Journal of Alloys and Compounds 320 (2001) 251261

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#
$%ase e&uili'ria and !%ermal analysis of (iC) ceramics
*+ans Jur,en (eifer!-. Jian&ian, $en,. +ans #eo #u/as. 0ri!1 Aldin,er
***2a34$lanc/45ns!i!u! f ur 2e!allforsc%un, and 5ns!i!u! f ur )ic%!me!allisc%e Anor,anisc%e 2a!erialien. 6niversi!a! (!u!!,ar!.
$ulverme!allur,isc%es #a'ora!orium. +eisen'er,s!r. 5. 70568 (!u!!,ar!. 9ermany
A's!rac!
:%e p%ase reac!ions. crys!alli1a!ion 'e%aviour and !%ermal de,rada!ion of !wo (iC) ceramics derived from precursors ;:50 and
)C$200. respec!ively. were s!udied 'y means of CA#$+A< !ype !%ermodynamic calcula!ions and e3perimen!al inves!i,a!ions 'y
<:A :9. =>< and (?2 ?<=. :%e p%ase reac!ion (i 3 ) @ 13C53(iC12) 2 proceeds durin, !%e !%ermal de,rada!ion of 'o!% ceramics.
Addi!ionally. !%e p%ase reac!ion (i 3 ) @ 53(i12) 2 occurs durin, !%e !%ermal de,rada!ion of !%e )C$200 ceramic. :o e3plain
&uan!i!a!ively !%e %i,% !empera!ure 'e%aviour of (iC) ceramics. !%ermodynamic func!ions. !%e reac!ion sc%eme. iso!%ermal sec!ions.
isople!%s. p%ase frac!ion dia,rams and p%ase composi!ion dia,rams (for ,as par!ial pressures) were calcula!ed. :%e compu!er simula!ions
were con3rmed 'y !%e e3perimen!s for 'o!% ceramics. A 2001 ?lsevier (cience B.;. All ri,%!s reserved.
CeywordsD (iC) ceramicsE CA#$+A<E :%ermodynamicsE :%ermal analysis
1. 5n!roduc!ion
Ceramics 'ased on non4o3ide compounds suc% as (i 3 ) @
and (iC are sui!a'le candida!es for %i,% !empera!ure
applica!ions. (iC4reinforced (i 3 ) @ composi!es are fa'ri4
ca!ed 'y addi!ion of w%is/ers. 3'res or pla!ele!s of (iC !o
(i 3 ) @ . (uc% ma!erials are conven!ionally prepared 'y
powder !ec%nolo,y usin, sin!erin, addi!ives (e.,. F 2 G 3 .
Al 2 G 3 ) or ni!ridin, a (i(iC compac! a! %i,% !empera4
!ures. :o predic! and con!rol !%e sin!erin, condi!ions
(!empera!ure. pressure. composi!ion of samples and a!mos4
p%ere) for suc% ma!erials numerous !%ermoc%emical analy4
ses of p%ase e&uili'ria in !%e (iC) sys!em %ave 'een
pu'lis%ed H110I. 2os! of !%ese pu'lica!ions !a/e in!o
accoun! !%e in3uence of !%e ni!ro,en par!ial pressure and
!%e ac!ivi!y of car'on on p%ase e&uili'ria. :%e resul!s
provided ,uidelines for !%e developin, of suc% ma!erials.
:%e presen! paper considers mos! recen! !%ermodynamic
da!a for !%e (iC) sys!em w%ic% are used for !%e
calcula!ion of p%ase e&uili'ria and p%ase reac!ions in
precursor4derived (iC) ceramics.
:%e use of precursors %as a!!rac!ed wide a!!en!ion as an
al!erna!ive approac% !o produce (i 3 ) @ (iC ceramics and
offers a num'er of advan!a,es compared !o classic powder
!ec%nolo,y. Ji!% !%e syn!%esis of (iC) ceramics from
-Correspondin, au!%or. :el.D 1@8471146K641105E fa3D 1@8471146K64
1131.
?4mail addressD seifer!Laldi3.mpi4s!u!!,ar!.mp,.de (+.J. (eifer!).
precursor polymers one can con!rol !%e ma!erials com4
posi!ion. s!ruc!ures and proper!ies on an a!omic scale
H1116I. +i,%ly %omo,eneous ceramics may 'e prepared
and s%aped wi!%ou! a sin!erin, aid. 0ur!%ermore. i! can
provide processin, oppor!uni!ies for some applica!ions
suc% as coa!in, or 3're prepara!ion. Accordin, !o !%is
rou!e polysila1ane is crosslin/ed and !%en pyrolysed in!o
amorp%ous (iC) ceramics wi!% a comple!ely %omo,e4
neous dis!ri'u!ion of !%e elemen!s and remainin, amor4
p%ous up !o 1700 C in ar,on or ni!ro,en and 1K00 C in air
H1@.15I. A! !empera!ures %i,%er !%an 1700 C in ar,on or
ni!ro,en !%is amorp%ous s!a!e is !ransformed in!o poly4
crys!alline ceramics consis!in, of !%ermodynamic s!a'le
p%ases. suc% as (i 3 ) @ . (iC and ,rap%i!e. (ince !%e
pyrolysis produc!s can 'e used as 'o!% amorp%ous and
crys!alline ma!erials. !%e unders!andin, of !%e %i,% !em4
pera!ure 'e%aviour of !%e ceramics and !%e p%ase reac!ions.
!%e crys!alli1a!ion 'e%aviour and !%e accompanied ma!erial
!%ermal de,rada!ion are of ,rea! impor!ance wi!% respec! !o
!%e p%ysico4c%emical proper!ies of !%e polycrys!alline
ceramics and !o !%e ma3imum applica!ion !empera!ure of
!%e amorp%ous ceramics.
:o simula!e and predic! !%e p%ase e&uili'ria and p%ase
reac!ions in ceramics of !%e (iC) sys!em. !%ermo4
dynamic calcula!ions 'y !%e CA#$+A< me!%od (CA#cu4
la!ion of $+Ase <ia,ram H17I) were carried ou!. ;arious
!ypes of p%ase dia,rams. p%ase frac!ion dia,rams. p%ase
composi!ion dia,rams and !%ermodynamic func!ions were
compu!er calcula!ed usin, modern sof!ware and !%e mos!
08254K3KK 01 M see fron! ma!!er A 2001 ?lsevier (cience B.;. All ri,%!s reserved.
$55D (08254K3KK( 00 )01@7K4=
252 +. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261
relia'le !%ermodynamic da!a for !%e (iC) sys!em. :%is
informa!ion can 'e used for !empera!ures %i,%er !%an a'ou!
1700 C w%ere !%e ma!erials s!ar! !o crys!alli1e H1K20I. A!
lower !empera!ures precursor4derived samples may remain
even af!er lon,4!erm %ea! !rea!men! in a none&uili'rium
s!a!e (amorp%ous. par!ially crys!alline) w%ere !%e p%ase
con3,ura!ion canno! 'e reproduced 'y e&uili'rium calcula4
!ions.
:%e compu!er simula!ions were con3rmed 'y e34
perimen!al inves!i,a!ions usin, !%ermal analysis. =4ray
diffrac!ome!ry and microscopic me!%ods.
2. :%ermodynamic calcula!ions
:%e CA#$+A< me!%od H17I was used !o simula!e and
unders!and p%ase reac!ions and crys!alli1a!ion 'e%aviour of
precursor4derived ceramics. :%e dia,rams were calcula!ed
usin, !%e sof!ware of #u/as H21I and :%ermoCalc H22I.
:%e !%ermodynamic da!a for !%e 'inary sys!ems (iC and
(i) used in !%is wor/ were !a/en from >efs. H23.2@I.
respec!ively. :%e assessmen! of !%ese sys!ems is 'ased on
da!a for !%e pure elemen!s (i. C and ) provided 'y
<insdale H25I and s!ored in !%e (9:? da!a'ase H26I. :%e
da!a for ,aseous species ) 2 . (i. (i 2 . (i 2 C. (iC 2 . C) and
C 2 ) 2 and some o!%ers were !a/en from !%e (9:? su'4
s!ance da!a'ase H26I. Beside !%e ,as p%ase. !%e li&uid p%ase
and !%e solid p%ases. silicon. ,rap%i!e. (i 3 ) @ and (iC were
!a/en in!o accoun!. '4(i 3 ) @ is !%e s!a'le modi3ca!ion of
!%e compound (i 3 ) @ w%ereas a4(i 3 ) @ is a me!as!a'le
modi3ca!ion H27I. A sin,le analy!ical 9i''s4ener,y de4
scrip!ion was used !o descri'e a4 and '4(iC. :%e !ernary
p%ases (iC 2 ) @ and (i 2 C) @ documen!ed 'y >iedel e! al.
H2KI. are repor!ed no! !o 'e s!a'le a! condi!ions !rea!ed %ere
( p 5 1 'ar. : . 1300 C). :%e pos!ula!ed compound C 3 ) @
H28I was no! found as solid p%ase un!il now.
2ore recen! discussions on !%e e3perimen!al informa!ion
on !%e !%ermodynamics of a4 and '4(iC were provided
recen!ly 'y Cley/amp H30I and a4 and '4(i 3 ) @ 'y #ian,
e! al. H27I and GN+are e! al. H31I. :%ese pu'lica!ions
con3rm !%e analy!ical descrip!ions used in !%e presen!
wor/.
:%e p%ase reac!ions in !%e !ernary sys!em (iC) can
'e simula!ed 'y e3!rapola!in, calcula!ions since all solid
p%ases %ave ne,li,i'le ran,es of solu'ili!y. :o simula!e
and predic! !%e p%ase reac!ions of precursor4derived
ceramics. !%ermodynamic func!ions. !%e reac!ion sc%eme.
iso!%ermal sec!ions. isople!%s. p%ase frac!ion dia,rams and
p%ase composi!ion dia,rams (for ,as par!ial pressures)
were calcula!ed.
($;()E +oec%s! A9. 0ran/fur!. 9ermany) wi!% composi4
!ion (i 1 C 1.6 ) 1.33 (25.@ (i. @0.7 C. 33.K )E a!.O) and
)C$200 (poly%ydridome!%ylsila1ane ($+2()E )ic%imen
Corp.. :o/yo. Japan) wi!% composi!ion (i 1 C 0.6 ) 1.02 (3K.2
(i. 22.8 C. 3K.8 )E a!.O). as descri'ed in de!ail elsew%ere
H32.33I. :%e polysila1anes were crosslin/ed a! !empera4
!ures 'e!ween @73 and 673 C under vacuum and in Ar
a!mosp%ere. and !%en !%ermolysed a! a !empera!ure of 1323
C under Ar a!mosp%ere in!o !%e amorp%ous ceramics. :%e
amorp%ous ceramics were milled for 20 min usin, JC
'alls. :%e mean par!icle si1e of !%e resul!in, powder was
measured 'y laser sca!!erin, (9ranulome!er +> K50. Cilas4
Alca!el). An avera,e value of a'ou! 10 mm was found. :%e
con!en! of o3y,en in 'o!% amorp%ous ceramics was less
!%an 1 massO measured 'y carrier ,as %o! e3!rac!ion wi!%
!%ermal conduc!ivi!y and infrared a'sorp!ion de!ec!ors (:C
@36. #eco).
5nves!i,a!ions 'y differen!ial !%ermal analysis (<:A)
and !%ermo,ravime!ry (:9) were carried ou! simul!aneous4
ly in B) cruci'les ((imul!aneous :%ermal Analysis. (:AE
*Ba%r (:A501 wi!% ,rap%i!e %ea!in, elemen!). 0lowin,
ni!ro,en a!mosp%ere (2esser49ries%eimE ni!ro,en 5.0.
o3y,en.5 vpm. 3owin, ra!eD 2 l %) was used. :%e %ea!in,
ra!e was 10 C min up !o 1273 C. and 5 C min up !o !%e
ma3imum !empera!ure of 2073 or 2273 C.
:%e p%ase con3,ura!ion was analysed 'y =4ray diffrac4
!ome!ry (=><E (iemens <iffra/!ome!er <5000 Cris!allo34
e3. Cu Ca 1 radia!ion). 2icros!ruc!ures and p%ase com4
posi!ions were inves!i,a!ed 'y scannin, elec!ron micro4
scopy ((?2E Peiss <(28K2 9?25)5) coupled wi!%
ener,y dispersive =4ray spec!roscopy (?<=E G3ford45n4
s!rumen! 5(5( 300).
@. >esul!s and discussion
@.1. :%ermodynamic calcula!ions
0i,. 1 s%ows calcula!ed iso!%ermal. iso'aric ( p 5 1 'ar)
sec!ions in !%e !ernary sys!em (iC) for !%e !empera4
!ures 16K7 C.: .1757 C (0i,. 1a). 1757 C.: .211@ C
(0i,. 1'). : 5 2123 C (0i,. 1c) and : 5 3000 C (0i,. 1d).
Below a !empera!ure of 16K7 C silicon e3is!s as solid
p%ase. 0rom !%e e3perimen!al poin! of view ni!ro,en
escapes a! 1 'ar. 'u! for !%e calcula!ion i! is in !%e ,as
p%ase and s!ill par! of !%e sys!em (included in !%e mole
frac!ion). :%e p%ase e&uili'ria. composi!ions of !%e as4
!%ermolysed amorp%ous ceramics made from ;:504 or
)C$2004precursors and correla!ed reac!ion pa!%s are indi4
ca!ed (arrows in 0i,. 1' and c. respec!ively). :%e reac!ion
pa!%s H3@I indica!e !%e c%an,e of !%e ,ross composi!ion of
!%e solid samples due !o !%e loss of ni!ro,en accordin, !o
!%e nonvarian! reac!ions
(i 3 ) @ (s) 1 3C (s) 5 3(iC (s) 1 2) 2 (,)E : 5 1757 C
and
(1)
3. ?3perimen!al procedure
Amorp%ous (iC) ceramics were derived from com4
mercially availa'le precursors ;:50 (polyvinylsila1ane
+. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261 253
0i,. 1. 5so!%ermal. iso'aric sec!ions in !%e (iC) sys!em a! 1 'ar. :%e composi!ions of !%e amorp%ous ;:504 and )C$2004derived ceramics (m. d) and
reac!ion pa!%s (arrows) are indica!ed. (a) 16K7 C.: .1757 CE (') 1757 C.: .211@ CE (c) : 5 2123 CE (d) : 5 3000 C.
(i 3 ) @ (s) 5 3(i (l) 1 2) 2 (,)E : 5 211@ C (2)
5n connec!ion wi!% reac!ion (1) !%e ;:50 ceramic wi!% a
ra!io CD(i.1 produces ni!ro,en un!il !%e indica!ed reac!ion
pa!% ends on !%e !ie line ,rap%i!e(iC (0i,. 1') w%ereas
!%e ceramic )C$200 wi!% a ra!io CD(i.1 produces
ni!ro,en and c%an,es !%e composi!ion !o !%e (iC(i 3 ) @ !ie
line. A! !empera!ures a'ove 211@ C !%e )C$2004derived
ceramic a,ain loses ni!ro,en (0i,. 1c) 'ecause !%e residual
(i 3 ) @ dissocia!es in!o li&uid silicon and ni!ro,en ,as
accordin, !o reac!ion (2).
0i,. 1d s%ows !%e calcula!ed iso!%ermal sec!ion in !%e
(iC) sys!em a! a !empera!ure of 3000 C. A! suc% %i,%
!empera!ures li&uid silicon dissolves some car'on and !%e
!ernary ,as p%ase re,ion is si,ni3can!ly e3!ended. :%e ,as
p%ase does no! only consis! of ) 2 'u! as well of o!%er
,aseous species suc% as (i. (i 2 . (iC 2 . (i 2 C. C) and C 2 ) 2
as ,iven in 0i,. 2 w%ic% s%ows !%e par!ial pressures of
differen! ,aseous species concernin, !%e ,as p%ase rela!ed
!o !%e ;:504derived ceramic a! a !o!al pressure of 1 'ar.
0i,. 3a s%ows !wo das%ed lines wi!%in !%e iso!%ermal
sec!ion valid a! !empera!ures 'e!ween 1757 and 211@ C
(0i,. 1') w%ic% are !%e composi!ion lines of !wo isople!%s
s%own in 0i,. 3' and c (C@2.8 (i. 57.1 )E C@8.5 (i.
50.5 )E a!.O) includin, !%e composi!ions of !%e ;:504 and
)C$2004derived ceramics. A! !empera!ures 'elow 1757 C
'o!% ma!erials consis! of ,rap%i!e. (i 3 ) @ and (iC. A!
%i,%er !empera!ures !%e composi!ions wi!%ou! ,as are
25@ +. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261
0i,. 2. $ar!ial pressures for !%e ,as p%ase in e&uili'rium wi!% ;:504
derived ceramics.
loca!ed ou!side !%e indica!ed composi!ion lines of !%e
isople!%s (see reac!ions pa!%s in 0i,. 1'). 5n accordance
wi!% !%e iso!%ermal sec!ion a! : .1757 C !%e condensed
ma!erials consis! of ,rap%i!e and (iC (;:50) or (i 3 ) @ and
(iC ()C$200). respec!ively.
Based on !%ese calcula!ions !%e (c%eil4reac!ion sc%eme
H35I for !%e (iC) sys!em (valid for p 5 1 'ar) was
derived (0i,. @). :%e sc%eme is similar !o !%e one
presen!ed 'y Jeiss e! al. H3I 'u! wi!% improved reac!ion
!empera!ures. :%e reac!ions (1) and (2) are indica!ed as 6 2
and p 2 . respec!ively. :%e mel!in, poin! of (i is indica!ed
'y reac!ion < 2 . Because of lac/ of da!a !%e !ransforma!ion
'4(iC a4(iC was no! !a/en in!o accoun!. :%e a4(i 3 ) @ '4
(i 3 ) @ !ransforma!ion was no! !a/en in!o accoun! as a4
(i 3 ) @ is assumed !o 'e a me!as!a'le p%ase H27I (see
(ec!ion 2).
:%e in3uence of !%e ,as p%ase on !%e p%ase reac!ions is
s%own in 0i,. 5 'y !%e calcula!ed po!en!ial p%ase dia,rams
for CD(i.1 (0i,. 5a. valid for e.,. ;:50 ceramic) and
CD(i.1 (0i,. 5'. valid for e.,. )C$200 ceramic). :%e
me!%od of calcula!ion of suc% dia,rams is descri'ed
elsew%ere H36I. +ere !%e ,as p%ase is considered !o 'e
ou!side !%e sys!em. 'u! may e3c%an,e ni!ro,en wi!% !%e
sys!em. Alon, !%e line iden!ical in 'o!% 3,ures !%e !%ree
p%ases. ,rap%i!e. (iC and (i 3 ) @ are in e&uili'rium and
s%ow !%e reac!ion (1). Below !%e line ei!%er !%e !wo4p%ase
3eld (iC1C (CD(i.1) or (iC1(i 3 ) @ (CD(i.1) e3is!s.
(i 3 ) @ decomposes a! low par!ial pressures of ) 2 accordin,
!o reac!ion (2) in!o ni!ro,en and li&uid or solid (i w%ic% is
in e&uili'rium wi!% (iC. )o!e !%e c%an,e of !%e reac!ion
!empera!ures wi!% !%e c%an,in, par!ial pressure of ni!ro4
,en. :%e reac!ion !empera!ures ,iven in !%e (c%eil reac!ion
sc%eme (0i,. @) are valid for a !o!al pressure of 1 'ar. :%e
dia,rams ,ive advice for !%e sin!erin, of (i 3 ) @ (iC
samples. 5f !%e ) 2 4par!ial pressure is a'ove !%e line (iC1
C1(i 3 ) @ !%e sample is s!a'le a! !%e sin!erin, !empera!ure.
0or sin!erin, of (iC1(i 3 ) @ !%ere are !empera!ure4depen4
den! upper and lower limi!s for !%e ) 2 4pressure for !%e
s!a'ili!y ran,e. 0or more de!ails see >efs. H5.K.36I.
Addi!ionally. &uan!i!a!ive mass 'alances and !%e en4
!%alpies of p%ase reac!ions can 'e calcula!ed for !%e
ceramics w%ic% appear in !%e e3perimen!al (:A inves4
!i,a!ions. 0or !%is purpose p%ase frac!ion dia,rams were
calcula!ed. 0i,. 6a s%ows !%is !ype of dia,ram calcula!ed
for a !o!al pressure of 1 'ar for !%e composi!ion of
;:504derived ceramic (CD(i.1) w%ere a! !%e aforemen4
!ioned !empera!ure of 1757 C accordin, !o reac!ion (1)
70.7 massO (i 3 ) @ . 28.2 massO ,rap%i!e and ne,li,i'le
amoun! of (iC form 60.7 massO of (iC and 2K.3 massO
of ni!ro,en. :%e predic!ed sample mass loss due !o
ni!ro,en evolu!ion is 2K.3O. :%e ,as p%ase in calcula!ion
s!ill 'elon,s !o !%e sys!em 'u! appears as Qmass lossN in :9
e3perimen!sE 11 massO e3cess ,rap%i!e remain. 5n ;:504
derived ceramics no (i 3 ) @ is found any lon,er. :%e
c%an,in, composi!ion wi!% !%e differen! ,aseous species
cons!i!u!in, !%e ,as p%ase a! differen! !empera!ures is
s%own in !%e calcula!ed dia,ram of 0i,. 2.
0or )C$2004derived ceramic (0i,. 6') wi!% a ra!io
CD(i.1 all car'on is consumed and !%ere is a mass loss of
13.7O due !o reac!ion (1). Af!er !%e reac!ion e3cess (i 3 ) @
remains. A! !empera!ures %i,%er !%an 1K@1KC (211@ C) !%is
residual (i 3 ) @ decomposes accordin, !o reac!ion (2)
causin, a fur!%er mass loss of 15.1O. :%e 'alanced
reac!ion ?&. (1) is only valid for a ra!io CD(i 3 ) @ de3ned
'y !%e in!ersec!ion of !%e inner !ie4lines C(i 3 ) @ and
)(iC of !%e four p%ase reac!ion (1) (78.6 massO (i 3 ) @ .
20.@ massO ,rap%i!e). 0or precursor ceramics wi!% lower
car'on con!en! (e.,. )C$200) all car'on is consumed
durin, reac!ion (2) and (i 3 ) @ remains.
:%e len,!% of !%e arrows indica!in, !%e reac!ion pa!%s in
0i,. 1' and c ,ives !%e value of !%e rela!ive c%an,e of !%e
ni!ro,en con!en! of !%e solid samples. 5n !%e case of
;:504derived ceramic a direc! comparison wi!% !%e resul!
of !%e calcula!ed p%ase frac!ion dia,ram is possi'le. :%e
composi!ion of !%is ceramic c%an,es accordin, !o !%e
se&uence (i 1 C 1.6 ) 1.33 (25.@ (i. @0.7 C. 33.K )E
a!.O)R(i 1 C 1.6 (3K.5 (i. 61.5 CE a!.O). :%e 3nal solid
sample los! !%e comple!e ni!ro,en con!en! of 33.K a!.O.
:%is value can 'e found from !%e indica!ed reac!ion pa!%
(arrow) for ;:504derived ceramics in 0i,. 1' and corre4
sponds !o !%e 2K.3 massO calcula!ed in !%e p%ase frac!ion
dia,ram (0i,. 6a). :%e rela!ions%ip 'e!ween !%e reac!ion
pa!%s and !%e calcula!ed p%ase frac!ion dia,ram for !%e
)C$2004derived ceramic is no! as o'vious as for !%e
;:504derived ceramics. :%e composi!ion of !%a! ceramic
c%an,es durin, !%e reac!ions (1) and (2) accordin, !o !%e
followin, se&uenceD
(a) ((i 1 C 0.6 )) 1.02 (3K.2 (i. 22.8 C. 3K.8 )E a!.O) R
((i 1 C 0.6 )) 0.53 (@6.8 (i. 2K.1 C. 25 )E a!.O)
+. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261 255
0i,. 3. 5sople!%s in !%e (iC) sys!em. Composi!ions of ;:504 and )C$2004derived ceramics are indica!ed. (a) 5so!%ermal sec!ion for !empera!ure ran,e
1757 C.: .211@ C wi!% indica!ed composi!ion lines of isople!%s s%own in (') and (c). (') 5sople!% C@2.8 (i. 57.1 ) (a!.O). (c) 5sople!% C@8.5 (i. 50.5
) (a!.O).
(') ((i 1 C 0.6 )) 0.53 (@6.8 (i. 2K.1 C. 25 )E a!.O) R
(i 1 C 0.6 (62.5 (i. 37.5 CE a!.O).
:%e len,!% of !%e correspondin, !wo arrows (reac!ion
pa!%s in 0i,. 1' and c. respec!ively) ,ive only !%e rela!ive
c%an,e of !%e ni!ro,en con!en! of !%e solid samples. Af!er
!%e 3rs! s!ep (a) !%e ni!ro,en con!en! of !%e solid sample is
25 a!.O. :%e p%ase frac!ion dia,ram ,ives a mass loss of
13.7O w%ic% corresponds !o 1K.5 a!.O. A! 3rs! ,lance !%is
value does no! a,ree wi!% !%e value of ni!ro,en loss
derived from !%e len,!% of !%e arrow in 0i,. 1' w%ic% is
13.8 a!.O. :%e da!a of !%e p%ase frac!ion dia,ram calcula4
!ion refer !o !%e !o!al sys!em includin, !%e ,as p%ase w%ic%
released durin, !%e reac!ion a! 1757 C. w%ereas !%e 25
a!.O are referred !o !%e solid residue af!er !%is reac!ion.
:%e calcula!ion assumes !%e ,as p%ase always as par! of
!%e sys!em as descri'ed in (ec!ion @.1. Gn !%e o!%er %and
!%e da!a from !%e indica!ed reac!ion pa!%s refer only !o !%e
composi!ion of !%e solid p%ases wi!%ou! !a/in, in!o
accoun! !%e released ,as p%ase. :%e calcula!ed mass loss of
!%e second s!ep is 15.1 massO (20.@ a!.O) of !%e ini!ial
sample or 25.0 a!.O referred !o !%e residue of s!ep 1.
0i,. 6a and ' s%ow !%a! a! !empera!ures %i,%er !%an 2600
256 +. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261
0i,. @. (c%eil reac!ion sc%eme for !%e (iC) sys!em ('4(iC a4(iC and
a4(i 3 ) @ '4(i 3 ) @ !ransforma!ions no! indica!ed).
C !%e (iC frac!ion decreases w%ereas !%e frac!ion of !%e
,as p%ase increases. :%is resul!s from !%e forma!ion of !%e
,aseous species C(i 2 and C 2 (i a! suc% %i,% !empera!ures
as s%own for !%e composi!ion of !%e ;:504derived ceramic
in 0i,. 2.
:%e <:A e3perimen!s can 'e simula!ed 'y calcula!in,
en!%alpy!empera!ure dia,rams (0i,. 7). :%e calcula!ed
en!%alpy!empera!ure dia,ram s%ows for ;:504derived
ceramic an endo!%ermic %ea! effec! of 152.3 /J mol
(moles of a!oms of !o!al sample) for reac!ion (1). Gnly par!
of !%e sample is involved in !%e reac!ion and !%erefore !%e
%ea! effec! is lower !%an e3pec!ed for a ra!io of p%ases
suf3cien! for comple!e reac!ion. :%e en!%alpy of reac!ion
(1) in )C$2004derived ceramic is 12K.5 /J mol and of
reac!ion (2) i! is 1@8.5 /J mol.
5! %as !o 'e decided w%ic% cruci'le ma!erial is sui!a'le
for !%e %ea! !rea!men! and !%ermal analyses of !%e ceramic
samples. i.e. i! mus! no! reac! wi!% !%e sample. 9rap%i!e
cruci'les are no! ade&ua!e 'ecause !%ey reac! wi!% (i 3 ) @ .
An al!erna!ive cruci'le ma!erial is B). :%e reac!ion of
;:504derived ceramics of composi!ion (i 1 C 1.6 ) 1.33 wi!%
B) was simula!ed. :%e resul! is s%own as p%ase frac!ion
dia,ram in 0i,. K. :%e calcula!ion s%ows !%a! B) does no!
!a/e par! in reac!ion (1) (i.e. 6 2 in 0i,. @). Accordin, !o
!%e e&uili'rium calcula!ion B) is formed a! !empera!ures
lower !%an 1000 C and remains iner! un!il !%e reac!ion of
B) wi!% (iC a! !%e !empera!ure of 25K6 C. Based on !%is
resul!. B) cruci'les were used for !%ermal analyses.
0i,. 5. $o!en!ial p%ase dia,rams for !%e (iC) sys!em H36I. (a) CD(i.
1E (') CD(i.1.
@.2. ?3perimen!al inves!i,a!ions
0i,. 8a and ' s%ow !%e <:A :9 curves for !%e ;:504
derived and !%e )C$2004derived ceramic. respec!ively.
:%e :9 analysis of ;:50 ceramic s%ows a mass loss of
28O 'e!ween 1600KC (1K73 C) and 1680KC (1863 C).
(imul!aneously an endo!%ermic reac!ion pea/ was found
'y <:A. :%is mass loss and endo!%ermic reac!ion pea/
can 'e e3plained 'y reac!ion (1) (0i,s. 1a.' and 6a)
al!%ou,% !%e reac!ion !empera!ure is %i,%er !%an !%e
calcula!ed one (1757 C).
:%is s%if! of !%e measured reac!ion !empera!ure for
reac!ion (1) can 'e e3plained 'y /ine!ic %indrance. As
s%own 'y Bill e! al. H37I an e3!ended %ea! !rea!men! of
;:50 precursor4derived ceramic is necessary !o comple!e4
ly crys!alli1e !%e ma!erial a! 1773 C and 3nd !%e e&uili'4
rium p%ases. Af!er %ea! !rea!men! for 50 % a! 1773 C in
ni!ro,en a!mosp%ere !%e ma!erial consis!s only of (iC and
car'on. :%is resul! con3rms !%a! reac!ion (1) occurs close
!o !%e calcula!ed reac!ion !empera!ure of 1757 C. +owever.
'ecause of !%e slu,,is%ness of !%e reac!ion i!s !empera!ure
+. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261 257
0i,. 7. Calcula!ed en!%alpy!empera!ure dia,ram for !%e ;:504 and
)C$2004derived ceramics.
) 2 4a!mosp%ere is very small (see (ec!ion 3) and immedi4
a!ely reac!s wi!% !%e ,rap%i!e %ea!in, elemen!s used.
5n !%e case of )C$200 ceramic. !%e !wo s!eps of mass
loss wi!% accompanied endo!%ermic reac!ions could 'e
de!ec!ed as predic!ed 'y !%ermodynamic calcula!ion (0i,s.
1a.' and 6'). 5n !%e !empera!ure ran,e from 1600KC (1K73
C) !o 1680KC (1863 C) 12O mass loss and an endo!%ermic
reac!ion pea/ was de!ec!ed. and 'e!ween 1K@0KC (2113 C)
and 1800KC (2173 C) 15O mass loss and an endo!%ermic
reac!ion pea/ was de!ermined. :%e 3rs! endo!%ermic pea/
0i,. 6. Calcula!ed p%ase frac!ion dia,rams in !%e (iC) sys!em. (a)
;:504derived ceramics (CD(i.1). (') )C$2004derived ceramics (CD(i.
1).
canno! 'e de!ec!ed e3ac!ly 'y !%ermal analysis usin, a
de3ned %ea!in, ra!e (!%is wor/D 5 C min. see (ec!ion 3).
:%e in3uence of !%e small o3y,en amoun! in !%e
samples (.1 massO) on !%e reac!ion 'e%avior is ne,li4
,i'le. )o (pro!ec!ive) (iG 2 layers were found 'y !ransmis4
sion elec!ron microscopy H37I in ;:50 precursor4derived
ceramics. Addi!ionally. !%e o3y,en frac!ion in !%e 3owin, 0i,. K. $%ase frac!ion dia,ram for !%e com'ina!ion of ;:504derived
ceramic wi!% B).
25K +. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261
0i,. 8. <:A :9 measuremen!s ((:A) for precursor4derived ceramicsE ) 2 a!mosp%ere. B)4cruci'le. 10 C min up !o 1000KC (1273 C). 5 C min up !o
2000KC (2273 C). (a) ;:504derived ceramicsE (') )C$2004derived ceramics.
can 'e a!!ri'u!ed !o reac!ion (1). al!%ou,% !%is !empera!ure
is %i,%er !%an calcula!ed for reasons similar as discussed
for ;:504derived ceramics. :%e second endo!%ermic pea/
is due !o !%e decomposi!ion of residual (i 3 ) @ accordin, !o
reac!ion (2). :%e !wo s!eps of mass loss a,ree &uan!i!a!ive4
ly wi!% !%e calcula!ed ones.
:%e ra!io of !%e !%ree e3perimen!ally derived en!%alpy
values (!%e area of !%e endo!%ermic pea/s) is similar !o !%e
ra!io of !%e calcula!ed en!%alpies (0i,. 8). :%e !empera!ure
of reac!ion (2) is in a,reemen! wi!% !%e calcula!ed one.
=>< and (?2 com'ined wi!% ?<= were used !o
con3rm !%e resul!s o'!ained 'y (:A and !%e !%ermo4
dynamic calcula!ions. 0i,. 10 s%ows !%e =>< pa!!erns of
!%e ;:504derived ceramic. :%e s!ruc!ure of !%is ma!erial
+. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261 258
0i,. 10. =>< pa!!erns of !%e ;:504derived ceramic. (a) Before (:A. (') Af!er (:A up !o 2000KC (2273 C).
'efore (:A is almos! comple!ely amorp%ous as s%own in
0i,. 10a. Af!er (:A wi!% upper !empera!ure of 2000KC
(2273 C. 0i,. 8a) !%e ma!erial consis!s of crys!alline '4(iC
and ,rap%i!e (0i,. 10'). w%ic% is in accordance wi!% !%e
calcula!ions (0i,s. 1a.' and 6a). 5n case of !%e )C$2004
derived ceramic. af!er (:A up !o 1K00KC (2073 C. 0i,. 8')
0i,. 11. =>< pa!!ern of !%e )C$2004derived ceramic. (a) Before (:A. (') Af!er (:A up !o 1K00KC (2073 C). (c) Af!er (:A up !o 2000KC (2273 C).
260 +. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261
0i,. 12. (?2 ima,es of )C$2004derived ceramics. (a) Af!er (:A up !o 1K00KC (2073 C). (') Af!er (:A up !o 2000KC (2273 C).
!%e p%ase con3,ura!ion c%an,es !o '4(iC a4(i 3 ) @ or !o
'4(iC (i. if !%e (:A is con!inued up !o 2000KC (2273 C.
0i,. 8'). Comparin, !%e =>< pa!!erns of !%e )C$2004
derived ceramics in 0i,. 11ac wi!% 0i,s. 1ac and 6'
s%ows !%a! !%e e3perimen!al resul!s are also correc!ly
simula!ed 'y !%e calcula!ion.
0i,. 12 s%ows (?2 ima,es of )C$2004derived ceramic.
+ea!in, up !o 1K00KC (2073 C. 0i,. 12a) clearly '4(iC
(i 3 ) @ can 'e reco,ni1ed. w%ereas af!er %ea!in, up !o
2000KC (2273 C. 0i,. 12') 'esides '4(iC silicon can 'e
seen w%ic% %as s!ill !%e s%ape of solidi3ed drople!s. :%e
p%ase composi!ions were con3rmed 'y ?<= analyses.
for 3nancial suppor!. 0or providin, samples we are
,ra!eful !o J. Bill. $. 9ers!el. (. $rin1 and J. (ei!1. :%e
au!%ors !%an/ 2. :%omas. +. Cummer and +. #a'i!1/e for
suppor! in e3perimen!al analyses.
>eferences
*H1I +. >assaer!s. A. (c%mid!. $lansee'eric%!e fur
$ulverme!allur,ie 1@
(1866) 11011@.
H2I ?. 9u,el. $. ?!!mayer. A. (c%mid!. Beric%!e <eu!sc%e Ceramisc%e
9esellsc%af! @5 (K) (186K) 385@02.
H3I J. Jeiss. +.#. #u/as. J. #oren1. 9. $e!1ow. +. Crie,. CA#$+A< 5
(2) (18K1) 1251@0.
H@I +.#. #u/as. J. Jeiss. +. Crie,. ?.4:%. +eni,. 9. $e!1ow. +i,%
:emp.+i,% $ress. 1@ (18K2) 607615.
H5I C.9. )ic/el. 2.J. +offmann. $. 9reil. 9. $e!1ow. Adv. Ceram.
2a!er. 3 (6) (18KK) 557562.
H6I +. Jada. 2.4J. Jan,. :.4F. :ien. J. Am. Ceram. (oc. 71 (18KK)
K37K@0.
H7I J. Jeiss. +.#. #u/as. 2a!er. (ci. 0orum @7 (18K8) @357.
HKI A.C. 2isra. J. 2a!er. (ci. 26 (1881) 6581658K.
H8I A. J%a. J. 2a!er. (ci. 2K (1883) 30683078.
H10I 6. )eid%ard!. +. (c%u'er!. ?. Bisc%off. 9. $e!1ow. Cey ?n,. 2a!er.
K881 (188@) 1K7182.
H11I J. Bill. 0. Aldin,er. Adv. 2a!er. 7 (1885) 7757K7.
H12I 0. Aldin,er. 2. Jeinmann. J. Bill. $ure Appl. C%em. 70 (188K)
@38@@K.
H13I J. Bill. 0. Aldin,er. P. 2e!all/d. K7 (1886) K27K@0.
*H1@I >. >iedel. +.4J. Clee'e. +. (c%onfelder. 0. Aldin,er. )a!ure 37@
(1885) 52652K.
*H15I >. >iedel. 9. $assin,. +. (c%onfelder. >.J. Broo/. )a!ure 355
(1882) 71@716.
*H16I +.4J. Clee'e. <. (u!!or. +. 2uller. 9. Pie,ler. J. Am. Ceram. (oc.
K1 (188K) 28712877.
H17I ). (aunders. $. 2iodowni/. CA#$+A< (Calcula!ion of $%ase
<ia,rams)D A Compre%ensive 9uide. inD >.J. Ca%n (?d.). 2a!erials
(eries. ;ol. 1. $er,amon. G3ford. 188K.
H1KI +.J. (eifer!. 0. Aldin,er. :%ermodynamic calcula!ions in !%e sys!em
(iBC)G. inD J. Bill. 0. Ja/ai. 0. Aldin,er (?ds.). $recursor4
<erived Ceramics. Jiley;C+. Jein%eim. 1888. pp. 16517@.
H18I J. $en,. +.J. (eifer!. 0. Aldin,er. :%ermal analysis of (iC)
*ceramics derived from polysila1anes. inD 9. 2uller (?d.).
Ceramics
5. Conclusion
:%e resul!s of !%e e3perimen!al inves!i,a!ion of ;:504
and )C$2004derived ceramics s%ow !%a! CA#$+A<4!ype
simula!ions can &uan!i!a!ively predic! !%eir %i,%4!empera4
!ure 'e%aviour. :%e presen! wor/ s%ows !%a! !%ermo4
dynamic calcula!ions can 'e used successfully !o suppor!
!%e developmen! of (iC) ceramics usin, !%e powder
!ec%nolo,y and !%e precursor rou!e. respec!ively. 0rom
!%ese calcula!ions !%e p%ase e&uili'ria. p%ase composi!ions.
p%ase reac!ions and !%e accompanied micros!ruc!ure de4
velopmen! can 'e derived. (uc% informa!ion provides
,uidelines for favoura'le sin!erin, and processin, con4
di!ions and !%e unders!andin, of !%e ma!erials reac!ions
durin, applica!ion. Addi!ionally. /ine!ic effec!s (e.,. durin,
crys!alli1a!ion of amorp%ous ceramics) and !%e forma!ion
of me!as!a'le p%ases (e.,. a4(i 3 ) @ ) %ave !o 'e !a/en in!o
accoun!.
Ac/nowled,emen!s
Je !%an/ !%e <eu!sc%e 0orsc%un,s,emeinsc%af! (<09)
and !%e Japan (cience and :ec%nolo,y Corpora!ion (J(:)
+. J. (eifer! e! al. Journal of Alloys and Compounds 320 (2001) 251 261
$rocessin,. >elia'ili!y. :ri'olo,y and Jear. ?6>G2A: 88. ;ol.
12. Jiley;C+. 2000. pp. 120126.
+.J. (eifer!. J. $en,. 0. Aldin,er. <ie Cons!i!u!ion von (iBC)
Cerami/en. inD J. +einric%. 9. Pie,ler. J. +ermel. +. >iedel (?ds.).
Cerami/ (imula!ion Cerami/. Jer/s!offwoc%e N8K. 1215 Gc!..
*2unc%en. ;ol. ;55. Jiley;C+. Jein%eim. 1888. pp. 3383@3.
+.#. #u/as. (.9. 0ries. J. $%ase ?&uili'ria 13 (1882) 5325@1.
B. (undman. B. Jansson. J.4G. Anderson. Calp%ad 8 (18K5) 153
180.
*J. 9ro'ner. +.#. #u/as. 0. Aldin,er. Calp%ad 20 (1886) 2@725@.
2. +iller!. (. Jonsson. B. (undman. P. 2e!all/d. K3 (1882) 6@K
65@.
A. <insdale. Calp%ad 15 (1881) 317@25.
(cien!i3c 9roup :%ermoda!a ?urope. 9reno'le Campus. 1001
Avenue Cen!rale. B$66. 043K@02 (ain! 2ar!in <N+eres. 0rance.
%!!pD www.s,!e.or,
J.4J. #ian,. #. :opor. A. )avro!s/y. A. 2i!omo. J. 2a!er. >es. 1@
(1888) 1858186K.
261
H20I
H21I
H22I
H23I
H2@I
H25I
H26I
H27I
H2KI >. >iedel. A. 9reiner. 9. 2ie%e. J. <ressler. +. 0uess. J. Bill.
An,ew. C%em. 108 (1887) 657660.
H28I $.+. 0an,. J. 2a!er. (ci. #e!!. 1@ (1885) 53653K.
H30I +. Cley/amp. Ber. Bunsen,es. $%ys. C%em. 102 (188K) 1231123@.
H31I $.A.9. GN+are. 5. :omas1/iewic1. C.2. Bec/ 55. +.J. (eifer!. J.
C%em. :%ermodyn. 31 (1888) 303322.
H32I J. (ei!1. $olymer4$yrolyse4Cerami/ auf (i C )4Basis. 6niversi!y
of (!u!!,ar!. 9ermany. 1886. $%.<. :%esis.
H33I J. (ei!1. J. Bill. J. 2a!er. (ci. #e!!. 15 (1886) 381383.
H3@I +.J. (eifer!. P. 2e!all/d. 80 (1888) 1016102@.
H35I +.#. #u/as. ?.4:%. +eni,. 9. $e!1ow. P. 2e!all/d. 77 (18K6)
360367.
H36I +.J. (eifer!. +.#. #u/as. 0. Aldin,er. Ber. Bunsen,es. $%ys. C%em.
8 (188K) 13081313.
*H37I J. Bill. J. (ei!1. 9. :%urn. J. <urr. J. Canel. B.P. Janos. A.
Jalowiec/i. <. (au!!er. (. (c%empp. +.$. #ampar!er. J. 2ayer. 0.
Aldin,er. $%ys. (!a!. (ol. (a) 166 (188K) 268286.