Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://chem.msu.ru/rus/journals/membranes/28/html/mb2814.pdf Äàòà èçìåíåíèÿ: Mon Feb 13 17:56:32 2006 Äàòà èíäåêñèðîâàíèÿ: Mon Apr 11 05:34:48 2016 Êîäèðîâêà:

­ - - ­ .. , .. , .., .. , .. , .. , .. , .. , ,

. , , . () ( SiC/SiC), . , «» , -, - . : (), - (), (). The basic questions of chemistry and technology for preceramic polymers of polycarbosilane (PCS) class are treated. These polymers give possibility to fabricate ceramic items with nanostructure by spinning and other formation technique from melts and solutions with thermochemical processing afterwards. They are typical representatives of science-based chemical compounds. Active R&D of these polymers is a part of resolving a priority problem leading to creation of critical technologies of new advanced ceramic matrix composites (CMC) with very high temperature and oxidizing resistance and new carbographites. The first place belongs to the CMC of SiC/SiC type. The results of home development of PCS, their usage with the effective "polymer" technology to fabricate composites components for CMC are represented. The results of the syntheses and characterization of original nanometalpolycarbosilanes, which are fabricated from organometallic compounds or nano-powders of siliceous and boron carbides, are demonstrated. Key words: preceramic polymers (k), nano-metalpolycarbosilanes (k), components of ceramic composites (n).

I. (), 68

, .

. . , 2005, 4 (28)


. . , . . , . . , . . , . . , . .

: [1-4]. . , (. 1), -

. 1.
1234. ; ; ;

. 2. " (1) -
(2) (3) (4). (5 ) , (6); (7), (8); (9); (10).

(. 2) ( 10000 ) 14000 [4]. 6,0-8,0 ·1/2 ( 3.0-4.0), - 600-700 ( 300-400), - 7500 ( 450). «» , , , [5, 6]. , . , , , . , , . - . . - [7, 13]. -, , , , - . 69

. . , 2005, 4 (28)




. II. . S.Yajima 70- . [14,15]. Nippon Carbon Co., Ltd. . . Nicalon, Hi-Nicalon Hi-Nicalon S. , , . (1). , , . , . R1 R3


[-Si - (C)n -]m


(1)

R2 R4 R1 - R4 = Alk, Ar, H . ()n = (­CH2­), ­CH2­CH2­, (­CH2­ )n (n>3), ­ CH=, ­CH=CH­, ­CC­, ­ CH2 ­ C C ­ CH2 ­, , . (), .

. , . , , , - (. 3). 800 ­ 2000 ( 10000) 2,0-3,5. , . , , Si-C. Si-Si, , , , . S. Yajima , , : 1. ( ). 2100 , 420 Â 4700 . 10-40 . , -, - .

. 3. .

70

. . , 2005, 4 (28)


. . , . . , . . , . . , . . , . .

2. , , . , 6800 (1 . .) - . . 3. . . . () ­ [-Ph2Si-O3B-]n, 350 Â 4100. , [­ (H)Si(CH3)­CH2­], [­(C6H5)Si(CH3)­]n, [­(CH3)Si(CH3)­]n [­ O­(C6H5)Si(C6H5)­CH2­]n (n = 2 Â 8), . , . , , . , , , ( 40%) (3,5 9-10 1 ), . ( 600 ./). 60-62% ­ 80%. , 15-25% , 10% . , -

, . , , , [16-20]. , , . , , , . [21, 22]. - 350 Â 4250 ( ) 1,5 Â 6 . 30 Â 40 1-4 . . 390 Â 4200 . , . n = 800-1200, 2,0-2,8, Si3C1,77H3,70O0,03 ( SiC1,40H0,05O0,04, 2,75/3), 190-2100, 250-2800. , . , , .

. . , 2005, 4 (28)

71




III. . - , , . 5-10 . . , 1200-13000 ( 20 ) 1300-14000 ( 40-100 ). 1600-17000 . (), , , Zr, Ti, Mo . - , , , 1600-17000. , - - () [7, 13]. - (-) , - [23] (, ). , ( -) , [24]. - , , -, 72

. 4. -ZrKC.
Zr 20-30 (-, 200 000)

. , , , . - . , . , . 6-8%. 3,5 %. , , . , , (. 4). - : , -, , . -

. . , 2005, 4 (28)


. . , . . , . . , . . , . . , . .

. 5. -ZrIIKC (1). - () (. 5) [13, 23]. , , «» ( ) . - , . - , . 3 - 5 , ( , ) [25]. ­ [26], -- . - , , . . 60 300 2/, , . - - , "" [27] (- ). , .
1. 26 Annual Conference on Composites, Advanced Ceramics, Materials, and Structures: Hua-Tay Lin, Mrityunjay Singh Editors. Ceram. Eng. Sc. Proc. 23, Issue 3 and 4, 2002.The American Ceramic Society, Westerville, OH, USA. ­ 884 + 884 p. 27th International Coca Beach Conference on Advanced Ceramics and Composites: Waltraub M. Kriven, Hua-Tay Lin Editors. Ceram. Eng. Sc. Proc. 24, Issue 3 and 4, 2003. The American Ceramic Society, Westerville, OH, USA. ­ 653+630 p. The proceedings from the 5th International Conference on High-Temperature Ceramic Matrix CompositesHTCMC5, 6-12 Sept. 2004. CD-ROM, 104 p. 4.CERAMIC FIBERS and COATINGS, Advanced Materials for the Twenty-First Century, Nat. Mater. Adv. Board, Publ. NMAB-494, p.54, Nat. Acad. Press, Washington, D.C. 1998. A.M. Tsirlin Inorganic Silicon Carbide, Tiranno and Silicon Nitride Fibers without Substrate. Soviet Advanced Composite Technology Series (Eds. J.N. Fridlyander and I.H. Marshal), v.5, Fibre Science and Technology , Ch. 5, pp. 457-556. Chapman & Hall, London, 1995. R.R. Naslain, The design of the fibre-matrix interfacial zone in ceramic matrix composites, Composites, Part A, 29A (1998) 1145-1155. 2125579 27 . 1999: « , , ». 8.V.G. Gerlivanov, N.A. Popova, Ye.K. Florina, Yu.Ye. Pronin. Ceramic - forming Polymetalcarbosilanes with Low Oxygen Content and Oxygen Free Methods of Polycarbosilanes Curing. Composite Materials, Technology and Automatization of Product Manufacturing. Proc.of the II-d Moscow Int. On
th

2.

3.

4.

5.

6.

7.

8.

. . , 2005, 4 (28)

73



Composites Conf. (MICC-II). "Istina i Zhizn", Moscow, 1997, pp.45-60. A.M. Tsirlin, V.G. Gerlivanov, N.A. Popova, S.P. Gubin E.K. Florina, B.I. Shemaev, "Stabilization of composite ceramics structure at high temperatures via nanopolymetallocarbosilanes", Proc. of Europ. Conf. on Composite Materials, ECCM-8, 3-6 June 1998, Naples, Italy. V. 4. pp. 137-144. S. Gubin, E. Moroz, A. Boronin, V. Kriventsov, D. Zyuzin, N. Popova, E. Florina, A. Tsirlin, "Nanoparticles of Ti and Zr in organosilicon polymer ceramic precursors", Mendeleev Commun., 2, 1999, pp. 59-61. V.V. Kriventsov, D.A. Zyuzin, S.V. Bogdanov, E.M. Moroz, S.P. Gubin, A.M. Tsirlin, "EXAFS and X-ray RED study of polymetalcarbosylanes", Nuclear Instruments and Methods in Physics Research, Section A, 1999, 3,1-4. .. , .. , .. , .. , .. , .. , . , , 2004, 46, 6, . 963-972. A.M. Tsirlin, E.K. Florina, N.A. Popova, G.I. Shcherbakova, S.P. Gubin, E.M. Moroz, R. Riedel, E. Kroke. Nano-Structured Metal Containing Polymer Precursors for High Temperature Non-Oxide Ceramics and Ceramic Fibers ­ Syntheses, Pyrolyses and Properties. J. of the European Ceramic Society, V. 22, nos. 14-15 (2002) pp.2577-2585. Yajima S., Hayashi J.//Chem.lett. 1975. 3. pp. 931934. Yajima S., Strong fibres, in: Handbook of composites. Horth-Holland, Amsterdam. 1985, pp. 207-237. A.Tazi Hemida, M. Birot, J.P. Pillot, J. Dunogues, R. Pailler, R. Naslain, Synthesis and characterization of new precursors to nearly stoichiometric SiC ceramics. Part II: A homopolymer route. J. Mater. Sci, 32 (1997) 3485-3490. B. Boury, R. Corriu, M. Enders, S. Huille, D. Leclercq, L. Lutsen, J. Moreau, H. Mutin, J-M. Planeix, A. Vioux. Synthesis, Properties and Ceramisation studies of Polycarbosilanes Containing Functional Groups. R.J.-P. Corriu, P. Gerbier, C. GuÈrin, and B. Henner, Organosilicon Polymers with Bis-acetilenic Units: Conductivity and Ceramisation Studies. The Proc. of Symp., organized by the RSC Macro Group, Univ. of Kent, Canterbury, UK, July 6-8, 1994. The Royal Society of Chemistry, 1995. L.V.Interrante, I. Rushkin and Q. Shen. Linear and Hyperbranched Polycarbosilanes with Si-CH2-Si Bridging Groups: A Synthetic Platform for the Construction of Novel Functional Polymeric Materials, Appl. Organometallic Chemistry, 12, 695-705(1998). 20. A. Idesaki, M. Sugimoto, S. Tanaka, Y. Morita, M. Narisawa, K. Okamura, and M. Itoh, Fine Silicon Carbide Fiber Synthesized from a Silicon-Based Polymer Blend Using radiation Curing, in: Proceedings of the ICM International Congress on High Temperature Ceramic Matrix Composites, ed by W. Krenkel, R. Naslain, and H. Schneider, Wiley-Vch (2001), pp.35-40. 2108348 10 .1998 (. 30 . 1996): " ". ... , .. , .. . . , 1992 ., 4, . 16 - 18. .. , .. . . , . 272, 5, . 1155-1158. .. , .. , .. , .. , .. . . IV. Zr Ti- , . . . , 2001, 37, 11, . 1317 - 1326. M. Takeda, A. Saeki, J. Sakamoto, Y. Imai, and H. Ichikawa. Effect of Hydrogen Atmosphere on Pyrolysis of Cured Polycarbosilane Fibers. J.Am.Ceram. Soc., 83 [5] 1063-69 (2000). E. Kroke, Y.-L.Li, C. Konetschny, E. Lecomte, C. Fasel, R. Riedel. Silazane derived ceramics and related materials. Materials Science & Engineering, R26, Nos. 4-6 (2000).- 199 p. K.L. Luthra, Oxidation resistant fiber coatings for nonoxide ceramic composites. J. Amer.Ceram.Soc., 80(12)1997, p.3253-3257.

9.

19.

10.

20.

11.

21.

12.

22.

13.

23. 24.

14. 15. 16.

25.

26.

17.

27.

18.

74

. . , 2005, 4 (28)