region of the HIPed materials con-
taining Y2O3 (2.3–1.7). The function of SrO seems to be pro-
tection for intermediate temperature oxygen diffusion into the
material since it forms low melting Sr silicates already working
as effective protective oxidation layer in the range of 10001C.
As mentioned above the high-temperature potential of AS
800 was focused to temperatures between 12001 and 13001C.
With the formation of low-temperature eutectics as the conse-
quence of the sintering additive combination of La2O3, Y2O3,
and SrO beneficial effects in sintering behavior were obtained,
however, elevated property degradation (creep, oxidation) espe-
cially at temperatures 413001C were observed.
However, in combination to a superior level in elevated tem-
perature properties up to 13001C the main feature of this ma-
terial was the high level of fracture toughness as the consequence
of a specific design of microstructure called in situ reinforced
Si3N4 with acicular grains (high amount of aspect ratios 44)
and an optimized bonding between Si3N4 grains and grain-
June 2010 Silicon Nitride for High-Temperature Applications
Fig. 10. Gas turbine components from AS 800 fabricated by Honey-
well. Courtesy B. Schenk, Honeywell.
boundary phase. The microstructure of AS 800 with a high
amount of elongated grains is demonstrated as a polished and
etched cross section in Fig. 11. Fundamental studies regarding
the development of high aspect ratio Si3N4 with superior
fracture toughness have been performed first by Becher and
colleagues in several studies.138–141 Based on Si3N4 with
Si–Al–Y-oxynitride glasses as intergranular phases, the effect
of toughness improving mechanisms (deflection, pull out) has
been correlated to the glass composition and the consequential
interaction between Si3N4 grains and the glassy grain-boundary
phase.
In comparison with other Si3N4 for high-temperature appli-
cations a considerably higher level in fracture toughness was
Fig. 11. SEM microstructure of polished and etched (plasma etching in
CF4) cross section of AS 800. H. Klemm.153
1511
Table I. Summary of Fracture Toughness in Comparison to
Creep Data of Various Silicon Nitride Materials
Stationary creep
Material KIc (MPa  m1/2) rate (h1)
S SiC 2.5 1.2  106
Si3N4 without sintering aids 2.8 2.0  106
GPSN SN 281 (Lu2O3) 4.8 2.2  106
GPSN 6 Sc2O3, SiO2/Sc2O3 5 3 5.0 2.1  106
GPSN 6 Sc2O3, SiO2/Sc2O3 5 2 6.1 4.5  105
GPSN 10 Y2O3, SiO2/Y2O3 5 2 5.4 4.0  105
AS 800 7.2 2.0  105
Si3N4  8Y2O3, 2MgAl2O4 6.8 4103
Si3N4  6Y2O3, 5Al2O3 6.1 4103
Fracture toughness measured by SEVNB (ro10 mm) according ISO 23156,
DIN EN 843-1; creep measurement in four-point bending geometry at 200 MPa,
1400 1C, DIN V ENV 820-4.
obtained, characterizing the high potential of this material for
commercial production and application up to 13001C. A com-
parison of fracture toughness and creep resistance data mea-
sured of various high-temperature Si3N4 under the same
conditions is summarized in Table I. In comparison with other
Si3N4 the toughness level of the high-temperature materials was
found to be rather poor confirming the general trend with the
opposite directions of creep and fracture toughness behavior.
The AS 800 exhibited the highest level in fracture toughness in
combination with superior mechanical properties at elevated
temperatures. This was found to be comparable to that of Si3N4
optimized in fracture toughness for ambient temperature appli-
cations with, e.g., Y2O3 and MgAl2O4 as sintering additive. This
behavior is attributed to the coarse microstructure of the mate-
rial with elongated grains as described above and the specific
design of the grain-boundary phase allowing a high amount of
intergranular crack propagation without significant property
degradation at elevated temperatures. The use of La2O3 as the
main sintering additive component should have significant effect
for the high degree of anisotropic grain growth and the follow-
ing high fracture toughness level as reported in.142,143
(2) Si3N4 with Lu2O3 and Sc2O3 as Sintering Additive
Si3N4 with Lu2O3 and Sc2O3 as sintering additive system were
found to be similar in their elevated temperature behavior, ex-
hibiting superior high-temperature stability in comparison with
other Si3N4 grades.
With the introduction of SN 281/282 (Kyocera Corp., Kyoto,
Japan) a new quality among high-temperature resistant Si3N4
was commercially available.144–149 Both materials have the same
sintering additive composition of about 8 wt% Lu2O3 and
2 wt% SiO2.149 The first special feature to note was the ability
to densify these materials by gas pressure sintering notwith-
standing the low amount of sintering additive. SN 281 was
HIPed resulting in a higher level in the room temperature
strength as result of a reduced defect size. Considering the
silica from the Si3N4 raw material powder a molar SiO2/
Lu2O3 ratio of 43 was calculated. The resulting grain-bound-
ary phase composition was situated in the SiO2-rich corner of
the Si3N4–SiO2–Lu2O3 system consequently leading to a strong
crystallization of Lu2Si2O7 in the multigrain junction of the
materials. An increasing amount of Lu31 in the sintering
additive system was found to cause silicon oxynitride phases
(Lu4Si2O7N2).150–152 In this case (lower molar SiO2/Lu2O3 ratio)
degradation of the elevated temperature properties (creep and
oxidation resistance) was observed.153
The first outstanding feature of SN 281/282 was their re-
markably higher creep resistance at elevated temperatures. The
results of systematic creep tests in tension reported by Lofaj
et al.149,154 and Wiederhorn et al.155,156 characterized this mate-
rial with an improved creep resistance of more than three orders
1512 Journal of the American Ceramic Society—Klemm
Fig. 12. Comparison of tensile creep of various high-temperature Si3N4
(data extrapolated to 150 MPa from NT 154/164,157 SN 88,91 AS 800,137
SN 281149).
of magnitude in comparison with other silicon nitride grades
described above. In this way an elevated temperature potential
up to 15001C was demonstrated, 150–200 K higher as the other
Si3N4 grades (NT 154/164,157 SN 88,91 AS 800137) (Fig. 12).
This behavior was explained by the creep mechanism identi-
fied as solution–precipitation processes up to temperatures of
15501C. It differs from those of the other Si3N4 grades, for
which tensile creep has been attributed to cavitation. Wieder-
horn et al.156 gave a reasonable explanation with an increase of
the viscosity of the residual amorphous films between two grain
boundaries to be responsible for a reduction of the ability of the
material to cavitate during creep, and forces the creep mecha-
nism to change from cavitation to solution–precipitation. Sev-
eral studies described an increase of transition temperature and
silicate glass viscosity with smaller Rare Earth ion radius in the
line from La31 to Lu31 suggesting the use of Lu2O3 as sintering
additive for high-temperature Si3N4.31,154,158–160 However, there
is still the question about the basic cause of the high improve-
ment in creep of the Lu31 material. In comparison with mate-
rials in the Yb2O3 system, Yb and Lu are neighbors in the
periodic table of elements and should actually produce silicates
as grain-boundary phase with similar glass transition tempera-
tures and viscosities. Deeper studies have been performed by
Lofaj et al.154 by analyzing the creep behavior of SN 88 (Yb2O3,
Y2O3) and SN 281 (Lu2O3). The comparison of glass transition
temperature (Tg) and viscosity of bulk lanthanide containing
oxide and oxynitride glasses showed only a small improvement
of Tg (26–33 K) and viscosity (26–32 times) by the replacement
of Yb by Lu. This, however, is not sufficient to explain the su-
perior creep resistance of the Lu2O3 material. Much more effect
was found with the incorporation of nitrogen ions to the glass.
The addition of 24 e/o N was found to increase the Tg in the
range of 85–100 K resulting in an increase of the viscosity by
about four orders of magnitude. This, however, was the case in
both the Yb/Y and the Lu-containing glasses. A plausible
explanation for a substantially higher nitrogen amount in the
Lu-containing glass is still pending. Differences in the redistri-
bution of the lanthanide ions between the triple junctions and
the amorphous intergranular films were proposed as a second
argument. With a lower Lu31 content in the amorphous inter-
granular films the composition and viscosity would be closer to
that of pure silica.
A similar behavior at elevated temperatures up to 15001C was
obtained on Si3N4 with Sc2O3 as sintering additive. Following
the tendency of the Rare Earth Sc31 is characterized by an even
smaller ion radius of 0.081 nm.
The high potential of materials in the Si3N4–Si2ON2–Sc2Si2O7
phase field was reported by Morgan et al.161 several years ago.
In comparison with other Si3N4 grades significant improvement
in oxidation and creep resistance was observed. High crystalli-
zation ability without additional heat treatment was reported in
glasses of the Mg–Si–Al–O–N system after Sc2O3 additions by
Vol. 93, No. 6
Fig. 13. Steady creep rate of Si3N4 materials with different SiO2/Sc2O3
ratio, creep measured in four-point bending 200 MPa, 14001C. H.
Klemm.153
Tredway and Loehman162 and Mecartney,163 suggesting Sc2O3
as a potential sintering additive for high-temperature Si3N4. The
elevated temperature properties of hot-pressed Si3N4 with
2.2 wt% Sc2O3 were investigated by Cheong and Sanders.164
The SiO2/Sc2O3 ratio of 43 indicates a SiO2-rich grain-bound-
ary phase composition comparable to that of the study of Mor-
gan. Strong devitrification of the glassy Sc-silicate phase to
crystalline Sc2Si2O7 in the multigrain junctions was proposed
to be the reason for the high level of strength at 13701C and
stepped-temperature stress rupture tests up to 14001C.
Similar to other additive systems there is also a clear depen-
dence of the elevated temperature properties on the SiO2/Sc2O3
ratio. The highest creep resistance was obtained for materials with
a high SiO2/Sc2O3 ratio as demonstrated in Fig. 13 comparing the
stationary creep rate of various Si3N4 at 14001C with sintering
additive compositions with different SiO2/Sc2O3 ratio. The creep
resistance of the materials with SiO2/Sc2O3 ratio 43 is compa-
rable to that of SN 281/282. A comparison of the creep behavior
of different Si3N4 described in this study is shown in Fig. 14.
The oxidation resistance was found to be the second out-
standing feature of materials in the systems with Lu2O3 and
Sc2O3. Comparable data of the oxidation behavior in compar-
ison with other Si3N4 grades for high-temperature applications
are summarized in Table II. Si3N4 with SiO2-rich sintering ad-
ditives in the Lu and Sc system are characterized by significantly
higher oxidation stability; a difference in weight gain with a
factor of about 3 was observed in comparison with standard
materials with Y2O3 or Yb2O3 as sintering additive. On the
other hand, the oxidation behavior (weight gain and thickness of
oxidation layer) was found to be in the same order of magnitude
of HIPed Si3N4 without sintering additives.
The microstructures of the surface region after long-term ox-
idation of both materials are presented as polished cross sections
in Fig. 15. The surface oxidation layer formed during the long-
term treatment at elevated temperatures was found to be com-
posed of mainly silica and RE2Si2O7 crystallites inside the glassy
layer. In contrast to Si3N4 with Y2O3 as sintering additive the
Fig. 14. Comparison of steady state creep rate of various Si3N4 materials
and S SiC, creep tests in bending 40/20, 14001C, 200 MPa. H. Klemm153.
June 2010 Silicon Nitride for High-Temperature Applications 1513

Table II. Comparison of Oxidation Behavior of Various Silicon Nitrides for High-Temperature Applications Illustrating the Superior
Oxidation Resistance of Lu31 and Sc31 Containing Materials
Material Dm (mg/cm2) a (mm) K (mg2/cm4  s) R (mm2/h)

Si3N4 without sintering aids 0.45 8 0.5  108 0.07

GPSN SN 281 (Lu2O3) 0.50 9 0.6  108 0.08
GPSN 6 Sc2O3, SiO2/Sc2O3 5 3 0.50 9 0.6  108 0.08
GPSN 10 Y2O3, SiO2/Y2O3 5 2 1.7 21 6.0  107 0.4
GPSN 18 Yb2O3, SiO2/Yb2O3 5 2 1.4 18 5.0  107 0.3
AS 800 420 470 4106 45
1000 h oxidation at 15001C; Dm and a weight gain and surface layer thickness after 1000 h, K and R oxidation constants, K calculated from Dm between 700 and 1000 h, R
calculated from final thickness after 1000 h.

microstructure of the upper bulk region was not significantly
affected by the oxidation processes. This should be the conse-
quence of the lower amount of diffusion oxygen and its reaction
mainly at the interface between oxidation layer and the bulk
material. Furthermore, in case of oxidation reactions in the up-
per region of the bulk, a strong chemical gradient to the inner
bulk should not be formed because a SiO2-rich grain-boundary
phase composition (SiO2/RE2O343) has already been adjusted
in the raw material composition.
The oxygen diffusion into the Si3N4 is strongly dependent on
the chemical composition of the oxidation surface scale, which is
composed of the oxidation product SiO2 and the sintering ad-
ditives. Usually, this layer consists of amorphous and crystalline
SiO2 and silicate components. The glass transition temperature
and viscosity of the glassy component determine the diffusion of
oxygen through the protecting surface layer as the rate-control-
ling step. As described in Sidebar 2 a pure silica layer exhibited
the lowest oxygen diffusion as all impurities cause lower glass
transition temperature and viscosity.
During oxidation tests of the materials with Lu2O3 and Sc2O3
as sintering additive a small weight gain comparable to that of
Si3N4 without sintering additives was observed. The oxygen
diffusion was found to be in the range to that of pure silica al-
though sintering additives were present, which usually act as
impurities and force higher oxygen diffusion. From this obser-
vation it is supposed that nearly all Lu31 or Sc31 ions have been
removed from the glassy silica oxidation surface layer into the
crystalline RE2Si2O7. In this way a nearly pure glassy SiO2 ox-
idation layer remained determining the small oxygen diffusion
into these materials. In principle the surface oxidation scale
consisted of RE ions distributed in an excess of crystalline and
amorphous SiO2. The number of RE31 ions bonded in the
amorphous SiO2 is determined by the equilibrium between the
RE31 ions bonded in the amorphous or the crystalline silicates
in the SiO2 oxidation layer represented as

x SiO2 ðcr:Þ þ RE2 O3  ySiO2 ðglassÞ2

(2)
RE2 Si2 O7 ðcr:Þ þ ðy  2ÞSiO2 ðglassÞ þ xSiO2 ðcr:Þ

In case of excess SiO2 (x, y-N) and Lu2O3 or Sc2O3 as

Fig. 15. Surface regions of polished cross-sections of Si3N4 after oxi-
dation at 15001C, 1000 h in air, (A) Sc2O3 and (B) Lu2O3 as sintering
additive, formation of small oxidation surface layer (right) of SiO2 with
crystallites of Sc/Lu2Si2O7, oxidation behavior comparable to that of
Si3N4 without additives, Table II. (H. Klemm153).
sintering additive this equilibrium was strongly shifted into the
direction of the crystalline disilicates consequently leading to a
SiO2 oxidation scale with only a minimum amount of Lu31 or
Sc31 impurities in the glass and a high-oxidation resistance.
This strongly directed equilibrium is also supposed to operate
in the amorphous grain-boundary films. A SiO2-rich grain-
boundary phase composition was adjusted from the raw mate-
rials compositions of both materials with Lu2O3 and Sc2O3 as
sintering additive. Regardless of the influence of nitrogen ions,
which will certainly have an effect on the viscosity of the grain-
boundary phase, this equilibrium determined a small amount of
Lu31 or Sc31 ions solved in the amorphous grain-boundary
films as result of the strong crystallization of the disilicates in the
multigrain boundaries. In this way the superior elevated tem-
perature potential of the materials with Lu2O3 and Sc2O3 as
sintering additives in SiO2-rich compositions can be understood
as materials with a structure and composition of the amorphous
grain-boundary films not far from that of HIPed Si3N4 without
sintering additives. However, additional investigations are re-
quired in order to explain the basic cause of the outstanding
properties of these materials in comparison with Si3N4 grades
with other sintering additive systems (e.g., Yb2O3). In this field,
detailed TEM studies for deeper understanding of grain-bound-
ary structure and composition of Si3N4 with Lu2O3 and Sc2O3 as
sintering additives as performed on other Si3N4 systems, are
recommended.143,165–168 Special focus should be placed on the
correlation between grain-boundary structure of SiO2-poor and
-rich compositions and their mechanical properties at elevated
temperatures.
1514 Journal of the American Ceramic Society—Klemm Vol. 93, No. 6

Sidebar 3. Requirements for Industrial Application

In the course of the development of high-temperature Si3N4 one should pay strict attention to the aspects and requirements of an
industrial production. The question, whether the Si3N4 optimized regarding their properties at elevated temperatures, can be
produced cost effectively with high reliability in the required geometry and in appropriate numbers is the deciding factor for a
successful industrial application.
In this focus the technical advances in ceramic powder processing, green body shaping methods, sintering and green or finish
machining achieved in the last years have crucial influence on the applicability of a well-designed and optimized material.
One of the first benefits to be mentioned was the development of high purity raw material powders essential for the design of the
intergranulary films between the Si3N4 grains.
The up-scaling of ceramic powder processing from laboratory to industrial scale has also been successfully performed. With
special focus on minimal incorporation of contaminations and high reproducibility ceramic industry is able to produce high-
quality ceramic powder mixtures with a capacity of 4100 kg/day. Similar results were obtained regarding the green shaping
technologies with the development of e.g., injection molding, slip, and gel casting or CIP with following green machining.
The sintering of high-temperature Si3N4 components is still a great challenge. Costly sintering methods like gas pressure sintering
or HIP at temperatures between 18001 and 20501C are required for densification since high refractory sintering additives systems
have to be used. Furthermore, special attention has to be placed on a homogenous sintering without distortion and an optimal
sintering surface condition with minimal defect size in order to minimize subsequent finish machining.
In order to use structural ceramics like Si3N4 reliably it is essential to have sufficient data for the prediction of reliability and
failure probability. The demands of industry are high. For automobile application a failure probability of less than one millionth
is tolerable. For that reason the control of the quality of the industrial production process from powder processing to sintering
and finish machining should be considered as a base requirement and has to be evaluated by the statistical evaluation (Weibull
parameter of the room temperature strength). The goal for material and processing development of high-temperature Si3N4
should be a strength (four-point bending) value of 4700 MPa with a Weibull of 420 measured from the material of the ceramic
component and not from the samples produced in laboratory scale. An example for a high-temperature Si3N4 fabricated in pilot
batch (10 kg) by gas pressure sintering is demonstrated in Fig. A2.

Fig. A2. Weibull plot of ambient temperature strength of gas pressure sintered Si3N4 with long-term potential up to 13001C; 6 wt% Sc2O3 as sintering
additive, SiO2/Sc2O3 5 2; s 5 803736 MPa; m 5 24; s14001C 5 500 MPa; KIc 5 5.8 MPaOm; e (14001C, 200 MPa) 5 2.0  105 h1. H. Klemm.153

Another important factor is the fracture toughness of the Si3N4. In comparison with metals an improvement in fracture
toughness from e.g., 4 to 7 MPa  m1/2 seems to be negligible, both materials are still very brittle. However, from application point
of view, materials with a KIco5 MPa  m1/2 are very difficult to handle in the whole application system as the consequence of their
very high damage and flaw sensibility. Such brittle behavior will definitely increase the failure probability to an inacceptable level.
Finally some important properties should be mentioned which were not discussed in detail in this paper. Based on the specific
conditions of use, properties like thermal shock resistance or thermal conductivity may have a great influence on the life time of
the Si3N4 component. Furthermore, some well-optimized Si3N4 for applications at temperatures 412001C failed at intermediate
temperatures between 6001 and 11001C on oxidation defects which have been formed as the consequence of insufficient formation
of the protecting oxidation layer. In this context the intermediate temperature properties should be considered in various high-
temperature applications as a limiting factor.
In summary it is concluded, that the successful application of Si3N4 in high-temperature processes does not only require superior
high-temperature properties, but the whole application process from cost effective industrial production, reliability, and failure
probability, industrial handling up to specific conditions during the application have to be focused during the development.

VI. Development of Environmental Barrier Coatings (EBC)
for Silicon Nitride
One of the most interesting applications for nonoxide ceramics
such as Si3N4 is the application as structural part in the hot gas
path of gas turbines. Besides the lower specific gravity the ad-
vantage of ceramic components is the possibility to increase the
operating temperatures with less cooling as compared with con-
ventionally used super-alloys consequently leading to an oper-
ation with higher efficiency and lower emissions.
Various Si3N4 grades reported above (NT 154, NT 164, AS
800, SN 88, SN 281/282) have been developed with focus to
these applications. Depending on the specific conditions of the
application (kind of structural part, temperature, mechanical,
and thermomechanical requirements) these materials showed a
high potential to be used in advanced gas turbines. Under dry
oxidative environments, the materials present an excellent
high-temperature oxidation resistance due to the growth of a
protective silica layer. However, one main problem preventing
silicon-based nonoxide ceramics like Si3N4 from being applied in
gas turbines were found to be the corrosion processes; especially
the reaction with the water vapor leads to surface recession and,
therefore, dimensional changes of the ceramic component oc-
cur.169–181 High water vapor pressure in combination with high
June 2010 Silicon Nitride for High-Temperature Applications
gas speed and high pressure led to rapid volatilization of the
surface protective SiO2 layer of the material by forming silicon
hydroxides (Si(OH)4). Models in order to assess the recession
rate have been provided by Opila et al.173 and Yuri et al.175 In
experimental studies, recession rates of 41 mm/h were found for
advanced Si3N4 and SiC materials destroying the materials after
serve in application-relevant times (410 000 h) in hot gas envi-
ronments.174–180 A weight loss of about 8 wt% observed after
high pressure burner rig tests at 14001C (P 5 5 bar, v 5 50 m/s,
PH2 O 5 0.9 bar) resulted in a material loss from the surface of
about 70 mm after 100 h. After an application relevant time of
about 10 000 h an unacceptably high material loss of about
7 mm would be found.179 Hence, EBCs are presented to be the
solution to protect the Si3N4 from corrosive environments at
high temperatures, preventing the corrosion attack of the water
vapor in the hot gas atmosphere. Several factors have to be
considered during the development of an EBC system:
1. Material selection: The main requirement of the EBC
material is its stability in the hot gas atmosphere (stability
against oxygen, water vapor and impurities in the hot gas).
2. Production of EBC: Besides a simple and cost-effective
coating method various morphology factors of the EBC-like
thickness, grain size distribution, and porosity have to be con-
sidered.
3. Long-term stability: The main problem in developing
EBCs should be their long-term stability up to application-rel-
evant times (410 000 h). This includes both a superior thermal,
mechanical, and chemical stability (diffusion, particle impact,
impurities) and problems as the consequence of thermal expan-
sion mismatch and shock cooling.
Several oxide ceramic material systems have been evaluated
as candidate EBC material for Si3N4.182–190 A summary of
the corrosion behavior of the possible candidates to be used
as corrosion-resistant EBC material has been provided in
Sidebar 4.183
A three-layer EBC system has been developed in a joint
research of NASA, General Electric and Pratt and Whitney
for SiC/SiC combustor liners. This system consists of a silicon
bond coat, a mullite or a mullite1BSAS ((1x)BaO  xSrO 
Al2O3  2SiO2, 0rxr1) intermediate coat and a BSAS top
coat.184,185 This system has been successfully applied for
430 000 h at temperatures of about 12001C. Lee et al.186 re-
ported an upper temperature limit of 13001–14001C, however, it
is doubtful that this reactive layer system can survive in long-
term service at this temperature as EBC coating for Si3N4. The
coatings still have significant oxygen permeability and contain
silicon, which makes them susceptible to the water vapor-in-
duced volatilization mechanism. Furthermore, the formation of
low-melting point phases from BSAS and SiO2 was reported.187
EBC systems containing CVD Al2O3, mullite, and plasma-
sprayed Ta2O5 have been investigated as protective layer on AS
800.188,189 This layer system was found to be effective in engine
tests at about 11001C for 41000 h. At higher temperatures,
however, reactions between the Al2O3 and the SiO2 formed dur-
ing oxidation would weaken the stability and functionality of the
EBC layer. Furthermore, the hot gas stability of these materials
was found to be insufficient, especially Al2O3 and mullite formed
volatile hydroxides (Al(OH)x) in hot gas atmospheres.183,191
EBC systems containing silicates of the sintering additives
used seem to have much more potential for long-term service of
Si3N4 parts at temperatures 412001C. In particular, the silicates
of the Rare Earths are suitable as primary coating materials
since they have a thermal expansion coefficient in the range of
Si3N4. Most advanced Si3N4 were densified with Rare Earths
sintering additive systems, and thus are already present in the
material. In many applications, however, simple silicate surface
layers are not sufficient, as they are not stable enough to impu-
rities (alkali and alkaline earth metal salts) in the hot gas atmo-
sphere. For this reason, multilayers with graded structures are
the most promising systems to be successful.
Detailed studies regarding the hot gas stability of Rare
Earth silicates have been performed by Fritsch.183 There are
1515
differences between various silicates of the Rare Earth. Usually
the disilicates are not stable in hot gas environment. Y, Yb, Lu,
La disilicates decompose to the monosilicates, which are stable
at hot gas conditions
Y2 Si2 O7 þ 4H2 O ! Y2 SiO5 þ SiðOHÞ4 þ 2H2 O (3)
In case of Sc2Si2O7, however, the decomposition proceeds up
to the pure oxides
Sc2 Si2 O7 þ 4H2 O ! Sc2 SiO5 þ SiðOHÞ4 þ 2H2 O
(4)
! Sc2 O3 þ SiðOHÞ4
The different behavior of the silicate systems with Y and Sc is
shown in Fig. 16 with a comparison of the weight changes of the
monosilicates during hot gas corrosion (T 5 14501C, v 5 100 m/s,
PH2 O 5 0.25 bar). Whereas the Y2SiO5 was found to be stable, in
the case of Sc2SiO5 the corrosion proceeded to pure oxide,
Sc2O3. The decomposition of the Sc2SiO5 was clearly demon-
strated by comparing polished cross sections of both materials
after hot gas corrosion (Fig. 17). A Sc2O3 layer at the surface of
Sc2SiO5 was formed during the test, the Y2SiO5 was found to be
unaffected.
With focus on the superior high-temperature stability of
SN 281/282 comprehensive studies have been performed by
Ueno using lutetium silicates as EBC material (Lu2SiO5/Lu2
Si2O7).194,195 Tests have been performed in high-speed steam jet
equipment at 13001C with a multilayer system consisting of
Lu2Si2O7 with an intermediate Lu2Si2O7/mullite layer on Si3N4.
The system sustained these conditions up to 500 h, however,
changes in microstructure of the EBC layer were observed. First
a surface corrosion with the formation of Lu2SiO5 was found.
Furthermore, cracks were generated through the coating allow-
ing oxygen diffusion into the material with the consequence of
oxidation processes at the surface of the base Si3N4.
Two opposite processes should be focused during the devel-
opment of surface coatings for Si3N4 for application in hot gas
environments in principle: oxidation of the base materials and
the actual corrosion processes. The protective SiO2 surface layer
formed during oxidation (Equation (5)) was found to be
removed in the hot gas atmosphere as the consequence of the
formation and evaporation of Si(OH)4 (Equation (6)).
Si3 N4 þ 3 O2 ) 3 SiO2 þ 2 N2 (5)
2 SiO2 þ 4 H2 O ) 2 SiðOHÞ4 (6)
In this way a well-balanced equilibrium between the forma-
tion of SiO2 and the evaporation of Si(OH)4 has to be consid-
ered. In case of strong oxidation processes during service at
elevated temperatures or already during the fabrication process
of the EBC an additional layer of SiO2 would be formed
between the base material and the protective layer. During
processes with smaller corrosion attack this layer would become
even stronger and crystallization processes in the amorphous
SiO2 layer would cause crack formation as the consequence of
volume contraction with the formation of crystoballite. In case
of periods with stronger corrosion this SiO2 layer primarily
formed would be attacked and evaporated finally leading to a
gap between the base material and the surface protective layer.
In both cases, these processes have a disadvantageous effect on
the mechanical strength leading to layer spalling of the overall
system after long-term exposure.
In principal it should not be expected that these processes can
be completely prevented during long-term exposure in hot gas
environments. Diffusion processes (O2 into and Si(OH)4 to the
surface of the material) will always proceed. Furthermore,
cracks can be opened allowing direct contact of the atmosphere
with the Si3N4 base material as observed by Ueno et al.194 In this
way the whole system, base Si3N4 and the EBC layer system,
should be considered as a dynamic equilibrium between oxida-
1516 Journal of the American Ceramic Society—Klemm Vol. 93, No. 6

Sidebar 4. Hot-Gas Corrosion Resistance of Ceramic Materials

Although ceramic high-temperature materials have been developed with superior mechanical properties the commercial applications
in the hot gas path of gas turbines were rather limited. Besides the common problems of ceramic materials such as insufficient damage
tolerance and reliability the main reason was found to be their insufficient stability in hot gas environments. Caused by the high water
vapor pressure in combination with high temperatures and gas velocities, corrosion processes were observed at the surface of the
materials resulted in the formation and evaporation of hydroxides. In this way, the standard ceramic materials for structural
applications like Si3N4, SiC, or Al2O3-based oxide ceramics suffer
Table A2. Summary of the Corrosion Tests in Atmospheric material loss by corrosion recession, which are too high
Burner Rig; Test Conditions: Temperature: 14501C, Flow for a long time use in the hot gas path of advanced gas
Speed: 100 m/s, Water Vapor Pressure 0.28 Bar turbines.106,173,175,176,181,191–193 Recession rates in the range of
Material 2
KW(mg  (cm  h)1
KS(mm/h) Kinetic 1 mm/h and more were found for advanced Si3N4 and SiC
ceramics destroying the materials after service in application-
Al2O3 0.04 0.1 Linear weight loss relevant times (410 000 h) in hot gas environments. For that
Mullite 0.038 0.12 reason the ceramic materials have to be protected by an additional
S  SiC 0.046 0.15 surface layer (environmental barrier coating, EBC) preventing the
Si3N4 0.052 0.16 corrosion attack of the water vapor in the hot gas atmosphere.
Sc2SiO5 0.006 0.016 In the context of the Ph.D. thesis of Marco Fritsch, FhG IKTS
Sc2Si2O7 0.005 0.015 Dresden,183 the corrosion behavior of various oxide and
AlTaO4 0.16 0.25 nonoxide ceramic materials in hot gas environment has been
Al2TiO5 0.029 0.083 studied systematically. The hot gas corrosion experiments were
Sc2TaO4 0.008 0.012 conducted in an atmospheric burner rig on bending bars
Y3Al5O12 0.002 0.005 3.8  3.0  36 mm3. The test samples were blown directly by the
LaPO4 0.008 0.016 hot gas in a tube of solid-state sintered SiC with an inner
MoSi2 0.03 0.05 diameter of 30 mm. The corrosion tests were performed at the
Y Si O
2 2 7 0.003 0.009 Parabolic weight loss following conditions:
Yb2Si2O7 0.002 0.003
- Temperature: 14501C
ZrSiO4 0.015 0.035
- Flow speed: 100 m/s
Yb3Al5O12 0.001 0.002
- Water vapor pressure: 0.28 bar
Y2SiO5 Stable - Testing time 100–700 h
Yb2SiO5
The calculated composition of the combustion gas was 0.64 N2,
ZrO2  3Y
0.24 H2O, 0.08 O2, and 0.04 CO2 (partial pressure for each gas
ZrO2  8Y
species) with a fuel/air ratio of about 0.5–0.6 (fuel lean
Hf3Sc4O12
conditions).
Y4Al2O9
The corrosion rate of the specimens was obtained by
Nd2SiO5 Small weight gain measuring the weight difference in relation to the surface area of
La2SiO5 the test specimen as the function of the hot gas exposure time.
Y2O3 By means of the density of the materials a surface recession rate
YbAlO3 [mm/h] was calculated.
The linear thermal expansion of the oxide materials was determined by The results of the corrosion tests on the materials investigated
thermodilatometry (Netzsch Model 402 E) in an argon atmosphere up to 14501C are summarized in Table A2 and are illustrated in Fig. A3 as the
with a heating rate of 2 K/min. The linear thermal expansion coefficient was surface recession rate as the function of the coefficient of
calculated between 201 and 14501C. thermal expansion (CTE) at testing temperature. Actually

Fig. A3. Corrosion behavior of ceramic materials investigated at14501C, depicted by the surface corrosion rate ordered by the coefficient of thermal
expansion of the materials. Courtesy M. Fritsch.183
June 2010 Silicon Nitride for High-Temperature Applications 1517

Sidebar 4. Continued
there is not a physical correlation between these parameters, however, with focus on the mechanical stability of the EBC system
the CTE of both the base material and the EBC coating is very important and has to be at a nearly similar level. In this way it is
easy to select suitable EBC materials for the standard structural ceramics distinguished by the red colored squares.
A linear recession rate was observed for the majority of the materials investigated (Si3N4, SiC, Al2O3, mullite, Sc2Si2O7). For
linear corrosion kinetics the weight loss rate Kw can be calculated with a linear fit. Some materials formed a more stable surface
layer during the corrosion processes which led consequently to decreasing recession rates with nearly parabolic mechanism
(Y2Si2O7, Yb2Si2O7, YbAG). A few materials were found stable without any corrosion attack in these conditions (ZrO2 and HfO2
compounds, Y2SiO5, Yb2SiO5), other stable materials exhibited a marginal weight gain caused of reaction of the material with
Si(OH)x in the hot gas atmosphere under formation of silicates (Nd2SiO5, Y2O3, YAlO3).
In case of the nonoxide ceramics like Si3N4 and SiC the monosilicates of the Rare Earth (Y2SiO5, Yb2SiO5) are the most
promising materials stable to corrosion.

tion and corrosion during exposure in hot gas environment VII. Summary
which should be minimized as much as possible.
1. The most important factor determining the elevated
An example of a surface protection system for Si3N4 is dem-
temperature properties of Si3N4 is the composition and condi-
onstrated in Fig. 18. The EBC consisted of a double layer from
tion of the silicate grain-boundary phase formed from the sinte-
Y2Si2O7 and a mixture of Y2Si2O7/Y2SiO5. A very small inter-
ring additives and the silica always present in the Si3N4 raw
mediate layer of SiO2 was formed during the manufacture of the
material powder. First requirements to obtain superior high-tem-
EBC by dip coating and thermal treatment. This silica was
perature properties are sintering additives forming high refractory
found to be evaporated during a hot gas test (T 5 15001C,
silicate phases and a minimal impurity level of the whole system.
v 5 100 m/s, PH2 O 5 0.25 bar), however, there was not signifi-
The crystallization of the grain-boundary phase was found to be
cant effect on the mechanical stability of the EBC after 160 h
an effective instrument to determine the grain-boundary phase.
testing. A comparison of the area of the EBC and the top Si3N4
2. The key requirement in the design of Si3N4 containing
base material before and after hot gas corrosion at 15001C is
sintering additive with crystallized grain-boundary phase is the
given in Fig. 19. With such kind of EBC the hot gas corrosion
residual amorphous grain-boundary phase in the intergranular
resistance of Si3N4 can be improved considerably. A comparison
films, which should be characterized by high viscosity and soft-
of the mass balance of the coated and uncoated Si3N4 after hot
ening point. Whereas the amount of the sintering additive was
gas tests at 15001C is presented in Fig. 20. Because of the pro-
tective effect of the surface layer a significantly reduced corro-
sion in the coated material was observed. The recession
measured was found to be in the range of Y2Si2O7 indicating
a corrosion process at the surface (Y-disilicates to the monosil-
icate) as described above. For long-term use at these tempera-
tures the protective effect of these layers is still not sufficient. A
multilayer system with corrosion resistant compounds like
ZrO2, HfO2 is recommended to improve the corrosion resis-
tance of the EBC. Furthermore, extensive studies have to be
performed in order to improve the mechanical stability of the
whole system, EBC base and Si3N4.
In summary, it is likely that the future development of effec-
tive EBCs should be focused on multilayered systems with self-
healing protection mechanisms designed in the material itself.
Both the EBC protection system and the base Si3N4 (condition
and composition of the grain-boundary phase) have to be sta-
bilized in order to maintain the material properties during the
whole duration of service at elevated temperatures.

Fig. 17. Surface regions of polished cross-sections of and Sc2SiO5 (cor-

rosion zone at the top of the material as the consequence of decompo-
sition of the monosilicate to Sc2O3, (A)) and Y2SiO5 (stable material,
Fig. 16. Comparison of the corrosion behavior of Y2SiO5 and Sc2SiO5 (B)) after hot gas corrosion (T 5 14501C, v 5 100 m/s, PH2 O 5 0.25 bar).
(T 5 14501C, v 5 100 m/s, PH2 O 5 0.25 bar). Courtesy M. Fritsch.183 Courtesy M. Fritsch.183
1518 Journal of the American Ceramic Society—Klemm
Fig. 18. Part of environmental barrier coating at the surface of Si3N4
consisting on a mixture of Y2Si2O7/Y2SiO5 bonded to the Si3N4 material
by a thin SiO2 interface. H. Klemm.153
found to have only a slight influence on the high-temperature
properties, if the two grain boundaries were not affected in
composition and shape, the composition of the grain-boundary
phase (SiO2/RE2O3 ratio) exhibited significant influence on the
elevated temperature properties.
3. A superior high-temperature resistance has been reported
for Si3N4 grades with Lu2O3 or Sc2O3 as sintering additives in
SiO2-rich compositions. Effective crystallization of the grain-
boundary phase to RE2Si2O7 leaving nearly clean amorphous
Fig. 19. Comparison of environmental barrier coating (EBC) before
(A) and after (B) hot gas corrosion at 15001C (v 5 100 m/s, PH2 O 5 0.25
bar, 160 h). EBC still intact, SiO2 interface between EBC and Si3N4
material was found to be evaporated as the consequence of hot gas cor-
rosion. H. Klemm.153
Vol. 93, No. 6
Fig. 20. Mass balance of coated and uncoated Si3N4 material after hot
gas tests at 15001C. H. Klemm.153
films between the Si3N4 grains is suggested to be the reason of
this behavior. In this way the high-temperature behavior of both
systems became comparable to that of HIPed Si3N4 without
sintering additives.
4. The oxidation of Si3N4 can be controlled using sintering
additives (Lu2O3, Sc2O3), which allows only minimal oxygen
diffusion into the Si3N4. Furthermore, microstructural and com-
positional alterations as the consequence of oxidation can be
minimized by a changed oxidation mechanism observed in Si3N4
composites with SiC or MoSi2.
5. The corrosion of Si3N4 in hot gas environments is still an
opened problem and must be solved for a successful application in
advanced gas turbines. Progress has been achieved in the devel-
opment of potential material systems with high stability under hot
gas conditions. Main focus on future research should be placed on
the long-term stability of the whole system, EBC and base mate-
rial, based on a detailed understanding of the processes during
application in hot gas environment at elevated temperatures.
6. Besides the optimized properties at elevated temperatures
special attention has to be placed on the industrial production of
components with cost-effective methods, high reliability, com-
plex geometries and in appropriate numbers. Increased efforts of
industrial research in this area are required in future to bring the
advanced Si3N4 currently available to industrial application.
7. From the current knowledge a temperature limit of ad-
vanced Si3N4 up to 15001C seems to be realistic. However, the
mechanical, thermophysical, and chemical requirements of a
particular application can limit the high-temperature potential
of the Si3N4 considerably.
Acknowledgments
During my studies in the field of high-temperature Si3N4 I had the possibility of
comprehensive scientific discussions with several colleagues contributing to this
paper. In particular I would like to acknowledge Giuseppe Pezzotti and Isao Tan-
aka for the collaboration during our time in Osaka University. High input was
obtained during collaboration in industrial projects with CFI Rödental (Gerhard
Wötting, Ernst Gugel), Siemens PG (Christine Taut, Ulrich Bast) and Honeywell
ES&S (Bjoern Schenk, Jim Wimmer, Mike Meiser, Chen Wei Li). Furthermore,
I would like to acknowledge the intensive scientific discussions with colleagues like
Shelly Wiederhorn, Frank Lofaj, William Luecke, HT Lin, Andy Wereszczak,
James Smialek, Beth Opila, and Andreas Rendtel. Finally, I thank my colleagues
from FhG IKTS Dresden especially Christian Schubert, Marco Fritsch and
Mathias Herrmann.
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Hagen Klemm studied Chemistry at the Technical University of Dresden, Germany, and received his
Ph.D. in Inorganic Chemistry from here in 1985. Prior to joining Fraunhofer IKTS Dresden in 1990 he
started to work in ceramics field in 1987 in the Institute of Solid State Physics and Materials Science
Dresden. His research interests concern material development, processing and characterization of
ceramic materials, especially for high-temperature applications. During his post-doc study in Osaka
University (ISIR) in 1991 he worked in the field of combustion sintering and high-temperature silicon
nitride. Dr. Klemm has published over 120 peer-reviewed scientific papers and conference
contributions mainly focussing on the high-temperature behaviour of silicon nitride. Since 2006 he
is the head of the department non-oxide ceramic materials in IKTS Dresden.