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1. lntroduction
Recently,it has beenshown that non-oxideceramics
suchascarbidesand nitridescan be obtainedby firing
suitablemetal-organicpolymer precursorsin controlled atmospheresn]. A common feature of the
polymerroute to carbidesor nitridesis the formation
of intermediateswhich are amorphoussolids.These
are formed after the removal of the organic components and before crystallization [2]. We have
alreadypointedout the importanceof regardingthese
amorphouscovalentceramics(ACC) as an entirely
new family of disorderedsolidswhosestructureand
propertiesare worthy of independentstudy [3, 4].
Among the various systemsalready synthesized,
SiC obtained from polycarbosilaneis certainly the
most widely studied [5-7]. Commercially available
Nicalon SiC fibresare obtainedfrom polycarbosilane
following the processfirst developedby Yajrma et al.
[8]. The feasibilityof this method in producingfibres
or coatings is not restrictedto this material. It is
mainly due to the polymeric nature of the ceramic
precursors,and it accountsfor the many research
effortsthat are currentlybeingconducted.Despitethe
increasingnumberofstudieson SiC fibresobtainedby
the Yajima process,the structuralconversionfrom the
starting polycarbosilaneto the resulting ceramic
matedal is not well understood.In this paper the
pyrolysismechanismof polycarbosilane,
the structure
ofthe intermediateACC phaseand its conversioninto
the microcrystallinesilicon carbideceramics,will be
discussedmainly basedon 2eSiand r3Cmagic-angle
(MAS-NMR),
spinningnuclearmagneticresonance
electron spin resonance(ESR), X-ray diffraction
(XRD) and transmissionelectronmicroscopy/selected
areaelectrondiffraction (TEM/SAED) experiments.
3886
nd Hall Ltd.
0022-2461/q0
$01.00+ .12 O 1990Chapman
ffi
50
-50
8.0
4.0
0.0
3. Results
3.1. Characterization
of the polymer
orecursor
The chernicalanalysisof PC, reported in Table I,
s h o w sa S i :C : H r a t i o o f l : 2 . 2 : 5 . b s i M A S - N M R
and 2esiCP MAS-NMR spectrahave beenrecorded
on this starting material (Fig. l). The two spectra
revealthe samefeatures,with an enhancement
of the
resolution for the cross-polarizedspectrum. The
spectra show two different silicon units, already
reportedin the literature[7]. The peakat - 0.8p.p.m.
is due to silicon atoms bondedto four carbon atoms
(SiCa) as type I units and the second peak at
- 17.6p.p.m.is due to type II units in which the
silicon atoms are surroundedby three carbon atoms
and one hydrogenatom (SiCrH). No distinct peaks
appeararound - 35p.p.m: Si-Si bonds,if they exist,
are thus not abundant in this starting PC [7]. These
two typesof units are shownbelow.
CH'
I
CH"_Si_CH,
- l
CH,
(r)
cH.,
CH"-si-cH,
I
H
OD
PC
PC8,l0
PCl200
PCt500
2.2
1.6
t.44
1.43
5
0.65
0.10
0.07
ffi
Chemicalshift ( p.p.m.l
F8rle 2"Si,rH andr3CNMR spectraof polycarbosilane
dissolved
in CDClr.
PC wasdissolved
in CDClr. 2esi,I H and ,,C NMR
spectrawererecordedin solution(Fig.2). The,,Si
NMR spectrumis quite similarto the CP MAS-NMR
spectrumon th powder. The ratio betweenthe two
kinds of units (I and II) appearsto be I : 0.8. The 'H
NMR spectrumof PC shows two regions for the
resonance,
from 4 to 5p.p.m. due to Si-H bonds and
around0 p.p.m.due to C-H bonds.The integrationof
the peaksgivesa valueof 11 for the C-H/Si-H ratio.
In the Si-H region,severalpeaksarepresentat 4.1,4.3
and 4.6p.p.m. due to differentSi-H sites.The C-H
regionshowsa mainpeakat 0.17p.p.m.,due to CHj
groups,and two shoulderswith lower chemicalshift
values,at 0 and 0.5p.p.m. assigned,respectively,to
CH, and CH groups.The '3C-{rH} spectrumof the
solution shows a broad peak centred on 3 p.p.m.
correspondingto the aliphatic carbon atoms present
in PC in CH3, CH, and CH units. Somesharppeaks
are superimposed,
certainlydue to somequite mobile
units insidethe polymer.
All the NMR spectraindeedhavebroad peaks,and
3887
no resolutionwasobtainedespecially
for rH and r3C
NMR experiments.
Thisseems
to indicatethata large
distributionof unitsis presentin thispolycarbosilane.
The structureof polycarbosilane
that emerges
from
theseresultsis morecomplicated
than a simpleIinear
chainof type I and II unitswith a I : I ratio suchas
CH.
t
CH
t
CH..
3.2. Characterizalion
of he pyrolysisprocess
prccursor
3.2.1. From the
polymer to the
ACC phase
The low molecularweightcomponentsof the polycarbosilanehave been previouslyremovedby melting the polymer in flowing nitrogengas. Thermogravmetricanalysis(TGA) performedon this material
(PCD) showedthat the weight lossesend at around
800'C.At thistemperature
polymerhas
theprecursor
beenconvertedinto an inorganicsolid that appea$
to be amorphousby XRD and TEM/SAED investigations(Fig. 3).
According to TGA experiments,the pyrolysis
processleading to the formation of the amorphous
slcon carbide phase,consistsof two stages:from
300 to 500'C with a weightlossof l37o and from
500 to 800'C with a further weight loss of 1270.
The PCD was heatedat 2'Cmin ' in argon up
to 500"c (PC500), 700'c (PC700) and 840.C
(PC840).The chemicalanalysisof PC840appearedto
b e S i : C : H : l : 1 . 6 : 0 . 6 5( T a b l eI ) . E x c e scsa r b o n
13ccp uls-t'tl,,ta
Chemicalshift (p.p.m.)
Linewidth (p.p.m.)
PC
PC500
PCTOO
PC84O
0
- 4.5
-6.3
-8.0
l0
12.5
3888
16
*ito---*-t*
-Zo-:n-*-
Chemicalshift (p.p,m
)
FErre 4 Evolutionwith the firing temperatureof DSi MAS-NMR
and ''C CP MAS-NMR spectraof polycarbosilane.
'.
r'-'.1
u- l.,.tn\,
r..,2"',.-lr
i,
St
,L.
I
,').,-'./"'t.-i.
I .r'"
,"/
-c' |
sl-"\ ,
I
|
-sr-c\
/
si-l
I
)sr..
r,-cr
/
-cH-t.
i'
cfl7.r
i,-
./
si-uc/
/ \
_sf\
Fr,g/fe Proposed
structure
phase
oftheamorphous
silconcarbide
obtained
from polycarbosilane-
FurJ ESRspectrum
recorded
at roomtemperature
on PC840of the network by the formation of Si C-Si bonds.
At the same time the evolution of the linewidth is
correlated to an increase of the disorder of the local
environment around the silicon atoms. During the
pyrolysis process, condensation reactions lead to
the consumption of CH., and CH, groups and to the
formation of CH or C units with the evolution of H,
or CH" [7]. These reactons obviously increasethe
number of different SiC, units that can exist in the
material and may account for the observed increaseof
the peak linewidth already mentioned. "Si MAS-NMR
study of the fired samples shows no other peaks than
thoseassignedto SiCaunits. No Si-Si nor Si O bonds
seemto be ormed during the pyrolysis process.
Information about the evolution of the local
environment of the carbon sites during the pyrolysis
processcan be obtained from the rrC CP MAS-NMR
spectrain Fig. 4. The spectrumof PC showsone peak
at 4.2 p.p.m. and a small absorption near 55 p.p.m.
that has been identified as a spinning side band. By
increasingthe firing temperaturethe main peak shifts
toward higher values of chemical shift with a corresponding increase of its line\,/idth. The resonance
presentat 4.2p.p.m. in the spectrumof PC is due to
t h e c o n t r i b u t i o no f a l l t h e c a r b o n g r o u p sp r e s e n ri n
the starting polymer, namely CH,, CH, and CH. It is
wel known that the chemical shifts of CH,, units
increasewhen the r value is decreased.
Then, according to thesedata, the shift of the peak with the firing
temperature reflects a consumption of the more
hydrogenated species due to the occurrence of the
condensationreactionsduring the pyrolysis process.
The ncreasein the linewidth has to be relatedwith the
same evolution in the resi MAS-NMR spectra. It
revealsan increasein the disorderofthe Iocaenvironment ofthe aliphatic carbon atoms during the pyrolysis
process.Moreover, an interestingfeature appearsat
above 700'C: new peaks are present in the 100 to
200p.p.m. range.Thesepeaksbecomemore intenseat
840'C. The broad peak centred around 135p.p.m.,
can be assignedto the presenceof aromatic carbon
atoms. and could be relatedto the formation of C:C
bonds. It has already beensuggestedthat such bonds
could be presentin the intermediateamorphousphase
but no experimentalevidencewas given.They should
be precursorbonds for graphiticcarbon that is formed
around 1200'C accordingto Raman data [9].
ESR was perormed on the sample fired at 840" C
ll0l.
3.2.2. Characterizationof the ACC phase
The proposed structure of the amorphous silicon
carbide phase obtained at 840'C is illustrated in
Fig. 6. It is basedmainly on rhe 2esiMAS-NMR and
rC CP MAS-NMR resultsalthough
the broadnessof
the NMR peaks in thesesamplesmade it diflculr to
obtain precise structural data. These amorphous
phasesshow a wide distribution of siliconand carbon
atoms types. However, some relevant features can be
pointed out. (a) The silicon carbide phase is not
stoichiometric,but an excessof carbon is present
(C/Si : 1.6). (b) All the silicon atoms seem to be
bonded to four carbon atoms and Si Si or Si-H
bonds,if they are presentshould be minimal. (c) Some
C:C bonds are presentasclearlyshown by the rrC CP
MAS-NMR experiments.(d) The residual hydrogen
content(H/Si : 0.65)should be mainly presentin the
structure as CH groups as suggestedby the chemical
shift of the main peak in the rrc Cp MAS-NMR
spectra. (e) The condensation reactions occurdng
during the pyrolysisprocesscan lead to the formation
of six-memberrings like those presentin crystalline
SiC, but the formation ofdistorted five- or seven-aton
rings cannot be ruled out and should lead to the
presence of C{ bonds. (f) The presence of paramagnetic defectshas been shown by ESR experiments
and these defects were assigned to carbon dangling
bonds.
A density of 2.21gcm r has been measuredon a
sample of fine powders of this phase. This value is
lower than the density of p-SiC (3.21gcm r). A
theoretical density (2.70gcm r) can be estimated
from the chemicalanalysisofPC840 (Table I) by using
the rule of mixtures and assumingthat all the silicon
atoms are engagedin forming amorphous SiC (density
3.0gcm r) [tl]while the remainingcarbon is present
as graphite(density2.2gcm 3;. The low value of the
densityof the amorphousphasecannot be ascribedto
the presenceof porosity in the material. SEM investigations (Cambridge Sterescan)have shown only few
3889
10000c
^
2.4
9500c
9000c
- 2.3
10
12
Time (h)
Figwe 7 Etoltion of the density,p, of the ACC phasewith the
lring time.
4."
f= 82 kcolmot-r
4.Q
4.1
4.2
1000
1041Rr
Fre 8 Arrheniusplot for the inital densificalionrate.
3890
Crystalsize(nm)
t 500
1700
16.0
,[
\--./q*JL_L
Pcl7oo
PC1500
\"*-/"..***--".-
PC1200
PC1000
\.-l\.*....-...,-
\-_-.r,r.*.,*.,.*"40
Pc84o
"t*"*,/
200 100
20 (des
)
Chemicalshift (p.p.m.)
d i s t i n cpt e a k sa t - 1 6 . 2 , - 2 0 a n d - 2 5 p . p . m . S u c h a
spectrumhas alreadybeenpublishedin the literature
the main peakat
[4, l5]. In a first approximation,
16.2p.p.m.can be assigned
to B-SiCand the two
minor peakscould be due to somea phase.However,
this assignmentwill be discussedlater in the discussion.
4. Discussion and conclusion
In the pyrolysisof PC, the removal of organic components occur via condensationreactions beween
CH.,and CH, groupsof the strting polymer.When
thisprocessis completethepolymerhasbeenconverted
into an amorphouscovalentceramic(ACC) phase.
The temperatureat which the condensationreactions
end and the ACC is formed can be obtainedfrom a
TGA experiment:it can be definedas the temperature
at which the weightlossesare completeand the curve
approaches
a constantweightvalue.However,this is
l6
- t6.2
20
- 16.2
-20
FBrre 10 TEM bright-fildmicrographof PC frredat 1500'C.
3891
80
40
-40
-B0
Chemicalshift (p.p.m.)
Fgrle / 1 Coparison betweenthe zesiMAS-NMR spectraof the
samplelired at 1700'Cand a commericall-SiC (Supriorcraphite).
TABLE
V Chemicalshifts of siliconcarbidepolytypes
Sample
Chemicalshift
(p.p.m.,
Reference
,-sic,3c
- 18.3
- 18.9
I2r]
a-SiC,6H
- 13.9)
-"-|
d-SiC,l5R
, r4.e
- 20.81
Present
[2t
12u
24.4)
Received 4 May
and accepted 29 September 1989
3893