journal
, 75 [21 259-76 (1 992)
Thommy Ekstrom” and Mats Nygren*
Department of Inorganic Chemistry, Arrhenius Laboratory,
Stockholm University, S-106 91 Stockholm, Sweden
The phase relations in and physical
properties of SiAlON ceramics pre-
pared by the hot isostatic pressing
technique or by pressureless sintering
with a sintering aid are reviewed. The
sintering aid used is an AIN and A1203
mixture either pure or in combination
with Y 2 0 3 and/or various rare-earth
oxides. Special attention is paid to the
amount and type of phase(s) formed
and to how properties such as hard-
ness (HVlO), fracture toughness ( K I C ) ,
and oxidation resistance vary with the
sintering aid used for different types
of SiAlON materials, i.e., 0’-,almost
monophasic a-,pure p-, and mixed
(a+/?)-SiAION ceramics.
I. Introduction
THEconcept of ceramic materials cov-
ers a vast number of very different sub-
stances if a broad definition is used;
thus, ceramics are nonmetallic, inor-
ganic materials that require processing
temperatures above 500°C. If the scope
of the definition is limited to the high-
performance engineering ceramics,
however, the list of candidates with
high strength, wear resistance, and
chemical inertness at high tcmpera-
tures is fairly restricted. In this more
restricted group the so-called silicon
nitride- (Si3N4-) based ceramics are
among the prime candidates, including
the fairly recently dcveloped SiAlON
(from Si-AI-0-N) ceramics described
in detail in this paper.
SiAlON ceramic materials have been
d e v e l o p e d m a i n l y d u r i n g t h e last
decade, and fully dense polycrystalline
R. E. Newnham-contributing editor
Manuscript No. 1Y63OY. Received Septem-
ber 27, I Y Y I ; approved December 10, 1 Y Y l .
*Member, American Ccramic Society.
J . Am. Ccrm. SOC.
SiAlON Ceramics
bodies can now be prepared by pres-
sureless-sintering techniques. Much of
the improvement in mechanical prop-
erties of SiAlON ceramics during the
last few years is the result of careful
control of Si3N4 starting powder qual-
ity, processing, and subsequent consoli-
dation. Sintering aids, besides AlzOi
and AIN, are normally used to allow
pressureless sintering to full density,
and in most cases this gives rise to a
residual intergranular phase in SiAlON
materials because the constituents of
the liquid phase formed at sintering
temperatures cannot be fully incorpo-
rated into t h e Si3N4 structure. O n e
negative consequence of this result is
t h a t many of t h e m e c h a n i c a l a n d
chemical properties of ceramics at
higher temperatures are in fact deter-
mined by the propcrties of the inter-
granular phase. This is especially the
case when this phase is glassy (amor-
phous), a n d t h e p r o p e r t i e s of t h e
ceramic rapidly deteriorate at tempera-
tures above the glass transition tcm-
perature, where the viscosity of the
glass decreases significantly.
Si3N4occurs in two structural modifi-
cations, a and p . T h e solid solution
in p-SinN4, formed by simultaneous
equivalent substitution of AI-0 for
Si-N was first called p ’ - S i j N 4 , later
p’-SiAION, and nowadays p-SiAION.’.’
P-SiAION has most commonly been de-
scribed by the formula Si6-zAlzOzN8-z,
since the unit cell contains two “Si3N4”
units. I n this formula the ‘‘z value”
can be varied continuously from zero
t o about 4.2.3-5 A formula using
modern nomenclature should b e
Si3-,AI,0,,N4-x, which clearly demon-
strates the SilN4 parent. This phase is
found in the technically very important
p a r t of t h e S i - A I - 0 - N system with
stable valence states, namely the quasi-
ternery Si3N4-SiO2-AlN-Al2O3 system
given in Fig. 1.’ T h e “behavior dia-
260 Journal of the American Ceramic Society -Ekstrom and ~Vygren Vol. 75, No. 2

Panel A Structure

Si3N4 o c c u r s in t w o different 7.818(3) A and c=4.591(4) A.75Thc

crystallographic modifications, de-
noted a and p.73,74 Both structures
are built up of corner-sharing SiN4
tetrahedra. T h e structures can be
regarded as consisting of layers of
silicon and nitrogen atoms in the
sequence A B A B . . . or ABCD-
A B C D . . . for the p and a modifica-
tions, respectively. The A B layer is
the same in the a and p phascs and
the C D layer in the a phase is re-
lated to the A B layer by a c-glide
plane. This also implies that t h e
silicon-nitrogen bonding distances
in the p modification arc more uni-
form than in the a modification.
The SiN4 tetrahedra in p-Si3N4 are
linked together in such a way that a
phenacite-like structure is formed
which contains tunnels running par-
allel to the c-axis of the unit cell as
shown in the accompanying figure.
(The smaller circles represent sili-
con atoms and the larger ones nitro-
gen.) Because of the glide plane
relating the AB and C D layers, the
a phase contains cavities instead of
tunnels. T h e symmetry of t h c a
modification is trigonal, a n d its
space group is P31c with the fol-
lowing unit-cell parameters: a =
corresponding data for the p modi-
fication areoPh3 (hexagonal) wi;h
a=7.595(1) A and c=2.9023(6) A ,
based on single-crystal refinement.7'
It has been suggested, and its also
seems to be generally accepted, that
a-Si3N4 is a low-temperature modi-
fication which transforms to p at
higher temperature^.^" T h e trans-
formation implies breaking a n d
formation of bonds, but the local
coordination is maintained. The rc-
verse reaction has, however, not
been observed, possibly because of
kinetic hindrance.?'
T h e structurc of S i 2 N 2 0is related
t o b o t h S i O z a n d SiiN4.77 T h e
oxynitridc is built up of SiN,O tc-
trahedra which are linked togethcr
to form a three-dimensional net-
work. T h e s t r u c t u r c c a n b e rc-
garded as consisting of puckcred
hexagonal laycrs comprising equal
numbers of silicon and nitrogen
atoms, and the laycrs are linkcd to-
gether by oxygen atoms which com- layer bclow. This implies that every
plete t h e tctrahedra around t h e oxygen atom is connectcd to two
silicon atoms. One-half of the sili- silicon atoms, as in S O z , and the
con atoms within a layer are, via nitrogen and silicon atoms are, rc-
these oxygens, linked to the layer spectively, three and four coordi-
above, and the other one-half to the nated, as in Si3N4.

gram" of this systcm at different tem- solution rangc, named O'-SiAION, by

peratures is bcst illustratcd as a
reciprocal salt system (see Fig. l(b)).3.h-K
One should, however, be aware that
most diagrams similar to this one of
nitride or oxynitride systems do not
necessarily represent true thermody-
namical cquilibrium phase rclation-
ships.
T h e silicon oxynitride phase
(Si2N,0) found in this system is also of
interest as an engineering ceramic. The
S i 2 N 2 0structure forms a narrow solid-
Al 3(Si02) 3AI2O3*SiO2 2(A1,03)
SI
0 Additions o f a n additional metal
B o x i d e ( o r n i t r i d e ) will c x p a n d t h e
I
the same mechanism as P-SiAION; i.e.,
Si+N is replaced by A1+0." 0'-SiAlON
can thus be rcprcsented by the formula
Si2~,A1,01+,yN2 ,, where the "x-value"
varies from zero to -0.2."' The five or-
dered SiAlON polytypoid phases occur
close to the AIN corner in this system,
and these phases arc structurally very
similar to each other and are based on
the wurtzite-type structure of the par-
ent AIN phase." Each of the phases has
a solid-solution rangc along lines with a
constant mctal: non-mctal ratio
A1,(O,N)x+,, and they arc named with
Ramsdell symbols, i.e., 27R, 21R, 12H,
15R, and SH.'." The SiAlON polytypoid
phases are not further discussed in this
paper.

-cW SiAlON phase diagram into a five-com-

5 poncnt system, Me-Si-Al-0-N. A conve-
rn
W
n i e n t way t o i l l u s t r a t e t h i s is by
12H
Si2N20 21 R a so-callcd J l n e c k e prism."," T h c
27R Janeckc prism that schematically de-
scribes the positions of the SiAION
phases in the wcll-known Y-Si-A1-0-N
StiNi 4(AIN)
Equivalent % Al system is shown in Fig. 2. Y20i has been
(6) one of the most successful oxide addi-
tives14-lh
Fig. 1. (A) Si-AI-0-N system and the subsystem Si02-SiiNI-AIN-A120,. (B) Behavior because a refractory glass is
diagram of the subsystem, illustrated as a reciprocal salt system at temperaturcs of 1700" formed. This is also the case with the
1730"c,'."-x rare-earth-metal oxides. Thesc SiAlON
materials are especially describcd in
this paper.
February 1992
a-SiAION is another solid solution
based on a Si3N4 structure: it i s iso-
structural with t h e low-tempcraturc
modification a-Si 3N4.Of special intcr-
est a r e t h e M e - S i - A I - 0 - N systems
where the a-SiAlON phase i s stabilized
by the added Me ion, whcrc Me is Li,
Mg, Ca, Y, and the rarc-earth metals
except La, Ce, Pr, and Eu.”-l” T h e
a-SiAION phase region has a two-
dimensional extension in t h e plane
Si3N4-;(Al2O3.AIN)-McN,3AlN of thc
Me-Si-AI-0-N phase diagram in Fig. 2.
The P-SiAION solid solution, which is
extended along t h e line Si3N4-
(Al2O3.AIN),thus falls on one border
of the plane mentioncd. The a-SiAION
unit-cell c o n t e n t , comprising f o u r
“Si3N4” units, can be given in the gen-
eral f o r m u l a M e ,n S I 2 ( I , ) n +?,,A1( I , i n + ,,)
-
OnNlh-,lfor a metal ion Me’”. Two sub-
stitution mechanisms may act; the first
i s similar to that of P-SiAION with
n(Si + N) being replaced by n(Al+ 0).
Thc sccond mechanism i s further re-
placement of p s i 4 +by pmAl”, thc
electron balance being retained by in-
corporation of mMe”+ into the a-phase
structure. a-SiAION has been most cx-
tensively studied in the Y-Si-AI-0-N
system, where t h e two-dimensional
phase field extension can be expressed
as YxSil-(i,+,)Al(i,+,,~0,N4-,,, with 0.08
<x<0.17 and 0.13 <n <0.31.’x~”’-z’ T h e
lower solubility limit is located at
x=-0.08 to 0.10, regardless of the mod-
ifying cation Me of the rare-earth se-
ries, whereas t h e higher limit i s at
x=-0.15 to 0.20 for cations with a ra-
dius of 0.095 to 0.1 nm, and signifi-
cantly higher, x=0.25, for small cations
such as ytterbrium with a radius of
-0.085 nm.24
By varying the overall composition
in the Me-Si-AI-0-N system, it is possi-
blc t o vary t h e a - S i A I O N : ( a + P ) -
SiAlON phasc ratio of sintercd ceramics
in a controllcd way, and this will give
rise to a series of materials where hard-
ncss and fracture toughness can be
tai lored.?%?h Besides the mechanical
properties, the chemical properties at
high tcmperatures are cqually impor-
tant in many applications, and these
will also be affected by changing the
phase composition. The presentation of
experimental results in following sec-
tions describes the SiAlON ceramics
and their properties. By using the rc-
sults from sintering Si3N4 with A1203
and A1N and various metal oxide addi-
tives, the effects of pressureless sinter-
ing or hot isostatic pressing (HIPing)
arc illustrated. It is shown that SiAlON
solid solutions that form during sintcr-
ing might allow transient liquid-phase
sintering by very careful processing,
lcaving a single-phasc SiAlON material
with no or very little glassy intcrgranu-
lar phase present. It i s also demon-
strated that the addition of even very
small amounts of a glass-forming oxide
SALON Ceramics 261
Panel B Calculation of Equivalents
The location of the Si;NJ-SiO:- in the diagram. Equivalcnts i n the
A1203-AIN phase area within the three-dimcnsional Y-Si-A1-0-N Jan-
ternary Si-A1-0-N diagram is illus- ecke prism are defined according to
tratcd in Fig. L(A). The phasc rcla- the following equations:
tions bctwccn Si?N,, S O 2 , Al2O1,
and AIN are, however, commonly
describcd by t h e phase diagram
given in Fig. 1(B). This diagram dif-
fers from the one in Fig. 1(A) in Sic,= 1-Alcq- Y,,
that the x-axis and y-axis scales are
expressed in equivalent percents of
aluminum and oxygen, rcspcctivcly, N,,=l -Ocq
instead of molc percents. YzO, is
one of the most successful sintcring where the indices eq and at. dcnotc
aids, and addition of this oxide will equivalents and atomic fractions, rc-
thus expand the phase diagram il- spectively. It can be shown that any
lustrated in Fig. 1(B) to a five-com- point in the Janeckc prism can be
poncnt systcm, Y-Si-A1-0-N. T h c describcd by the formula
phase rclations in the Y-Si-AI-0-N
systcm arc schematically shown in
Fig. 2 by means of a so-called Jan-
eckc prism.’’,’’ Only the phases of with O s l - A l c q - Y c ~ l s l .
interest in this paper are illustrated
to such a SiAlON ceramic will detcrio-
rate the high-temperature propertics.
11. Microstructure and Properties of
Y203-DopedP-SiAION
Addition of cquimolar amounts of
A1203 and AIN to Si?N4 prior to high-
tempcrature sintcring will form t h c
important singlc-phase P-SiAION ce-
ramics. Studies by high-resolution
transmission clcctron microscopy
(TEM) of such matcrials prepared by
glass-encapsulatcd HIPing have shown
that the microstructure contains no. or
only extremcly small amounts of, glassy
g r a in - b o u n d a r y p h a s c .’.’ T h e grain
sizc at low x values in S i 3 - ~ , A l , 0 , -
N, i s -1 p m , and it increases to
I
-5 p m at x = 2 . The crystal shape at
low x values is gcnerally roundcd or
slightly elongated grains with the typi-
cal hexagonal cross section. The grain
morphology is practically unchanged at
p-SiAlON
high x values. despite the larger crystal
sizc. The mcchanical properties of the Fig. 2. Part of the Y-Si-AI-0-N system
low-substituted P-SiAlON are very simi- drawn schematically as a Janecke prism to
lar to those of P-Si3N4,but both hard- illustrate the positions of the a-, p-, and
ncss and fracture toughness deteriorate 0’-(“Si2N20”)SiAlON phases.
with increasing x value, as demon-
strated in Fig. 3. T h e significantly
lower hardness observed at high x values
might be explained by the coarscning of
the grain structure. The absencc of a
glassy grain-boundary phase in these
matcrials allows thcm to retain the me-
chanical properties to high tempera-
tures, and thcy have good hot hardness
to at least 1200°C.
A small amount of Y 2 0 3 , corre-
sponding to 1 to 3 wt%, added prior to
the sintering of P-SiAION ecramics re-
sults in 2 to 6 vol% of residual glass in
the microstructure? Even with only
1 wt% Y2O3 added, -2 and 3 vol% of
 Journal of the American Ceramlc Society - Ekhtriim und N y p e n
262
1800
-0 1600
I 1 wt% YzOJ addition
?
j, 1400 # m
a
E 9
1200
,"""
0 1 2
x value
(A)
Fig. 3. (A) Vickers hardness (HVIO) and (B) indentation fracture toughness ( K K ) as
functions of the com osition of p-SiAION ceramics, Si;_,AI,0,N,-4, w i t h and without
1 w t % Y,O, addition.
R,,
Various methods have been used
t o characterize SiAlON materials
described in this paper.
Density measurcments in combi-
n a t i o n w i t h optical microscopy
studies of carefully polished sec-
tions have been used to determine
t h e degree of solidification. T h e
densities of the sintered specimens
have been determined by the Archi-
medes principle. Because of the fact
that SiAlON ceramics contain inter-
granular phase(s), it is not possiblc
to make any reliable calculation of
the theoretical density of a SiAlON
c e r a m i c w i t h a specific overall
composition. To experimentally es-
tablish t h e maximum attainable
density, SiAlON ceramics have been
densified by hot isostatic pressing,
using glass-encapsulated samples.
Optical inspection has shown that
t h e porosity is well below 0.5%
of the total volume in these samples,
and they are accordingly described
as fully dense."
Phase analysis has normally been
based on analysis of X-ray powder
patterns obtained in a Guinier-Hagg
focusing camera with C u K a , radia-
tion with silicon as internal stan-
dard. The lattice parameters of the
different phases have been refined
with a least-squares program. The
equations a=0.38015+0.001484~nm
and c=0.14535+0.001277~nm have
been used to calculate the x value
of the P-SiAION, Si3-LA1,0,N4-,.5
A recently revised method for quan-
titative estimation of the amounts
of Q and p phases in Si3N4-based
ceramic materials has been devel-
oped.28The method is based on de-
termination of intensity ratios of
the reflections (101) and (210) of the
p phase and (102) and (210) of the a
phase, and it allows the presence of
impurity phases. It has also been
shown that the use of peak height
measurements instead of integrated
intensities is confined to cases where
5
4
I
1 wt% Y 2 0 J addition
; E 3
#
a
Single phase ~ S I A I O N
2 2
1 Sir A1 0 N1
0
0 1
x value
(6)
Panel C Characterization
the studied material consists of well-
crystallized phases with similar
structures. X-ray diffraction has
been used to characterizc the crys-
talline phase(s) in the oxide scale
formed upon oxidation of Si3N4-
based ceramics.
T h e microstructure of sintered
SiAlON specimens has been studied
by scanning electron microscopy. To
avoid charge effects, the polished
surface studied is coated with a
thin layer of carbon or gold. In mi-
crographs obtained with back-scat-
tered electrons, the brighter areas
contain more of thc heavy elemcnts
than do the darker areas. To the
extent that a sintering aid such as
Yz03 is used in connection with the
preparation of SiAlON ceramics, an
intergranular phase rich i n t h e
added sintering aid is formed, be-
sides the a and p modifications of
the SiAlON phases. Because some
of the added sintering aid is incor-
porated into the a phase but not
into the p phase, the darkest arcas
in a micrograph of a SiAlON ce-
ramic c a n b e ascribed to t h e /3
phase and the brightest areas to the
intergranular phase. The amount of
intergranular phase can be visually
estimated by the relative amount of
bright areas, measured by a grid
technique on the micrographs, or it
can b e more accurately found via
computer-controlled measurements
of areas of different darkness. The
latter technique can also be used to
follow how the size and shape of
the crystals formed vary with pro-
cessing parameters such as amount
of sintering aid used, temperature,
and pressure applied.
In connection with transmission
electron microscopy and high-resolu-
tion electron microscopy studies, it
is necessary to use thinned samples.
Thin plates (<0.2 mm) are cut with
a diamond or wire saw and dimpled
to a thickness of about 40 pm. The
Vol. 75, No. 2
glac\ are found in the matcrialc with
v
x=0.25 and x=1.9, respectively. Analy-
sis of the glass composition by energy
dispersive spectroscopy (EDS) is possi-
t
I
ble only in the x=l.9 material, where
8 the glass volumes are larger. The analy-
sis result varies somewhat from one
glass pocket to another, but to a good
Single
phase
I
I
Mull1
phase approximation the elcment proportions
region , region are Si:Al:Y=2:2:1. Thus, the added
YzOi rcacts with thc S i 0 2 present and
7
2
also with some of the initially added
Al2O3,which explains why even small
additions of an oxide such as Y20, can
initiate the formation of considerably
greater amounts of glassy phase. The
hot hardness is negatively influenced
final thinning is made by argon
milling. To prevent charging in the
microscope, the specimens are cov-
ered with a thin carbon o r gold layer.
Oxidation studies have been per-
formed by the thermogravimctric
(TG) method, which implies con-
tinuous rccording of the weight in-
crease with the time of oxidation
under isothermal conditions. T h e
carefully polished specimens are
connected to the TG unit via a plati-
num wire. Oxidation of this wire
occurs at higher tcmperaturcs undcr
formation of gaseous PtO,. To ob-
tain reproducible data, one normally
has to apply a correction for the
drift of the baseline, originating
from the drift of the measuring unit
and from the loss of platinum. In
the case of a low degree of oxida-
tion and high tempcratures, such a
correction is of great importance.
Thc best experimental setup is one
provided with two furnaces record-
ing the weight diffcrcnce between a
dummy and the specimen. The oxi-
dation curves described in this ar-
ticle have been obtained with use of
such a unit having a resolution of
2 p g and a drift of the baseline
of 2 5 pg over 20 h.
In connection with hardness
(HV10) and indentation fracture
toughness ( K I c )measurements, spc-
cia1 care in the polishing has to bc
taken to minimize any influence of
introduced compressive s u r f a c e
stresses on the measurements. The
hardness and indentation fracture
toughness values rcportcd in this ar-
ticle have been obtaincd by a Vick-
ers diamond indenter using a 98-N
(10-kg) load, and the fracture tough-
ness has been evaluated by t h e
method of Anstis et al.'" Repeated
measurements on the same sample
showed the precision of the mcasure-
ments to be ?30 and k0.2 MPa.
for the hardness and toughness
values, respectively.
February 1992 SiAlON Ceramics 263

even with only 1 wt% YzOi

and the matcrial is not suitable for usc
at tempcraturcs above -1000°C. This is 4
4
commented on further in Section VI(I).
However. for applications at low or
medium tcmpcratures, a small addition 3 3

of sintering aid has a positive influ-

ence on thc fracture toughness.?" The
glassy grain-boundary phase that forms
is a preferred crack path, and crack
fl SiAlON x ~ 0 25 I P-SiAION x = 1 9
14OO'C

branching occurs, thereby incrcasing 1

the fracture energy. For example, the

r o o m - t e m p e r a t u r c t o u g h n e s s of a 0 0
P-SiAION ceramic is significantly in- 0 5 10 15 20 0 5 10 15 20
creased by the addition of 1 wt% Y203 Time (h) Time (h)
(A) (6)
(Ref. 5) (cf. Fig. 3). Thesc results are in
accordancc with the recent findings of Fig. 4. Oxidation resistance a t 1400°C of single-phase p-SiAION ceramic? w i t h (A)
Tanaka et al.,'* who have found that x=0.25 and (B) x = l . 9 . As a comparison, the oxidation behavior of p-SiAION ceramics
the fracture toughness is greatly de- with 1 and 3 wt% Y;O? added prior to the sintering is included."
pendent on thc grain-boundary proper-
ties. When thc grain-boundary bonding 2100
6 *
is sufficiently strong, c.g., i n t h e 2000
absence of a glassy grain-boundary
phase, cracks propagatc transgranularly -0 1900 5 -

in t h e matcrial a n d t h e toughness 5 1800

is low. E 1700
4

Similarly, the oxidation resistance is n

affected by small Y203additions to a 1600

p-SiAION material, as shown in Fig. 4.
The oxidation resistance at 1400°C of
single-phasc P-Si AION ceramics pre-
pared without a sintering aid is good
because of the formation of a protec-
tive oxide scale. The oxidation rcsist-
ance varies with the x value of t h e
B-SiAlON, howevcr, and it seems to
decrease in the ordcr x=O.25, 0.5, and
1.9. Microstructural and X-ray investi-
gations have shown that t h e oxide
scale contains cristobalite and mullitc
besides an amorphous phase. Cristo-
balite is found in materials with low
x values (0.25) a n d mullite i n P -
SiAlONs with high x values (1.9),
whereas, for intermediatc composi-
tions, both mullite and cristobalite are
present."
T h e a m o u n t a n d composition o f
t h e amorphous phasc in t h e oxide
scale also vary with the overall compo-
sition. The increased oxidation rate of
materials with higher x-valucs is be-
lieved to be due to oxygcn diffusing
more rapidly through an aluminum-
c o n t a i n i n g a m o r p h o u s phase t h a n
through amorphous S O ? .
When 1 wt% Y 2 0 3is used as sinter-
ing aid, implying that yttrium is present
in the intergranular phase, higher oxi-
dation rates are obscrved. The oxida-
tion resistance decrcases in the order
x=0.5, 0.25, and 1.9, but the differ-
ences between the rate constants are
small, and, accordingly, the composi-
tion of thc amorphous phase is almost
the same for all compositions. As the
Y 2 0 3 contcnt is further increased, the
oxidation rate increases rapidly. T h e
Y203 is depleted from the ceramic and
gathered in the oxide scale. The dcgra-
dation of the oxidation resistance is
substantially more pronounccd for
3~ o p SiAlON
1500
5
1400
0 05 1
cl'(o+p) ratio
(A)
Fig. 5. (A) Vickers hardness (HVIO) and (B) indentation f r x l u r e toughness (KIc.)as
functions of the cu:(a+p) phase ratio in (n+p)-SiAION materials.-'.-'
P-SiAION with x=0.25 than that for
x = l . 9 . Microstructural studies show
that the oxide scale on materials with
low x-valucs and prepared with YzOi
contcnts of 3 wt% or morc is very dis-
rupted, implying that a solid protective
layer is ncver formed.
111. Pressureless-Sintered p- and
(a+P)-SiAION Ceramics
(I) General
T h e best-known group of SiAlON
ceramics is P-SiAION containing a
substantial excess of sintering aids,
which allows prcssureless sintering.
T h e s e matcrials contain elongated
grains in their microstrueturc and also
a considcrable a m o u n t of residual
glassy phasc, and they have the highest
obscrved fracture toughness values at
room tcmperaturc among the different
SiAlON materials. By changing t h e
overall composition in the Y-SiAION
phasc diagram, (a+P)-SiAION ceram-
ics can be prcpared with a varying
a-SiA1ON:P-SiAION phasc ratio."." a-
SiAlON always appcars as cquiaxed
grains in the microstructurc of the ma-
terial a n d p-SiAION as elongated
fiberlikc grains with an aspect ratio
typically in the rangc of 4 to 7. Hard-
ncss incrcascs markcdly with increas-
ing a-SiAlON phase content, whereas
thc fracturc toughncss decreases (see
Fig. 5). This dccreasc in toughness has
264 Journal of the American Ceramic Society - Ekstrijm ar;id Nygren
been thought to be caused by the fact
that the a-SiAION grains do not have
t h e typical elongatcd shape of t h e
/3 grains, but other factors, such as the
intrinsic strength of the glassy phase
and the bonding between the glass and
thc elongated P-SiAION grains, may
also have an influence.
T h e possibility of varying the a-
SiAlON : p-SiAION phase r a t i o by
slightly changing the overall composi-
tion opens many possibilities to pre-
pare Y-SiAION ceramics with desired
properties. This is of the utmost im-
portancc in connection with tailoring
the properties for specific applications.
Other ways of changing the properties
of SiAlON ceramics arc also available,
for instance, replacing Y 2 0 3 by othcr
oxide additives. A wide range of metal
oxides have been tried, but the most
interesting ceramics a r e still those
formed with additives giving refractory
glasses upon cooling, i.e., the rare-earth
oxides. Therefore, effects on solidifica-
tion, phase content, microstructure,
and mechanical and chemical proper-
ties are shown below for a number of
rare-earth-metal oxides. These rare
earths have been chosen to represent a
group of more readily available and
less expensive metal oxides ( C e 0 2 ,
N d 2 0 3 , and L a 2 0 3 ) and a group of
more cxclusive ones ( D y 2 0 3 , S m z 0 3 ,
and Y b 2 0 3 ) . T h e latter rare-earth
metals have been selected for a wide
variation of atomic number (Z).
(2) Effects of Type and Amount of
Sintering Aid on Solidification
The p- and an (a+p)-SiAION ma-
terials used for this comparativc study
are both located close to the Si3N4cor-
ner of the Si-AI-0-N phase diagram.
The two compositions have the same
a l u m i n u m : silicon equivalcnt r a t i o
(x=0.095), and the oxygen: nitrogen
equivalent ratios of the materials are
y=0.070 and 0.048 for the P-SiAlON
3.35 1
3.30
.
-
0)
3.25
.->
I 3.20
I
D
3.15
3.10 ,
~7 1 ficult to obtain. The high solubility of
1oo:o 75:25 50:50 25:75 0:lOO
Y203:Nd203ratio
Fig. 6. Variation in density as a function of amount of sintering
aid and the Y z O ~N: d 2 0 3 ratio after pressureless sintering at
1825°C for 2 h.”
Vol. 75. No. 2
and the (a+P)-SiAION materials, re-
spectively (cf. Fig. I@)). A constant
molar amount of added oxide was used
here in all preparations to simplify
comparison of the observed properties,
i.e., 6.0, 8.4, 8.9, 9.2, 9.3, 9.9. and
10.5 wt% of thc oxides Y z O ~ La203, ,
N d 2 0 i , CeOz, S m z 0 3 , Dyz03, and
Y b 2 0 3 ,respectively. The samples were
either pressureless sintered at 1700” to
1825°C for 1 to 2 h in a powder bed of
submicrometer BN or glass cncapsu-
lated and HIPed at 1550” to 1900°C
with 200 MPa of argon.
The composition of the added sinter-
ing aids and the sintering temperature
and time are factors which influence
the solidification process. In general,
more oxygen-rich overall compositions,
r e p r e s e n t e d i n t h e s e examples by
P-SiAION material, are easier to sinter
to full density than the nitrogen-rich
(a+P)-SiAlON materials. The sintering
conditions for obtaining fully dense
materials with a minimum of rcsidual
glassy phase are fairly restricted. Tem-
peratures above 1825°C cannot be used
because of rapidly increasing decompo-
sition of the Si3N4.Temperatures below
1750°C extend the sintering time un-
duly and may even cause some micro-
porosity to remain, and the complete
a to p transformation is also very slow.
If the YzOl content is reduced below
4 wt%, the porosity level incrcascs in
the materials, implying that the 4 wt%
level is about the lowest Y 2 0 3 addition
t h a t c a n be used t o o b t a i n dense
Y-SiAION materials by pressurcless
s i n t e r i n g . A d d i t i o n of m o r e t h a n
6 wt% Y 2 0 3is not needed for p or for
low a content (a+P)-SiAlONs, but it
might be justified in preparing ceram-
ics with very high a-SiAION contents.
Thus, at sintering temperatures in the
range 1750” to 1825”C, and 4 to 6 wt%
Y203 additive, fully dense materials
are obtained both for p- and (a+p)-
SiAlON ceramics.
The replacement of Y 2 0 3 by N d 2 0 3
or C e 0 2 at the “6 wt% Y 2 0 3 level”
gives dense materials for all Y : M e
compositions, whereas, at the “4 wt%
Y203 level,” only P-SiAION material
attains acceptable dcnsities, as shown
for Nd203 in Fig. 6. With this low
amount of sintering aid, the (a+p)-
SiAlON materials prepared with NdzOi
as a sintering aid are very poorly den-
sified, sometimes even below 95% of
theoretical density (TD). L a 2 0 3is a less
attractive sintering aid because, even
at the “6 wt% level,” fully dense ma-
terials with only L a 2 0 3 added arc dif-
nitrogen in the La-SiAION liquid at the
sintering temperaturc, with a corre-
sponding increase in viscosity, docs not
promote densification. It is known that
the solubility of nitrogen in rare-earth
glasses prepared at high temperatures
can reach at least 25 at.%,, whereas in
February 1992
-
._
0.4-
(0
-
0 Ce3’
1oo:o 75:25 5050
Y2O3:Me2O3ratio
Fig. 7. Variation of the a-SiAION content determined by X R D
for an (a+p)-SiAION with different Y 2 0 3 : M e Z 0 3additions at
1825°C. Two Y-Me-SiAION systems have been chosen to illus-
trate t h e situation where Me=Nd stabilizes an a-SiAION phase
and M e = L a does not.”-”
the Y-SiAION system the highest solu-
bility is only about 15 at.%.
The use of a more expensive sinter-
ing aid can be helpful in special cases,
but the more expensive rare-earth ox-
ides do not necessarily result in better
sintering behavior. S m 2 0 3 and Dy203
results in fully dense (a+P)-SiAlON
materials at both sintering temperatures
used, 1775” and 1825”C,whereas Yb203
does not give densc (a+@)-SiAION ma-
terials by pressureless sintering at either
temperature. For the more oxygen-rich
P-SiAIONs, however, a fully dense ma-
terial has been obtained with ytterbium.
Y b 2 0 3is thus found to be a poor sinter-
ing aid, whereas the other two rare-
earth elements (samarium and dyspro-
sium) are very good, and it is known
that the viscosity of the low-Z rare-
earth-SiAlON liquids for a given level
of nitrogen appears to be less than that
of the high-Z rare-earth-SiAION liq-
uids. Even at fairly low temperatures
the use of samarium or dysprosium ox-
ides has proved to be very effective.
(3) Effects of Type and Amount of
Sintering Aid on the Phase Ratio of a-
and P-SALON
The use of different oxides as sintcr-
ing aids will also affect other proper-
ties of the sintered materials, such as
the a : P phase ratio. T h e a-SiAlON
phase is not stabilized by lanthanum,
and replacement of Y201 by L a 2 0 3in
any “(a+P)-SiAlON” composition will
therefore diminish the a :(a+P) phase
ratio, as determined by X-ray diffrac-
tomctry (XRD)”.’” (cf. Fig. 7). Re-
placement of Y 2 0 3by N d 2 0 i also gives
a lower phase ratio for the same (a+P)-
SiAlON composition, but some
a-SiAION is still present when N d 2 0 3
is used as a sintering aid.27.37Studies of
other rare-earth-metal oxides as sinter-
ing aids for the same elemental com-
position give varying values of t h e
a : ( a + P ) phase ratio.3K When the ob-
tained phase ratio is plotted against
the ion radius, an obvious trend is ob-
served (see Fig. 8). Figure 8 shows that
SiAlON Ceramics 265
La3‘
2575 0: 100 0.09 0.10
lon radius (nm)
Fig. 8. Effect of t h e ionic radius of yttrium and other rare-earth
metals on the amount of a-SiAION phase formed after sintering,
as determined by XRD for a n (a+P)-SiAlON material.’8
a maximum size limit for a-SiAION
formation is an ion radius of -0.1 nm
and that the smaller cations generally
cause larger amounts of a-SiAION to
form. The upper size limit for a metal
ion to fit into the cages formed in the
a-SiAION crystal structure seems to be
fairly sharp, but an interesting case is
Cc3’ with an ionic radius close to the
limit. It has been shown that if cerium
is added with yttrium, the latter metal
ion will stabilize the a-SiAlON phase,
and minor amounts of cerium are, in
this case, also able to enter the crystal
structure.3K
(4) Effects of Type and Amount of
Sintering Aid on Microstructure and
Mechanical Properties
Microstructure is also affected by the
choice of sintcring aids, and this subse-
quently has an influence on mechanical
properties. Especially the development
of the elongated P-Si3N4 or P-SiAION
grains has been stated to be of impor-
tance for obtaining high fracture tough-
ness. Despite this opinion, there has
been little understanding of the funda-
mental mechanisms of microstructural
development in these ceramics. T h e
influence of the starting material and
its impurities, the metal dopant, and
the liquid-phase viscosity at the sinter-
ing temperature are factors involved
because elongated crystals form by a
solution-reprecipitation process. Some
typical microstructures of a P-SiAION
and an (a+P)-SiAlON with the sinter-
ing aids S m 2 0 3or Y b 2 0 3are shown in
Figs. 9(A) to (D). In the P-SiAlON ce-
ramic, the addition of Sm2O3results in
a finer overall grain size in the micro-
structure and grains of a slightly higher
aspect ratio than from the addition of
Y b 2 0 3 . In t h e (a+P)-SiAlON micro-
structure the difference between the
sintering aids is even more evident, be-
cause the Y b 2 0 3 causes formation of
considerably more a-SiAION grains
(gray contrast in Fig. 9)(see the prcvi-
ous paragraph on the effect of ion ra-
dius on a-SiAlON formation).
The observed structural differences
260 Journal o f the Americarz Ceramic Society - Ekstriim and Nygren Vol. 75,No. 2

can be cornparcd with thc cffccts on
t h c room t c m pcra t u r c m cc h ii n i ca 1
~ sium, samarium, or ytterbium oxidcs in
propcrtics whcn YzOl is rcplaccd by
thc rare-earth oxidcs (cf. Fig. 10). In
thc case of samarium, a higher fracture
toughncss is shown, and in thc casc of
ytlcrbium a significantly higher hard-
ncss is noted. For samarium this result
agrees well with thc previously shown
microstructurc, containing P-SiAION
grains of a high aspect ratio. In the lat-
ter case (ytlcrbium), t hc ( a+ P)-SiAION
microstructure contains considcrably
more of the hard a-SiAION grains.
(C) (1))
Fig. 9. Micro5tructure5 o f (A) and (B) B-SiAION and (C) and (D) (a+P)-SiAlON for (A)
aiid (C) 9.3 wt% SmzOi and (B) and (D) 10.5 wt% Y b z O i .
*Oo0 1
-z -
>
I
In
1500
i5
a
E E
-
I I Sm DV Yb I $ 4
Howcvcr, the more cxpcnsivc dyspro-
gencral have only a small, if any, posi-
tivc cffcct on the room-temperature
propcrt ics.
Rcplaccmcnt of Y 2 0 Dby thc even lcss
expensive lanthanum, ncodymium, or
cerium oxidcs prcscrvcs the overall
good propcrties of t h e SiAlON cc-
ramics .14-37,1‘) T h c room-temperature
mcchanical propcrtics o f thc different
SiAlON matcrials with these sintcring
aids, at an additional lcvcl corrcspond-
ing to 6 wt% Y,03, arc s u m m a r i d in
Figs. 11 and 12. Thc fracturc toughncss
is of the samc magnitudc as that found
for yttrium-doped SiAIONs, but t h e
hardness of the (a+p)-SiAION ceramic
predictally dccreascs in all cascs, as the
a-SiAlON phase contcnt decreases in
the matcrials.
Reducing the additions of sintcring
aids to a lcvel corresponding to 4 wt%
Y203 is another parameter change that
also affects thc mechanical propcrtics.
A comparison of the use o f “4 wt%
level” with thc mcasurcd rcsults ob-
tained previously for “6 wt% Icvcl” is
given in Figs. 11 and 12. To ensure that
all matcrials are fully dense, they arc
prepared by t h e glass-cncapsulatcd
HIPing techniquc. For both P-SiAION
and (a+P)-SiAION matcrials, thc rc-
duction in thc amount of sintcring aid
causes the hardncss to increase and
the fracture toughness to dccrcasc.
T h c incrcase in hardncss of the materi-
als can be explained from thc Pact that
a lcss “soft” glassy phasc (with a hard-
ness HV10=-900 to 1000) is present in
the microstructures. T h c decrcasc in
fracture toughness may to somc cxtcnt
be causcd by t h e p-SiAION grains
being sterically hindcrcd to grow with
high aspect ratios, whcn lcss liquid
p h a s c is p r e s c n t a t t h e s i n t c r i n g
temperature.
(5) Effects of Type and Amount of
Sintering Aid on Oxidation Behavior
T h e cffect of thc amount and type of
sintering aid on the oxidation bchavior
is illustrated in Fig. 13 by a comparison
of the oxidation curves vicldcd bv thrcc
/?-SiAION 0 A

- 7

1oo:o 50:50 0:lOO 1oo:o 50:50 0:100

Y203:MeZ03ratio Y2O3:Me2O3ratio
(A) (6)
Fig. 10. (A) Vickers hardness (HV10) and (B) indentation fracture toughness (K,,.) of SiAlON ceramics measured as functions of the
Y ~ O I : M ~ratio ~ Me=Dy, Sni, and Yb.
~ Ofor
February 1992
SiAlON Ceramics 267

SiAlON ceramics of different overall to C and labeled 3; i.e., the oxidation

compositions. Each composition was
prepared at 1825°C by pressureless
sintering and with the following sinter-
ing additions: Y 2 0 3 (samples A), Y203
and N d 2 0 3 in a molar ratio of 1 : l
(samples B), and Nd2O3 (sample C ) .
T h e SiAlON compositions labeled 1
are pure P-SiAlON with x values of
-0.25, while compositions labeled
2 consist of a n (a+P)-SiAlON, and
compositions labeled 3 possess a high
a-SiAION content.
These nine samples have recently
been oxidized at 1350°C (Ref. 40), and
the oxidation curves obtained at this
temperature are reproduced in Figs. 13
(A) to (C). The following general con-
clusions can be drawn:
(i) Independent of the sintering aid
used, t h e most oxidation-resistant
SiAlONs are those with the highest
a-SiAION content, and the P-SiAlONs
oxidize most easily. This is in accord-
ance with the fact that the amount of
intergranular phase decreases with in-
creasing a-SiAION content.
(ii) T h e effect of the type of sinter-
ing aid used is illustrated by the oxida-
tion curves of the samples A to C and
labeled 1, A to C and labeled 2, and A
1900 fiI
behavior of the SiAlONs prepared with
Y203as the sintering aid is substantially
better than both that of SiAlONs pre-
pared with the N d 2 0 3 and Y2O3 mix-
ture and Nd203.
(iii) The SiAlON ceramic with high
a-SiAION content prepared with Y 2 0 ?
addition (A3) exhibits a very good oxi-
dation resistance.
IV. a-SiAION Ceramics
In the past, single-phase a-SiAION
has been most extensively studied in
the Y-Si-AI-0-N system." 2'1-23 Thc cx-
tension of the a-SiAION phase field has
clearly been demonstrated to be two-
d i m e n s i ~ n a l . ~ 'As
. ~ ~mentioned above,
however, a-SiAION is also stabilized by
a number of other cations such as single
lithium,42 single calcium,17 and a
number of single rare-earth oxides.24
Formation of a-SiAlON can also occur
by combinations of cations, e.g., neo-
dymium along with calcium or lithium
ions43or even yttrium with cerium.3KBy
addition of balanced mixtures of Y 2 0 3
and AIN (Y~03+9AlN)to pure SiiN4,
a straight l i n e , Y,Si3-1 1 2 5 x A l1l2 5 , -
Y Nd La Ce
I 1 1 4
I I

-- 1700
~
Y Nd La Ce I
4
>
E.
8 1600
:
$ 3
D
E
I" 1500 G

1400 Oxide
additive 1
(Wt%)

1300 0
10 1:1 0:1 6 10 1:1 0:1
Y:Me oxide ratio Y,Me oxide ratio
(A) (6)

Fig. Ll. (A) Vickers hardness (HV10) and (B) indentation fracture toughness ( K l c )as functions of the CeOz, LarO?, or NdzO? contents
for Y-Me-P-SiAION ~ e r a r n i c s . ~ ~ - ~ ~ . ~ '

V Y Nd La Ce

1900
6

1800
5

-
0
1700 4

r_
8 1600
0,

m
m
I 1500

Oxide Oxide
1400 additive 1 additive
(Wt%) (wi%)
1300 I 0
l:o 1:1 0'1 l f i 10 1 1 01 4
Y:Me oxide ratio Y Me oxide ratio
(4 (8)
Fig. 12. Vickers hardness (HV10) and the indentation fracture toughness ( K r ) as functions of the C e 0 2 , L a 2 0 3 ,or Nd203 contents for
Y-Me-(a+P)-SiAlON ~ e r a r n i c s . ~ ~ - ' ~ ~ ' ~
268 Journal of the American Ceramic Society - Ekstrom and Nygren
Oo375xN4-,1 37Sx, in the plane Si3N4-
YN~3A1N-(AIN~AI2O3) in Fig. 2, is
followed, which traverses the single-
phase a-SiAION area, and monophasic
samples are formed for 0 . 0 8 < ~ <
0.17.20-2’,44-46
The oxygen inherently present in all
5.0 commercially available Si3N4 starting
materials, however, shifts the overall
composition toward Si02 in the Mc-Si-
4.0
AI-0-N phase diagram and causes a
residual glassy phase to be present in
-5F
i;-
3.0 the sintered materiaL4’ In practice it is
very difficult to prepare single-phase
Y
a-SiAION ceramics without some
<s 2.0 small amount of residual glassy phase.
4
Howcver, by hot-pressing mixtures of
1 .o SilN4, AIN, and Y203, a fine-grained
(a+p)-SiAlON ceramic composite was
made by Ukyo and Wada.48With high-
0 investigations by Mitomo and co-work-
0 2000 4000 6000
resolution TEM, only a very small
Time (s) amount of the grain-boundary phase
(A) was found at the multiple-grain junc-
tions. Subsequent measurements of the
5.0 bending strength at different tempera-
tures showed the beneficial effect of
the absence of a continuous glassy
4.0
phase between adjacent grains. The ob-
- served bending strength at room tem-
perature was 1.3 GPa, and was found
-F 3.0
as high as 1.0 GPa at 1400°C.
0
sf 2.0
The effects of the oxygen “impurity”
Q in the starting materials are demon-
strated below by the results of attempts
1 .o
to prepare a single-phase a-SiAION ce-
ramic along the line given above, using
two basically fine-grained starting ma-
0 terials: powder A , with a somewhat
0 2000 4000 6000
Time (s) “high” oxygen content (3.4 wt% as
(B) Si02) and a “coarse-grained” starting
material, powder B, with somewhat
5.0 lower oxygen content (2.8 wt% as
Si02).49The two high-quality Si3N4
starting powders solidified very well
4.0 even by pressureless sintering at 1775”
C
to 1825°C. Densities above 99.4% of
c-
.
5 3.0
T D were obtained with t h e fine-
grained starting material and about
YF 97% to 98% of T D with the other
3
0
2.0 (coarse-grained) material. The subse-
4
quent XRD analysis of the sintered
materials showed that the major phase
1 .o
was a-SiAION, with traces of melilite
as t h e only additional crystalline
0 phase. The subsequent analysis by elec-
0 2000 4000 6000 tron microscopy showed, however, a
Time (s)
considerable amount of glassy inter-
(C)
granular phase to be present in the
Fig. 13. O x i d a t i o n c u r v e s of t h r e e materials, and the amount of residual
SiAlON ceramics of different overall com- intergranular phase was about 10 vol%
positions with sintering additions: or higher. This high value can partly
(A), YzO3, (B) Y203 and Nd2O3 in a molar be explained by the fact that the over-
ratio of 1:1, and (C) Nd203. Compositions all composition of the samples was not
labeled 1 are almost pure P-SiAION with
corrected for the excess SiOz present
x=0.25, compositions labeled 2 represent in the powders.
(a+P)-SiAION material, and compositions
labeled 3 have a high a ~ o n t e n t . ~ ” Adding an “excess” of 2 wt% AIN to
the starting mixtures had a very nega-
tive effect on the densification process,
and this was especially notable for low
x values. The fine- and coarse-grained
starting materials thus yielded ceramics
with densities of 97% and 94% of TD,
Vol. 75, No. 2
respectively, at x=0.09, and 99% and
97% of TD, respectively, at ~ = 0 . 1 8 . ” ~
On the other hand, the amount of
residual intergranular phase was re-
duced to one-third of that observed
previously. Post-HIPing heat-treatment
of pressureless-sintered materials with
excess AIN yielded fully dense mono-
phasic a-SiAlON ceramics containing
the same low amount of intergranular
phase as before the post-HIPing.
The room-temperature mechanical
properties of the dense a-SiAlON ma-
terials differ very little between the
samples made in this study by presure-
less sintering, pressureless sintering
and HIPing, or HIPing!7,49 The frac-
ture toughness is of the order 4 to 4.5
and the hardness (HV10) is -1900 to
2100. This is in accordance with the
e r ~ ~of ~a-SiAlON
, ~ ~ ceramics;
, ~ ~ their
fracture toughness is 4.5 to 5.5, hard-
ness -2000, and bending strength 600
to 900 MPa. Note that the observed
hardness values are remarkable for
Si3N4-based materials. This group of
materials are interesting candidates in a
number of applications, especially as a
sinter-HIPed cycle, which will make
complicated shapes fairly easy to attain.
The oxidation behavior of an almost
monophasic a-SiAION is discussed in
Section IV(5). Note that there is no ex-
perimental evidence showing that the
a phase is more resistant to oxidation
than the phase or vice versa.
V. 0’-SiAION “SitNZO”Ceramics
(1) Sintering and Formation of
0’-SiAlON
The Si2N20phase is of interest as a
ceramic engineering material mainly
because of the expected oxidation
resistance at high temperatures. The
formation of Si2N20from mixtures of
high-purity Si3N4 and S i 0 2 heated
at high temperatures is very sluggish
because of kinetic hindrance. It has
been shown in a number of reports
that additions of various sintering aids,
which form a liquid phase at t h e
sintering temperature, greatly facilitate
the process,5o352 but they may also
have a strongly negative influence on
the oxidation resistance at elevated
temperatures.
For S i 2 N 2 0 materials intended for
high temperatures, addition of metal
oxides, such as Y2O3 alone, which
forms a refractory glass, is the most at-
tractive alternative. Similarly, C e 0 2
has been used in a number of investi-
gations because of the high eutectic
temperature with S O 2 , but also be-
cause it is among the least expensive of
the rare-earth o ~ i d e s . ’ ~Otherwise,
-~~
the most effective sintering aid is a
combination of Y203 and A1203,which
allows pressureless sintering.”-6’ A1203
forms 0’-SiAION, which is described
in more detail below.
February 1992
First, thc cffects of using Y201 alone
as a sintering aid is dcmonstratcd.
Pressureless sintering at 1775°C of
Si,N,+ SiOL mixtures with an addition
of Y 2 0 Rrcsults in a high yield of
SilNl@ and a material with lairly good
density (98% to 99% of TDj.62 because
the densification is facilitated by the
presence of a liquid phase. Pressurclcss
sintering at lowcr temperatures results
in highly porous materials, but hot-
pressing or HIPing can be used to ob-
t a i n fully dense materials even at
1600°C. Equimolar ratios of SilNl and
SiO? with small a m o u n t s of C e O ?
added (2 to 3 molY';,) produce a similar
behavior. Thus, at temperatures above
1750°C the reaction to form S i 2 N 2 0
proceeds and the process
can be further promoted by introduc-
ing sced crystals of S i 2 N 2 0 into the
powder mixture prior to sintering.'5
As mcntioned previously, t h e
S i 2 N 2 0 phase forms a narrow solid-
solution range rcprcsented by thc for-
mula Si2-,A1,0, FA wherc x varies
from o to -0.2.j8
terials along this line, with only A1203
and AIN added, rcsults in fully dense
urclcss sintcring at
ion o f YZO3further
aids the solidification process to take
place at 160O"C.""-"" The effect on the
formation of the O'-SiAION phase by
Y 2 0 i addition is similar to that rc-
portcd abovc for the Y,O? addition to
Si 2 N 2 0 .
T h e l a t t i c e p a r a m e t e r s of 0 ' -
Si AION, Si2-,AI,,O I -,rNz-,!, increase in
a very typical way with the x value and
can be used to determine t h e alu-
minum content." Y 2 0 3 is frcquently
used as a sintering aid for preparation
of 0'-SiAION materials. Y203, a good
glass formcr, has a greater affinity for
the A1203(initially added to form the
0'-SiAION) than does the 0'-SiAION
phase, implying that the 0'-SiAION
formed contains less aluminum than
expected, and the ceramic material
will comprise substantial amounts of
glassy phase. Refinement of the 0'-
SiAlON phase lattice parameters in
these materials can be used to prove
this reaction pattern.
(2) Mechanical Properties of
O'-SiAlON
The mechanical properties of mono-
phasic S i 2 N 2 0 are difficult to deter-
mine because of preparative difficulties
in obtaining a monophasic S i 2 N 2 0ma-
terial without the use of a sintering aid.
A good approximation is, however, a
Vickers hardness (HVIO) of 1600 and a
fracture toughncss of -3.3 MPa . m' ',
obtained from measurcmcnts on materi-
als HIPed at 19OO"C, consisting of al-
most pure, crystalline SilN20.62
A slight improvcmcnt of the tough-
ness has bccn found in O'-SiAlON
(x=O.1) material with Y z 0 3 addition
SiAlON Ccmrnics 269
(see Fig. 14). The modulus of rupturc
of similar O'-SiAION materials mcas-
ured by T r i g and Jack" is -420 MPa.
A possible explanation for the gener-
ally poor toughness behavior of t h c
0'-SiAION ceramics is that bonding is
so strong between the SizN20 crystals
and the SiOl-rich glassy phase that the
-0 2000
crack proceeds straight through both I
glass and crystals. Therefore, no pull-
s
m
out or crack-branching effects con- P
tribute to the fracture toughness in the I
1500
manner described abovc for t h e p-
SiAlON mr-iterials. This hypothesis is
supported by the findings of Ohashi
et .,14,bl who have reported that an
S i 2 N 2 0 material with a glassy grain-
boundary phase has a fracture tough-
ness of 2.5 M P a m " . Howcver, heat
treatment of the material to crystallize
this phase has a dramatic effcct on the
toughness, increasing it to about 5.5
MPa.m"*. In the heat-treated matcrial,
the bonding between the crystallized
intergranular phase and the S i 2 N z 0
crystals is much weaker. The hypothe-
sis is also supported by t h e rcccnt ff '3
findings of Tanaka et ul.'? on Si3N4
compositc ceramics without sintering HIP 1600°C
aids and Kishi et al." on single-phase 0 HIP 1 7 5 0 6
P-SiAION ccramics. HIP i900°c
T h e hot hardness of S i 2 N 2 0 is pre-
served at tcmperatures at least up to
1200°C. Thc combined addition of Y:O3
and Al2O3 in an O'-SiAION material,
however, has a pronounced negative
Fig. 14. (A) Iiardness (HVIO) and (B) in-
effect, giving poor high-temperature
dentation fracture toughness ( K I c )of sili-
properties. con oxynitride ceramics Siz-tAI,N2-xOI+,,
where x=O.1.
(3) Oxidation Resistance of Siz N2O
Fully dense S i 2 N 2 0 ceramics, pre-
pared by the HIPing techniquc without
a sintering aid, have been used for oxi-
dation studies in the temperature range
1300" to 1600"C.h4~,"5 S i 2 N 2 0 exhibits a 16.0
very good oxidation resistance up to 70
14 0
1600°C. Typical oxidation curves arc 6 0 i;
given in Fig. 15. The only oxidation s
c u r v e w h i c h s e e m s t o follow t h e
parabolic rate law is the one obtained -p - 5-
50
<-
4.0
at 1300°C. The weight-gain curves ob- 8.C
30
~
tained at 1400°C cannot be interpreted % 6C
4 3,
with the parabolic rate law, and curves 2 4c
2.0 s
I
of this type are obtaincd in the tem- 10
perature ( T ) range 135o"C~Ti145o"C.
At t e m p e r a t u r e s r1500"C, all t h e 0
curves obtained are similar, implying 25000 50000
Time (s)
t h a t t h e parabolic rate law in not
obeyed until after a certain time ( t o ) . Fig. 15. Oxidation curves of SilN.0 at
T h e microstructure of t h e oxide 1300", 1400", and 1500°C. Symbols ( O ) ,
scale formed at 1600°C is shown in (W), and ( 0 ) represent weight-gain values
Fig. 16. A n X R D study of the same which a r e calculated according to t h e
surface shows that it contains a-cristo- Eqs. (2), ( S ) , and (6) stated in Panel E,
balitc, and from the appearance of the respectively.h4.fi'
microstructure it seems clear that the
dcgree of crystallinity of the surface is
rather high. Similar microstructures
are observed for all samples oxidized
at T21350"C. Thc microstructure of
the surface of the oxide scale obtained
at 1300°C appears amorphous. Scan-
ning electron microscopy (SEM) stud-
270 Journal of the American Ceramic Society - Ekstrom and Nygren
Fig. 16. SEM micrograph of the surface of Si2N20 oxidized at
1600°C showing a-cristobalite crystals surrounded by a glassy
phase.
It is well established that the oxi-
dation of SiiN4-based ceramics is
controlled by the diffusion of reac-
tants. The rate of diffusion is given
by Fick's first law:
dm
_- dc
-DA,,-
dt dx
where dm is the mass of the reac-
tant diffusing across a distance dx
in time dt, dc is the concentration
gradient across the oxide scale, A,)
is the cross-section area through
which the reactant diffuses, and D
is the diffusion constant of the re-
actant. If the oxidation process of
Si3Nd-based ceramics is monitored
by studying the weight increase (Aw)
as a function of time at a specified
temperature, the parabolic rate law
can be rewritten as
(2) =K,t +R
whcrc Kr, is the parabolic rate con-
stant and B is a constant. Thus, if a
uniform compact oxide scale is
formed, if A , ) is constant during thc
oxidation process, and if the reac-
tion is diffusion controlled, this re-
lation should be valid. Oxidation of
chemically vapor deposited SiiNJ
exhibits parabolic oxidation behav-
ior according to the overall rcaction
Si3N4+302=3Si02+2N2
It ha5 been shown that, in this casc,
Panel D Oxidation
the diffusion of oxygcn within the
oxide scale-rather than the out-
w a r d diffusion of t h e nitrogen
formed by the oxidation-controls
the kinetics of the growth of the
Due et a L X Xargue, how-
ever, that the low oxidation rate of
S i i N 4 in comparison to that ob-
served for oxidation of silicon and
Sic, is due to formation of a thin
layer of S i 2 N 2 0between the Si3N4
and the SiO, scale, and the rate-de-
termining step of oxidation is the
diffusion of oxygen through this
S i 2 N 2 0 layer. The oxidation rate of
SiAlON-based ceramics prepared
without, or with various amounts
and types of sintering aids is gener-
ally higher than that of Si3N4.
Oxidation of a P-SiAION ceramic
of the composition S i 2 A I I 0 , N 3will
have the overall reaction stoichiomc-
try
2Si2AI 0,N3+4.50,
=4Si02+ A1203 3N2 +
Depending on t h e tempcrature of
o x i d a t i o n , a complete o r p a r t l y
amorphous scale is formcd. In the
latter case, the crystalline product
most probably consists of mullite. In
this reaction it is assumed that the
SiAlON ceramic is prepared without
t h e use of a sintering aid. Densc
SiAlON compacts arc, however, fre-
quently fabricated with sintering aids
such as Y203and MgO. These addi-
Vol. 15, No. 2
ies of the cross sections of the oxide
scales show that they contain nitrogen-
gas bubbles. These observations sug-
gest that the curves obtained in the
temperature range 135OoC5T51450"C
should be interpreted with use of the
arctan function given in Panel D. The
same equation should also be appli-
cable for t h e curves obtained at
Tr1500"C and t<to, whereas, for t > t o
Eq. (6) in Panel D should be used. In
Refs. 64 and 65 it is shown that all ob-
served weight-gain curves can be inter-
p r e t e d . w i t h equations, and a com-
parison of the calculated and observed
weight gain at 1300", 1400", and 1500°C
is given in Fig. 15. The method applied
also gives diffusion coefficient values
for the oxygen diffusion in amorphous
S i 0 2 ranging from 5 . 2 8 ~ cm2/s at
1350°C to 2.98~10-"cm2/s at 1600"C,65
which compares favorably with those
values obtained by other m e t h ~ d s . ~ ' , ' ~
tives form an intergranular phase,
which affects the oxidation so that
a more complex process is expected
to take place. The influencc of dif-
ferent sintering aids on the oxida-
tion behavior has been discussed by
several authors.x"-" At higher tem-
peratures, oxygen ions are assumed
to diffusc from the scalc-gas intcr-
face toward the ucaie-ccramic in-
t er f ac c , a n d , s i mu 1tan cou s I y , t hc
cations in the intergranular phase(s)
are assumed to diffuse from the in-
terior of the ceramic to the oxide
scale as illustrated in the accom-
panying f i g u r e . It s e e m s t o b e
generally accepted that the rate-
determining step is the outward dif-
fusion of cations from t h e intcr-
granular phasc(s). T h c oxidation
behavior of S i 2 N 2 0at high temper-
aturcs, prepared without a sintering
aid, and of various SiAlON ccram-
ics, p r e p a r e d without a n d w i t h
Y 2 0 3N , d 2 0 3 , or a mixture of Y 2 0 3
and Nd201, as a sintering aid, is dc-
0u
/-\
<'
Oxidation
scale
I
N2 bubbles r\2.
W
1
a-SiAlON 0-SiAION
Fcbriinry 1002 SiA10 N Cerum ics 27 1

VI. Applications will therefore not be elaborated hcrc.

(1) General
The combination of excellent chcmi-
cal i n e r t n e s s w i t h high h a r d n e s s ,
toughness, and strength at tcmpcra-
turcs well above thosc where most
stccls and a l l o y s cease to function
makes the Si3Nz1-bascdmaterials, in-
cluding the SiAIONs, premium candi-
dates for metal-cutting tool inserts,
metal-forming tools, ctc. The thermal
shock resistance, with very little thcr-
ma1 fatigue, is much bcttcr for SilN4
than for any competitive ceramic oxidc
material, implying that other applica-
tions can bc found in heat engines or
cncrgy systems with fluctuating tcm-
pcrnturcs. For example, the potential
use o f SilN,I materials in both rccipro-
caf ing and gas-turbine engines has
;\ttr:ictcd attention for two to thrcc
decades, and a vast number o f publica-
tions have cxplorcd this arca, which
A comprchcnsivc review o f the appli-
cations o f Si3N4-bascdmaterials has rc-
ccntly been published in Ref. 94. In
this section a few cxamplcs arc given
to show that the combinations o f prop-
erties obtainable with different SiAlON
ceramics also make these materials
suited for a variety of applications. The
original idea in the development of p-
SiAlON (with the trade name Syalon)
by Lucas-Cookson-Syalon, Ltd. (Shir-
Icy, West Midlands, U.K.), was to ob-
t a i n a m a t e r i a l a s good a s S i 3 N 4
ceramics at a lower cost."""" This goal
has been fulfilled, and, in addition, in
specific applications, different SiAlONs
may havc an even greater potential.
As shown above, SiAlON materials
must be thought of as a family of "al-
loys," with a wide range of properties.
This variety is advantageous, since a
profile of desirable material properties
for an application has a good chance

Panel D (continued)
scribcd in this paper. In the case
of S i 2 N 2 0 , t h e o x i d a t i o n ratc-
controlling step must bc the dilfu-
sion of oxygen ions through t h e
oxide scale because no sintcring aid
is used. Simultancoiisly, because the
oxygen ions have t o diffuse from
thc surface of the oxide scalc t o the
interface hctwccn this scale and the
ceramic, the oxidation-formed ni-
trogen has t o migrate the opposite
direction. This can occur via diffu-
sion of nitrogcn ions o r nitrogcn-
gas molecules, or by migration o f
n i t rogcn-gas bubbles.
The overwhelming part o f t h e
oxidation studics o f Sil N,-based
ceramics has bccn intcrprctcd with
the parabolic rate law given above.
This law is dcrivcd under the as-
sumption that t h e phase composi-
tion of the oxidc scale is constant
during the oxidation process, imply-
ing that n o nitrogen-gas bubbles are
formed, and, t o the extent that an
amorphous oxidc scale is formed
in i t i a I I y , no cry st a II i zat ion occurs
during the experiment. Recent oxi-
dation studics o f S i z N z O havc
shown that the oxidation curve ob-
tained at 1300°C can be intcrprctcd
with this parabolic ratc law. How-
ever, thc (Aw/All)' vs t curves ob-
tained at higher tcmpcraturcs could
not at all or only partly (c.g., for t
exceeding a certain time tll) be thus
i ~ i t c r p r c t c d " ~ (. s" e~e a l s o S c c t -
ion V(.?)). Subscqucnt microstruc-
tural and X-ray investigations of the
oxidc scalcs formed by oxidation
show that thc scalcs contain cristo-
balitc crystals. If the crystallization
occurs during the oxidation cxpcri-
mcnt, the cross-section arca (All)
must vary with time. Not only crys-
tallization but also formation of ni-
trogen-gas-containing bubbles and
cracks at the intcrl'acc between the
oxidc scale and the ceramic con-
t r i b u t e t o t h e reduction of t h e
cffcctivc cross- section arca available
for oxygen diffusion.
A function A(t) has been dcrivcd
w h i c h d e s c r i b e s how t h e a r e a
through which oxygen diffuses dc-
creases with the time o f oxidation:"'
(3)
where A l l is the cross-scction area
at t=O, f the fraction of A,, that rc-
mains constant at ~ > t , ) ,and /3 a
constant which describes the rate by
which A,, decreases. This function
has the following propcrtics:
(i) A(t)=A,, for f = 1 and t11=0,
implying that a parabolic oxidation
behavior is expected.
(ii) When All dccrcases during
t h e entire oxidation experiment,
then tll=t,, which gives A(t,)=fA,,
with O < f < l , implying that a non-
parabolic behavior is expected.
(iii) If the cross-section arca be-
comes constant after a certain time
tll during t h e experiment, i.c., ii
steady state is established, then O <
to<t and A(t)=f& for l>tll. I n this
casc a mixed nonparabolic/parabolic
behavior is expected.
T h e function A(t) is incorporated
in thc parabolic rate law according
10
d w KA(t)
-
dt x
where K is a constant and X = ( L Y / ) " ~
(whcrc a is the rate constant for the
growth of t h e scalc). Integration
yields
Aw
T = u arctan (h~)"'+ctI'~
A 0
Within the framework of thi4 ap-
proach the parabolic ratc law lor
t z tll reads
Equations (2), ( S ) , and ( 6 ) havc
shown to be applicable to the oxida-
tion of S i 2 N 2 0as shown in Fig. IS.
From the refined values o f u , h , c,
and f ,K,] in Eq. 2 can be calculated
according to K,,=(~h"~+c)'or from
the relation Kij= K J 2 . An claboratc
derivation of Eqs. (3), ( S ) , and (6)
and a discussion of their physical
implications arc given in Ref. 65.
272 Journal of the American Ceramic Society - Ekstrom and Nygren Vol. 75, No. 2

to be met by a tailor-made SiAlON A recent example of a more specific

material or composite. On thc other
hand, one cannot test only one arbi-
trary SiAlON material in a specific ap-
plication, as one has to be awarc of
some general limitations of different
ceramics." The most important draw-
back for the pressureless-sintered /3-
or (a+P)-SiAION ccramics is that they
a r c s u i t e d only for long-time use
at application t e m p e r a t u r e s below
- 1"00"C ,Y5.Y6 However, the simplicity
of the solidification techniquc, which
has a complex shapc capability, still
makes the pressureless-sintcrcd SiAlON
ccramics attractive in a number of
applications, such as non-ferrous metal-
tube or wire-drawing dies, seals, bear-
ings, and valvcs.h.U5-4K Thus, the main
rcason to use /3- or (a+P)-SiAION in
low- or medium-temperature applica-
tions, instead of HIPed or prcssure-
sintcrcd Si3N4 ceramics, is t h e low
preparation cost of sintered bodies,
whereas the gcneral propcrties of the
materials arc similar. As described in
Panel E, a post-heat-treatment to pro-
mote crystallization of the glassy phasc
can raise the possible application tem-
perature scvcral hundred degrees.
use of onc of the SiAlON "alloys" is
the usc of 0'-SiAION ceramics as sub-
merged pouring nozzles in the continu-
ous casting of steel." T h e expected
oxidationicorrosion resistance at high
temperatures of this special SiAlON
material implies that other similar rc-
fractory applications, e.g., refractory
linings, might be developed. At very
high application temperatures, single-
phase a- or P-SiAION ceramics have
the potential to be strong competitors
to the low-doped Si3N4 ceramics in
heat engincs or energy systems. This
latter area still remains to be further
explored.
In this section, three diffcrent ex-
amples of applications are given to il-
lustrate the range of uses of SiAlON
ceramics. In the first example, thc cx-
cellent wear resistance at low tempera-
tures is demonstratcd by the application
as a milling mcdium. In ths second ex-
ample, the good chemical resistance at
medium-high temperatures is shown by
functions as wire- or tubc-drawing dies
for copper alloys. The third example
shows the extraordinary combination of
mechanical and chemical rcsistancc in

Panel E Crystallization of Glassy Grain-Boundary Phase

In most cases the added metal
ions of t h e s i n t e r i n g a i d s have
n o solubility in t h e precipitated
SiAlON crystals, and they will form
a residual nitrogen-containing metal
silicate intergranular phase, which
can be glassy (amorphous) or crys-
talline, depending on factors such as
t h e overall composition and t h e
cooling conditions applied. The in-
tergranular phase is to a large ex-
tent found at multigrain junctions or
between adjacent grains as t h i n
glassy films that may be only a few
tenths of a nanometer thick."," The
structure and composition of these
grain-boundary phases in SilN4-
based ceramics is critical in de-
termining t h e mcchanical and
chemical properties of the material,
especially at high temperatures.
One way of improving the high-
temperature properties is to post-
heat-treat thc ceramic material to
promote crystallization of the glassy
phase. It has been shown that the
ability to fully crystallize the glassy
phase depends on the overall ma-
terial composition in relation to that
of the formed SiAlON phase(s) and
the potential crystalline phase in the
actual Mc-Si-AI-0-N system.""-84
There are also kinetic factors which
may inhibit complete crystallization;
e.g., nucleation kinetics may be im-
paired if there is a large volume
change causing stresses in the glass
residues which are constrained by
surrounding grains.x4
The temperature at which strength
degradation is observed is t h e n
raised from t h e glass transition
temperature (typically about 900" to
100O'C) t o t h a t of t h e e u t e c t i c
temperature along t h e SiAION-
grain-boundary phase join. For a
P-SiA1ON-Y3Al5O12 (yttrium alu-
minum garnet, YAG) ceramic, this
temperature is 1320"C, which is an
improvement of several hundred
degrees over a P-SiAION-glass-
ceramic.'",x5
The amount of nitrogen incorpo-
ration into an oxide glass is fairly
low compared with t h e range of
compositions that can be achieved
by cation variations. Dcpending on
the oxynitridc system involved, the
maximum nitrogen content is esti-
mated to be 15 to 30 at.%, implying
one nitrogen atom for every three
to six oxygcn anions. Therefore, the
concentrations of nitrogen that can
be incorporated into a homogeneous
oxynitride glass tend to favor the
primary crystallization of oxide-
silicate species. Thc crystallization
path in intergranular regions of
oxide-dopcd Si3N2 materials during
post-hcat-treatment may also be dif-
ficult to predict, becausc the com-
positions of intergranular phascs are
usually neither particularly well-
known nor uniformly distributed,
and t h e stress states during t h e
crystallization of glass confined to
multigrain junctions or thin grain
boundaries are quite different. Onc
example of typical results is found
in an article reporting how Si3NJ
was sintered with a Y-Si-AI-0-N
glass additive a n d subsequently
heat-trcated to crystallize thc grain-
boundary phase.x" At a post-heat-
treatment temperature of 1350"C,
only crystalline p-Y2Si207was de-
tccted at t h e g r a i n boundaries,
whereas at slightly higher tempcra-
turcs (1450°C) morc complex crys-
tallization paths occurred, giving
primarily YSiOIN and Y4Si207N2
with some minor amounts of Y2Si05
and p-Y2Si207.
Crystallization of thc glassy grain-
boundary phase in SiAlON ceramics
is one way of improving the high-
temperature propcrtics up to about
1300°C. T h e eutectic temperatures
are rarely much higher than 1300°C
in metal-SiAION systems, but a
search is going on for improvcd re-
fractoriness w i t h new or mixed
oxide combinations of
February 1992
metal-cutting operations at high tem-
peratures.
(2) SiAION as a Milling Medium
SiAlON materials perform excellently
in a number of wear applications. Wear
occurs by several mechanisms, but in
this example a hard material is milled
by a hard milling medium, and abrasive
wear will therefore be of prime impor-
tance. In this application an (a+p)-
SiAlON material with a high content of
a-SiAION is t h e natural choice for
milling bodies because of t h e high
hardness combined with acceptable
fracture toughness of the material.
Ceramic powders, such as Z r 0 2 ,
Al2O3,or Si3N4,can also be milled by
traditional balls of sintered alumina. If
commerical, low-cost 92% to 94% a h -
mina balls are used in a vibratory high-
energy mill, there occurs considerable
wear and "contamination" from thc
alumina balls, which can be of t h e
order of up to 0.5 wt% for normally
used milling times (10 to 30 h). This
is a substantial contamination of the
milled powder, which cannot always be
acceptcd. By using a SiAlON milling
medium t h e wear and consequently
t h e contamination c a n be reduced
considerably.
The effect of using 10-mm balls in a
vibro energy mill using alcohol slurrics
of high-purity Si3N4 or A1203 is illus-
trated in Fig. 17.'"" Two gradcs o f
alumina have been used: a 92% alumi-
na-silica-type and a 99% alumina-
silica-type. These are compared with
an (a+B)-SiAlON material. The weight
loss of the SiAlON milling media is
lower, both in the case of Si3N4 and
A1203 powders, as shown in Figs. 17
(A) and (B), respectively. Subsequent
chemical analysis of the milled slurries
shows that the contamination lcvels of
aluminum in the Si3N4 slurry are very
low using SiAlON milling media com-
pared with that using alumina balls (cf.
Fig. 17(C)). Similarly, the contamina-
tion of silicon was chemically analyzed
in the Al2O3 slurry and was found
to be of the order 2 ppm of silicon per
hour in the case of using SiAlON balls
(cf. Fig. 17(D)). Thus, especially when
milling Si3N4 powder mixtures with
SiAlON balls, t h e low wear of t h e
SiAlON milling media results in a
low contamination level in the milled
powder.
(3) SiAlON in Metal-Forming Tools
SiAlON materials have been used in
metal wire- or tube-drawing tools for
non-ferrous alloys, especially alu-
minum and copper a110ys.".y55-yxSiAlON
ceramics that have been in contact
with thcsc metals for long times at ele-
vated temperatures show no reaction in
the absence of oxygen or metal oxidcs
that can act as fluxing agents in form-
ing new metal-SiAION glasses. No re-
action is observed at the contact zone
SiAlON Ceramics 273
0.16 1-0.16l f
-E 0.12 z l
D 0.12
-s
0
g
v)
3 008
-g 0.08 -
z E
P
20, 0.04 2 004
0 n
AS92 AS99 SY70 AS92 AS99 SY70
(A) (5)
Y
AS92 AS99 SY70 AS92 AS99 SY70
(C) (D)
Fig. 17. Weight loss of ceramic milling balls in a vibro energy mill using alcohol slurries
of high-purity (A) Si3N4and (B) AlzOi powders.""' Ceramic materials in the balls are 92%
alumina-silica (AS92), 99% alumina-silica (AS99), and Y-doped (cu+p)-SiAION (SY70).
Chemical analysis of the contamination of t h e milled powders is given as (C) aluminum
and (D) silicon contents.
between the SiAlON material and the
copper metal.hx Dies in practical use
for copper alloys havc performed well
and are better than the traditionally
used Stellite metal tools (Stoody De-
loro Stcllite, Inc., Industry, CA), for
which the lower metal wear resistance
with concomitant loss of dimension
tolerances is a problem.
The situation is quite different, how-
ever, if copper oxide ( C u 2 0 ) is mixed
with the copper metal, because con-
siderable attack is seen after very short
heating times.h8 A complex reaction
takes place at the contact zone. This
situation, however, never occurs in
metal forming where oxides a r e
avoided, but must be stressed as an
important limiting factor for other
applications.
(4) SiAlON in Metal-Cutting Tools
Metal-cutting tool inserts are used
for turning, milling, drilling, and other
operations in the fabrication of metal
components by machining."'~7'~y~~"~'~"'?
T h e ceramic inserts are cxposed t o
both stress and chemical aggression at
very high temperatures at the tip of the
tool. Heat due to friction and distortion
of the metal chip can build up tempera-
turcs locally to well above 1200°C. The
rate of chemical reaction between
ceramic, metal, and atmosphere can be
extremely fast if the wrong material is
used. A large thermal gradient is also
found in the ceramic insert, and very
rapid temperature fluctuations of sev-
eral h u n d r e d degrees might c a u s e
microcracking by thermal fatigue.
A1203 cutting tools were commcr-
cially introduced on a larger scale dur-
214 Journal of the American Ceramic Society - EkJtriim and Nygren
ing the late 19SOs, but they were not
vcry succcssful because of poor reli-
ability duc to low toughncss and inade-
quate thermal shock resistance. T h e
AI2O3-bascd cutting tools have now
entered a ncw application era in the
form of different composite materials.
The first generation of composites were
t h e Tic- or TiN-particle-reinforced
Feed 0 3 mmlrev
A120i materials, and the latcst devel-
Depth of cut 20 mml o p m e n t is S i c - w h i s k e r - r e i n f o r c e d
AlzOi cutting tools.’* In many applica-
tions, however, Si3N4 materials could
0 10 20 30
Cutting time (min) offer an alternative to or even a sub-
stantial improvement upon the Al;Oi-
Fig. 18. C o n t i n u o u s turning of gray c a s t based cutting-tool inscrts. In general
iron w i t h di f f er ent Si3N4-based m a te ria ls .
it is the combination of toughness,
F l a n k w e a r of the c u t t i n g tool is plotte d as
a function of cutting time.'"^"" strength, and thermal shock resistance
that results in good performance.
1
C
e pSi3N4 I cation, and the longest tool life is ob-
0 0.1 0.2 03 04 0.5 0 0.1 0.2 0.3 0.4
il ( 0 + p) ratio o : ( w + ~ )ratio
(4 (6)
Fig. 19. Rel at i ve t ot al tool life i n c o n t i n u o u s t u r n i n g of t w o nickel-based superalloys:
(A) Incoloy 901 and (B) Inc one l 718 ( H u n t i n g t o n Alloy P r o d u c t Division, I n t e r n a t i o n a l
Nickel Co., H u n t i n g t o n , WV).2”,b‘’
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Thommy C. Ekstrom is Manager of the
Ceramics R&D Department of AB
Sandvik Hard Materials, Sweden, and
part-time Professor of Chemistry of
Ceramics in the Inorganic Chemistry
Department of Stockholm University,
Sweden. He has a broad scientific
background with 24 years of practical ex-
periences in different governmental and
industrial analytical o r research
laboratories within Sweden. Dr. Ekstrom
has worked with Sandvik AB since 1980
in a wide range of materials research, in-
cluding cemented carbide, but has been
concentrating on ceramic materials since
1984, especially the silicon nitride-based
ceramics. Dr. Ekstrom will soon become
Mats E. Nygren is Professor of Material
Chemistry at the University of
Stockholm, Sweden. Dr. Nygen earned
his BSc. and Ph.D. in chemistry from the
University of Stockholm and has been
employed by the University since 1975.
He is author or coauthor of more than
90 publications and has conducted
research in a wide variety of fields, in-
cluding ceramic materials, metal-
insulator transitions, solid electrolytes,
amorphous metals, and high-T, super-
conductors. He has also been involved in
development of various types of thermal
and electrical measuring apparatus. Dr.
Nygren has for various periods of time
worked at different laboratories in the
Vol. 75, No. 2
Applications,” Trans. J. Br. Cerum. Soc., 81, 141-
44 (1982).
”M. H. Lewis, “Ceramics: Applications and
Limitations”; pp. 1-20 i n Materials UI Their Lim-
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a full-time Adjunct Professor in the
Department of Inorganic Chemistry,
Stockholm University, and, as chairman
of the working committee of the newly
initiated Powder Technology Center of
Stockholm, will coordinate industrial
research toward this center which is com-
prised of the major materials research in-
stitutes in Stockholm. He received his
Ph.D. in inorganic chemistry in 1975 at
Stockholm University, where his thesis
work was on ternary-transition-metal ox-
ide systems with molybdenum or tungsten
as one of the major elements.
United States, France, England, and Ger-
many. He is presently a delegate on the
board of directors of the research pro-
gram for high-T, superconductors in
Sweden.