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PRECURSORS FOR CARBIDE, NITRIDE AND BORIDE
SYNTHESIS
N.T.Kuznetsov
Institute of General and Inorganic Chemistry of Russian Academy of Sciences
117907 GSP-1 Moscow Leninsky prosp. 31 Russian Federation
Contents
1. Introduction
2. Classification of Ceramic Precursors
3. Ceramic Precursors for Metal Carbides of Elements
3.1. Precursors for Boron Carbide
3.2. Precursors for Silicon Carbide
3.3. Precursors for Transition Carbide
4. Ceramic Precursors for Nitrides of Elements
4.1. Precursors for Boron Nitride
4.2. Precursors for Aluminium Nitride
4.3. Precursors for Silicon Nitride
4.4. Precursors for Transition Metal Nitrides
5. Ceramic Precursors for Metal Borides
6. Conclusion
References
1. Introduction
The classical methods of preparation of non-oxide ceramic
materials based on direct reaction of elements, carbothermal reduction of
oxides and reduction of halides do not always provide required
stoichiometry, homogenity, microstructural composition, high purity,
desirable grain size and forms such as fibres, films and coating, foam
and microporous membranes, submicron powders, as well as some
multicomponent systems. Hence the development of chemical synthesis
of ceramics through preceramic routes at moderate temperature and
pressure is an essential current problem, determining progress in
advanced ceramic thechnology.
An optimal approach to the problem from the chemist's point of
view is that of ceramic precursors.
The ceramic precursors can be referred to as a chemical compounds
containing all (or almost all) the elements to be present in the final
92
ceramics and that can be reprocessed into the end ceramic product.
Practically all known advanced ceramic materials can be produced via
ceramic precursors routes. Nevertheless, chemical compounds should
satisfy a number of common and technological requirements to be
ceramic precursors. Some of them were listed above. In addition one
should mention the environment stability, solubility in common
solvents, high ceramic yield, relatively inexpensive starting materials
and exclusion of toxic substances from the process.
Progress in preceramic routes has led to the development of nonclassical methods for ceramics preparation such as gas phase reactions,
thermal decomposition, non-aqueous liquid reactions, sol-gel processing,
polymer pyrolysis, etc.
2.Ceramic precursors classification
All known chemical compounds used as ceramic precursors can
be divided into five basic groups:
ordinary inorganic compounds
coordination compounds
metal organic compounds
organometallic compounds
polymers
The selected examples are listed in Table 1.
Table 1
Groups and types of
compounds
1
Ordinary inorganic
compounds
Halides
Hydrides
Oxides
Amides
Imides
Azides
General formula
Selected examples
2
3
MXn
Mn,Hm,
Mn,0m
M(NR2)n
M(NH)n
R2MN3
93
SiCl4, TiCl4, BCl3
B10H14, NH3
Ti02, Nb2O5
T(NR2)4,Nb(NR2)5
Si(NH)2
R2A1N3, R3SuN3
1
Coordination
compounds
Amine complexes
n-Complexes
Carboranes
Tetrahydroborates
Polyhedral Boranes
Metalloboranes
Metallocarboranes
Metal organic
compounds
Metal alkoxides
Metal carboxylates
MOC with mixed
functional groups
Organometallic
compounds
Metal alkyls
Metal aryls
Metal alkenyls
Metal carbonyls
Mixed
organometallic
ligands
2
3
[MLn]X
MXnmNH3
(C5H5)2MXn
CxByHz;
M(BH4)n
M(BnHn)x
B10H14-xLx
(C5H5)xMyBnHn
-
M(OR)n
M[OC(0)R]
-
[Ni Phen3] B12H12
H3AlNH3 B2H62NH3
(C5H5)2Fe, (C5H5)2TiCl2
C2B10H12, C2B6H8
A1(BH4)3, Ti(BH4)3,
Zr(BH4)4
CaB6H6, (RxNH4-x)2B12H12
R4N[(C5H5)3Ni3B6H6]
[(C5H5)2Ni2CB7H8]
Ti(OC3H7)4
A1[OC(0)CH3]3
(C2Hs)2AlN(CH3)2
MRn
MRn
M(CO)n
-
A1(CH3)3, Pb(C2H5)4
Ca(C6H5)2
A1(CHCH2)3
Ni(CO)4, Co2 (C0)8
(C2H5)3Ti(CH3)
Polymers
Polysilanes
Polycarbosilanes
-[Si(RR')]-n
-[(RR')Si-CH2] -n
94
-[Si(CH3)(C2H5)]-n
-[(H)(CH3)SiCH2]-n
1
Polysiloxanes
Polysilazanes
Borazines
and
Polyborazines
Polyamides
2
-[Si(RR')-0] -n
-[(RR')Si-NR]-n
(RBNR')3
-[B(R)N(R)]-n
=[M-NR] -n
3
-[Si(CH3)20]-n
-[(CH3)2SiN(CH3)]-n
(HBNH)3
[CH3BNH]6
=[AlN(CH3)] -n
=[Ti(NCH3)2]=
The preceramic route includes the following stages: synthesis of
monomer units, their conversion into oligomer/polymer precursors and
crosslinking into a preceramic network. The stages of ceramization and
crystallization will be considered only schematically.
3. Ceramic Precursors for Carbides
The chemistry of precursors for carbide ceramics has remained
limited to boron carbide, silicon carbide and to a certain degree to
transition metal carbides.
3.1. Boron carbide B12C3
Non-classical methods of boron carbide preparation based on
precursor route include carboranes, boron hydrides and polyhedral boron
hydride systems. Thus the polymer precursor [-CH-CH 2- ]n obtained by
the reaction
B5H8,
Catl
B5H9 + CH  CH
T
B5H8CH = CH2
0
polymer on heating
25
at 1200°C results in the amorphous boron carbide B12C3 [1].
The most preferred boron carbide precursors are carboranes - cluster
systems containing closo - frame - works of boron and carbon atoms
(Fig.l).
95
Fig.l
Closo-carboranes.
Such as carborane C2B10H12, due to its high chemical and
thermal stability, , structural similarity and B/C ratio close to boron
carbide (Fig2), molecular crystal lattice with high volatility at 100120°C and very low toxicity. Carborane C2B10H12 obtained via the
reaction
CHCH
B10H14+2CH3CN
B10H12 (CH3CN)z
C2B10H12 at 700°C
forms the polymeric precursor (C1,9B10H8,3)4 that yields boron carbide at
900-1000°C. The reasonably high temperature dependence of vapour
pressure and deposition rate (0,6 mm/h at 1050°C and 3,0 mm/h at
1260°C) makes the carborane an outstanding precursor for CVD
preparation of boron carbide films and coating [2].
96
Fig.2. Boron carbide (B4C) and related structures consist of icosahcd-ral B12 ;
building blocks with the equatorial (B I) and axial (B2) boron atoms and the
three-atom chain inserted between them. The icosahedra are linked via B2 in a
rhombohedral unit cell.
Many other monomeric and polymeric carborane derivatives can
be used for boron carbide preparation:
[NC-C6H4-C-C]2=C6H4
\°/
B10H10
-[C6H4-C-C-C6H4-CC]-n
\°/
B10H10
Similar precursors yield boron carbide on heating up to 1500°C
in an argon atmosphere [3].
Boron carbide can also be obtained via pyrolysis of lewis base
adducts of decarborane [4-6].
The polyhedral boron hydride compounds (RxNH 4-x)2BnHn
represent novel types of precursors for boron carbide and boron
carbonitride preparation [3]:
97
B12C3+/-x
(RxNH4-x)2BnHn
B12C2,12N1,6
R = CH3, C2H5, C4H9
n=10,12
x=0-4
The pyrolitic decomposition of these compounds at 400°C leads
to polymer precursors; heating them up to 1500°C yields boron carbide
or boron carbonitride, depending on C/N ratio.
The saturation of organic anion exchange polymers based an
polyacrylnitrile or cellulose with B10H102-, B12H122-, B20H182- and B20H193anions in aqueous or organic solutions followed by heat treatment and
pyrolysis of obtained compositions results in core-free boron carbide
fibres.
3.2. Silicon Carbide SiC
The organosilanes and organohalosilanes are ordinary ceramic
precursors for silicon carbide preparation [8-11]:
Selected examples are listed below:
CH3SiCl3
(CH3)2SiCl2
(CH3)3SiCl
CH3SiHCl2
(CH3)4Si
(C6H5)3SiH
(C6H5)3SiCH=CH2
(C6H5)3Si(CH3)3
1000-1700°C
SiC
H2
As a rule silicon carbide obtained in this way contain excess carbon
in most cases. Organosilicon polymers are more convenient precursors
for silicon carbide. These are polysilanes, polycarbosilanes and
98
polysiloxanes [12-16]. Their suitability as precursors is determined by
facility of synthesis in the pure form, processing conditions and silicon
carbide grade. These polymers are usually prepared from relatively
inexpensive reagents.
The polymer preparation routes are presented
below[17]:
саt
-Thermolysis: (CH3)4Si
[(CH3)2Si] -n,
T
-[(CH3)H Si CH2]-n
T
Solv.
- Dehalocoupling: (CH3)R Si Cl2
-[(CH3 R Si]-n
M,T
-[RH Si CH2 Si HRCH2]-n
T
(M=Li-K,R-alkyl)
cat
- Dehydrocoupling: RSiH3
-[RSiH]-n
T
cat
- Hydrosilylation: = = - Si R2 H
H-[Si R2 CH2 CH2]-n
T
-[SiR2CH(CH3)SiR2]-m= =
cat
- Ring Opening Polymerisation: [R2 Si CH2]2
-[R2 Si CH2]-n
T
- Redistribution: [R Si Cl2]2
R Cl2 Si - [R Cl Si]-n Si Cl2 R
T
The thermal treatment of polymers up to 1000 - 1700°C in inert or
reducing atmosphere leads to silicon carbide.
The polysiloxanes countaining oxygen always require reducing
media for the preparation of pure silicon carbide :
1500°C
-[Si(CH3)2O]-n
SiC
H2
99
3.3. Carbides of transition metals
The preparation of transition metal carbides from ceramic
precursor is essentially limited to compounds containing a direct metalcarbon bond as well as some polymer derived from metal alkoxides and
coordination compounds [18-23]:
Ar
(C5H5)2Ti(CH3)2
TiC
T
Ar
[(C5H5)(CO)2 W(CR)]2
W2C
T
Ar+H2,
[(C6H402)2Ti]n
TiC
T
[CoEn3]W04
WC+Co(23°/o)
T
(NH4)8[H2Co2W11040]
WC + Co
T
(R - alkyi. En - ethylene diamine ).
Ni(CO)4+CO
Ni3C
T
Solid carbide nanorods of TiC, NbC and Fe3C have been prepared
by reacting pure carbon nanotubes with volatile metal iodides [23].
4. Ceramic Precursors for Nitrides
The last ten years have seen a great growth of research in the
ceramic nitride precursor chemistry. At the same time this area of
research is mostly limited to the nitrides of boron, aluminum and silicon
and to a smaller extent to the preparation of nitrides of transition metals.
It should be emphasized that most precursors for nitride preparation are
air and/or moisture-sensetive compounds. Nevertheless, many
100
compounds, particularly those with polymeric structure have been
suggested as suitable precursors for nitride ceramics preparation in the
form of powders, bodies, fibres, coating, films and binders.
4.1. Boron nitride BN
The majority of precursors for boron nitride preparation are
based on borazene, substituted borazene and their polymeric forms [10].
The basic compound borazene B3N3H6 is easily available
according to the reaction [24]:
T
3NaBH4 + 3NH4Cl
B3N3H6 + 3NaCl + 9H2
Numerous substituted borazenes obtained both by direct
substitution of hydrogen atoms in borazene and by reaction between
boron halides or boron alkyls and ammonia or amines make a large part
of borazenes are presented below:
C13B3N3H3
C13B3N3R3
R3B3N3R'3
(R3N)3B3N3R'3 etc.
R, R'-alkyl, aryl
Borazene and its derivatives have structures similar to benzene
with alternating B-N bound in the ring.
The pyrolysis of borazene and its monomeric derivatives
proceeds with condensation through BN - analogues ofnaphtalenes and
biphenyl derivatives and with further crosslinking up to boron nitride
[25].
Substituted borazenes form polymers upon heating in the range
300-400°C. These are good precursors for the boron nitride in the form
of powders, green bodies, fibres, films and coating and binders [26]
A large variety ofbarazene polymers have been prepared by
cross -linking according to the following scheme:
>B-C1+H-N<
——————> >B-N<
>B-C1+H2NR<
——————> >B-NR-B<
>B - Cl + (CH3)3 Si NRR'—————— >B-NRR'
101
Polymer pyrolysis usually needs to be carried out in ammonia
atmosphere to obtain pure boron nitride.
Some examples of polymerization are presented below:
The obtained macromolecules are soluble in common organic
solvents thus providing a variety of boron nitride forms.
Functional groups in these polymers are capable of substitution
reactions [27]:
NMe2
B
HN
NH
N
B
N
H
H3B*THF
HN
B
N
N
n
B
H
B
N
H
NH
B
N
n
102
Another approach to the borazene polymers involves
ammonolysis ofaminosubstituted borazenes, such as [(CH3)2NBNH]3,
[(C2H5)2NBNH]3 for the preparation of pure inorganic aminosubstituted
borazenes with give high purity boron nitride at 1200°C with a good
yield [28-34].
Boranes can be used as starting compounds for polymer
precursors preparation according to scheme [4,5]:
T
B10H14 + H2NCH2 CH2NH2
[B10H12(H2NCH2 CH2 NH2)]n
Borane - derived polymers being deficient in nitrogen, their pyrolysis
proceeds under ammonia atmosphere to produce BN [1]:
H H
C -C
H
H H
C C
H
B5H9
+ 5NH3
HN
HB
B
N
H
N
B
H
B
N
H
+ 8H2
NH
BH
n
NH3
-[B10H12(H2NCH2 CH2NH2)]-n
BN
10000C
Thise polymer gives BN/B4C composite on pyrolysis under
argon atmosphere at 1000-15000C. Such polymers are suitable binders
and have been used to prepare fibres and monoliths [4,35].
Boron nitride can also be prepared by pyrolysis of some boron
cluster compounds [7]
103
NH3
(RX NH4-X)2 BnHn —————— BN
1000°C
R — CH3, C2H5, C4H9
n= 10, 12
x = 0 - 4.
Pyrolysis in argon results in boron carbonitrides similar to pyrolysis
of some borane coordination compounds.
4.2. Aluminum nitride A1N
Aluminium nitride can be prepared via a precursor mainly
byammonolysis of organoalanes [36,37]:
T
T
T
R3Al+NH3 —— [R3AlNH3]—— [R3AlNH2]3 ——
NH3
[RAlNH]n
A1N
R - alkyi CH3 – C10H21
Aluminium hydride can also be used [38-39]:
Scheme I
-300C, THF
AlH3 + 3NH3
20-1000C
Al(NH2)3
4300C
Al(NH)NH2
3H2
4300C
AlN1,27Hx
Scheme II
AlN1,13Hx
-800C, THF
AlH3 + NH3
-450C
AlH3NH3
1000C
HalNH
200C
H2AlNH2
1500C
H0,27AlNH0,27
H0,23AlNH0,23
The reaction of methylsilylamine with aluminium culoride also
leads to aluminium nitride [40-42]:
60°C
>200°C
AlCl3 + [(CH3)3 Si]2NH —— [Cl2AlNHSi(CH3)3]2 ————
500°C
1200°C
— [ClAlNH]n ——— Al(amorphous) ———> AlN(crystal).
104
Ar
Aluminium nitride fibres were prepared by pyrolysis of
(CH3)2AlN3 and (C2H5)2A1N3 [43]:
T
T
T
R2A1N3 ——>R2A1N ——A1NH2 ——— A1N
Polymeric aluminium compounds were also used [44]:
T
[C2H5CH =NA1(C4H9)2]2 ———— [(C2H5NA1C4H9)x (C2H5NAl)y]n
NH3
1300-1600°C
A1N
4.3. Silicon nitride Si3N4
The first step to obtain silicon nitride is the Si - N bond
formation leading to silazane. All precursors for silicon nitride
production are based on the silazane chemistry. The reaction of silicon
tetrochloride and ammonia proceeds stepwise forming silicon imide
precursors that are converted to silicon nitride at 1400°C [45-47]:
Process scheme for the production of Si3N4 powder by precipitation reactions.
Ammonolysis and aminolysis ofmonomeric or polymeric chlorosilanes
is a common synthetic route for silicon-nitrogen bond formation [48]:
>Si-Cl+H-N<———— >Si-N<+>NH HC1
105
Hexamethyldisilazane can also be used to replace the Si-Cl bond by the
Si-NH bond thus producing silicon-nitrogen precursor [49];
[(CH3)3Si]2NH + HsiCI3 ————— (CH3)3SiCI +
+ [-HSi(NH)1,5]n [HSiNH(NHSi(CH3)3-]m
The product of ammonolysis with primary amines give off amines
under ambient conditions and then undergo a condensation reaction [23]:
R
>Si(NHR)2________
R
R
N-Si-N-Si-N
-RNH2 H
|
|
H
The silicon-nitrogen bond can be produced by catalytic
dehydrocoupling [51]:
Cat
>Si-H+H-N<
—————Si-N<
-H2
Extensive efforts have been made to develop the method
silazane polymerization because direct methods ofpolysilazane synthesis
are limited and often give low yields. The pyrolysis of polysilazanes is
the most convenient way to prepare silicon nitride materials.
Polymerization
ofsilazanes
is
based
on
base-catalyzed
dehydrocyclodimerization, hydrosilylation, transition metal-catalyzed
dehydrocompling and acid-catalyzed rearangement [52,53].
Some examples:
106
The silazanes are bound to have Si-H bounds to possess
polymerization ability.
High molecular weight polysilanes can also be prepared directly
from pyridine-modified halosilanes reacting with ammonia [54]:
NH3
RHSiCl2 + 2C5H5N ——— [RHSiCl2 2C5H5N] ————>
T
———— - [RHSiNH]-n
Aminosilane (C2H5NH)4Si polymerizes by refluxing at 120180°C during three days [55]:
T
(C2H5NH)4Si ————polymer+C2H5NH2+(C2H5)2NH
The fragments of the structure are presented below:
107
The copolymers can also be prepared by the reaction of
CH2=CHSiCI3 and CH3SiHCl2 with ammonia on heating to 220°C [56]:
Rl,R2 = H, Alk(en)yl
R3 = Alk(en)yl
a > 0, b > 0, n = 2 – 12
The silicon nitride obtained from silazane and polysilazane
precursors containing organo-groups bouded to silicon include a
quantity of silicon carbide or carbon.
The more organo-groups there are on silicon the greater carbon
content is found an silicon nitride. Pure silicon nitride Si3N4 can be
prepared via pyrolysis ofpolysilazanes under ammonia atmosphere
according to the reaction:
Si – CH3 + NH3
Si – NH2 + CH4
108
Amorphous silicon nitride forms -Si3N4 above 1300°C
transforming to -Si3N4 above 1600°C
4.4. Precursors for transition metal carbides
It is known that transition metal chlorides interact with ammonia
to form in soluble, nonvolatile metal amides and on heating at high
temperature under nitrogen then convert to transition metal nitrides [29]:
T
MClx + NH3
T
M(NH2)x
MN
Transition metal amides containing organogroups can be
converted to transition metal nitrides only under ammonia atmosphere
[57-64]:
NH3
(R2N)4M —————— MN(M=Ti,V)
NH3
(R2N)4M —————— M 3N 4(M=Zr,Nf,Nb,Ta)
T
NH3
(R2N)4M —————— M3N4 (M = Zr, Nf, Nb, Ta)
T
NH3
(R2N)5Nb —————— Nb3N4
T
R = CH3, C2H5
NH3
(R2N)5Ta —————— Ta3N5
T
The high temperature ammonolysis of transition metal amides is
followed by the formation of a wide voriety of polymeric forms.
109
5. Ceramic Precursors for Metal Borides
Zittle information is available on preceramic routes for metal
borides. They include a theiwal decomposition oftetrahydroboranes,
some borane derivatives and cluster boron hydride compounds. Most
metals form tetrahydroborates that can be transformer into boride phases
on pyrolysis according to the following scheme [65-72]:
MClx + BH4- —————M(BH4)x + xClT
M(BH4)x —————— MBx + 2xH2
Temperature limits of transformation depend on the metal nature (Table 2).
Table 2
Tetrahydroborate
Boride
1
A1(BH4)3
Temperature of
transformation, °C
2
300
Cr(BH4)3
430-450
CrB2
Ni(BH4)2
320-450
NiB
Mo(BH4)3
160-170
MoB3 + Mo5B18
W(BH4)3
170-190
WB
Ti(BH4)3
400-420
TiB2
Zr(BH4)3
250
ZrB2
Hf(BH4)3
250
HfB2
110
3
A1B2
The limitation of these routes consists in air and/or moisturesensetivity of tetrahydroborates. The use of coordination compounds
allowed this problem to be solve partically:
T
[Ni(NH3)6](BH4)2—————NiB2 + (H3BNH3)n + NH3 +H2
T
[Cr(NH3)6](BH4)2 ——————> CrB2 + (H3BNH3)n + NH3a + H2
The cluster boron compounds consisting of a polyhedral closed
cage or open polyhedral fragments can be used as perspective ceramic
precursors for metal borides. The basic structures of clusters consist of
polyhedrons (Fig 3) wich can involve either only boron atoms or one or
a few carbon atoms. On the other hand the metal atoms can be
incorporated into the boron cage, forming polyhedral metalloboranes
and metallocarboranes (Table 3).
Table 3
Types of polyhedra in reactions of polyhedral expansioa
Number
of
vertices
in
the
initial
polihedron
6
Anion
Ni
[B6H6]2-
Co
Ru
Introduced metal atom
Rh
Pd
Os
Ir
Pt
Zr
[NiB6]
[Ni3B6]
[CB5H6]8
[B8H8]2[СB7H8]-
[IrCB7]
2-
9
[B9H9]
[СB8H9]-
[NiB9]
10
[B10H10]2-
[Ni2B10]
-
[СB9H10]
11
12
[Ir2B4]
[IrCB8]
[RuB10] [RhB10]
[OsB10]
[Co2CB9]
2-
[B11H11]
[NiB11]
[СB10H11]- [NiCB10]
2-
[B12H12]
[СB11H12]-
[PdCB10]
[PtCB10]
[RuB12]
[ZrCB11]
111
Finally, boron clusters can play on outer sphere role in
coordination compounds of transition metals.
Pyrolysis of abovementioned boron clusters can lead to metal
borides or metal carborides [73]:
T
M12B12H12 —————— MB6 + H2 (M+ = K+ – Cs+)
MB6H6 ———————— MB6 + H2 (M+2 = Ca+2 – Ba+2-, Eu+2, Sm+2)
530-550°C
800
[NiPhen3] B12H12 ——————— [NiB12H12] ———>NiBx + B
- phen
-H2
(phen - phenantrolyne).
Fig.3 Idealized structure and numbering order of the atoms in the closopolyhedral frameworks (number of vertices n =6- 12).
112
The advantages of these routes consist in the presence of the
required structure that provides stoichiometry in many cases.
Fig.4
CaB6 structure
Fig.4 shows that the boride sublattice in CaB6 contains the
octahydrones B6 wich form the cage of the starting precursor B6H62-.
Another preceramic route to borides is based on the reaction of
monomeric and polymeric decarbone derivatives with metal oxides or
metal ponders [74-77].
The ceramic precursors were prepared by dispersing metal or
metal oxide powders in decaborane derivative solutions. Then the
solvent was vacuum evaporated and the resulting solid dispersion was
ground into fine powder. The metal borides or metal boronitrides were
prepared by pyrolysis of obtained precursors at 1300-1500°C.
B10H14+2RCN—————B10H12(RCN)2
(R=alkyl)
T
B10H12(RCN)2 + MO2 ————— MB2
(M = Ti, Zr)
T
B10H14+2A _____ B10H12A2 ————
[B10H12A2]n
NH3
[B10H12A2]n + Ti—————TiB2/TiN (A=amine)
113
80°C
B10H14+NC(CH2)5CN —— -[B10H12NC(CH2)5CN]-n
Ar
[B10H14 + NC(CH2)5CN] + M205(M02)————— MB2
14500
(M = Ti, Zr, Hf, Nb, Ta).
The ferraboranes Fe2(CO)6B6H6, HFe3(CO)9BH4 and
HFe4(CO)12BH2 served as valatile precursors for amorphous iron boride
films having approximatelly the same Fe/B ratio as the precursors used.
Annealing the films results in the formation of principally crystaline
FeB, Fe3B, Fe3B/B respectively [78].
The composite TiB2 / TiN was prepared by pyrolysis of the
precursor involving the suspension of titanium powder in polymeric
borazine [79]:
T
[B3N3Hx]n + Ti ————>• TiB2 / TiN + H2
6. Conclusion
The chemistry of ceramic precursors is a relatively new field of
material science that grows intensively at the present time. Although
preceramic techniques can not certainly replace the classical methods of
advanced ceramics technology due to their relatively high cost.
Nevertheless ceramic precursors are indispensable where ceramics with
rigidly or other specific properties have to be manufactured.
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