王兰英等:以甲苯为前驱体化学液气相沉积法制备碳/碳复合材料 Bo.dor cH-50a (7) CH3 or cha (9) 首先侧链甲基与苯环之间的C_C的σ键均裂产生苯基自由基和甲基自由基[式(1)],其次苯基自 由基或甲基自由基夺取甲苯环上的氢和甲苯侧链甲基上的∝H生成苯或甲烷,并产生甲苯基自由基和 苄基自由基[式(2),然后自由基之间或自由基和生成的中间产物之间发生反应得到各种产物 [式(3)式(8)],随着裂解反应的进行,生成的产物的分压逐渐增大,当生成的产物的分压增大到超 过沉积温度下的该物质的饱和蒸汽压时,这些产物或通过直接凝缩沉积或通过物理吸附或化学吸附在 基底表面的活性点处开始反应,并进一步缩聚、脱氢形成热解碳 参考文献 [I] Fitzer E. Carbon]1987,25(2):163_190 [2]Han H. M, LiH J, Lik Z et al. Carbon[J], 2004, 42(14): 3033 3036 [3] LiH J, Jiang K Y, Lik Z. Materials L etters[J ], 2003, 57(16_ 17): 2366 2370 [4] XING XIn-Bo(熊信柏),L1 He-Jun(李贺军), HUANG JEn-Feng(黄剑锋)eal.Cham. Chinese u niersities(高等学校化学 学报)U],2004,25(7):13631367 [5 Houdayer M., Spitz J., Tran D. V, US Patent 4 472 454(P], 1984 [6 Bruneton E, Nancy B, Oberlin A. Carbon[J, 1997, 35(10 11):1593 1611 . M ater Res J].2002,17(8):19041913 [8 SunW. C, LiH. J, Han H. M. et al. Mater Sci Eng [J], 2004, A 369(1 2): 245 249 [9] ZHANG Shou-Yang(张守阳)PhD. Thesis(D], northwestern Po lytechn ical niversity(西北工业大学博士论文),1999 [10] DobasvaL, Stary V. Carbon[J], 1999,37(2):421_425 [11] Deutsch S, Kreger K A. I Phy Chem. [], 1962, 66(9):1569 1573 [12] Hu Zijun, Huttinger K 1. Carbon[J], 2001, 39(9):10231032 3] Ooya Sugiru, Sanada Yuzu T rarsated by Zhang M nga(张名大), YANG Jun-Yng(杨俊英) Introducton to carbon paton Engneering(炭化工学基础)pMl, L anzhou: Gansu Culture Press,1985 Fabr ica tion of Carbon /Carbon Com posites by Chem ical L iquid-vapor ized Deposition with Toluene as Precursors WANGLan-Yng, L IHe-Jun ,LU J in-Hua, BA IRurCheng, GUO L gun, ZHANG XuL ian (CarbonCarbon Can posites M aterial Eng ineering and Technology Research Center, N orth estern Poly technicalUniversity, X i an 710072, China) Abstract Carbon-carbon com po w ith a density of 1. 63 g/am were prepared by chem ical liqu id vapor ied deposition w ith to luene as the precursors and stratum carbon-cb th as the preform at 950C in 9 hours Itsm crostructure, X-ray diffracton and m echan ical p roperties were m easured The results ind icate that the hom ogeneousm aterials can be prepared by chem ical liquid vaporized deposit in using to luene as the precursors The ingredient of the recovered to luene was also analyzed w ith GCMs The possible m echa nim of in it ial py ro ly sis and polym eric p rocess of to luene w as discussed Keywords Carbon-carbon composites Chen ical liqud-vaporized deposit Dn; Toluene; C rack ing m echa nism (Ed: D. D 2 01994-2010 China cademic Journal Electromic Publishing House. all rights reserved. hp: /nww cnki. net© 1994-2010 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net CH3õ + õ or ·CH 3 CH2õ + or CH 4 (7) CH2õ + õ or ·CH 3 CH2õ õ + or CH 4 (8) (9) 首先侧链甲基与苯环之间的C_ C 的 Ρ键均裂产生苯基自由基和甲基自由基[式(1) ], 其次苯基自 由基或甲基自由基夺取甲苯环上的氢和甲苯侧链甲基上的 Α2H 生成苯或甲烷, 并产生甲苯基自由基和 苄基自由基[式 (2) ], 然后自由基之间或自由基和生成的中间产物之间发生反应得到各种产物 [式(3)～ 式(8) ], 随着裂解反应的进行, 生成的产物的分压逐渐增大, 当生成的产物的分压增大到超 过沉积温度下的该物质的饱和蒸汽压时, 这些产物或通过直接凝缩沉积或通过物理吸附或化学吸附在 基底表面的活性点处开始反应, 并进一步缩聚、脱氢形成热解碳. 参 考 文 献 [ 1 ] Fitzer E. . Carbon[J ], 1987, 25 (2): 163_ 190 [ 2 ] Han H. M. , L i H. J. , L i K. Z. et al. . Carbon[J ], 2004, 42 (14): 3033_ 3036 [ 3 ] L i H. J. , Jiang K. Y. , L i K. Z. . M aterials L etters[J ], 2003, 57 (16_ 17): 2366_ 2370 [ 4 ] X ION G Xin2Bo (熊信柏) , L I He2Jun (李贺军) , HUAN G Jian2Feng (黄剑锋) et al. . Chem. J. Chinese U niversities(高等学校化学 学报) [J ], 2004, 25 (7): 1363_ 1367 [ 5 ] HoudayerM. , Sp itz J. , T ran D. V. . U S Patent 4 472 454[P ], 1984 [ 6 ] Bruneton E. , N ancy B. , Oberlin A. . Carbon[J ], 1997, 35 (10_ 11): 1593_ 1611 [ 7 ] Okuno H. , T rinquecosteM. , Derre A. et al. . J. M ater. Res. [J ], 2002, 17 (8): 1904_ 1913 [ 8 ] Sun W. C. , L i H. J. , Han H. M. et al. . M ater. Sci. Eng. [J ], 2004, A 369 (1_ 2): 245_ 249 [ 9 ] ZHAN G Shou2Yang (张守阳). Ph. D. Thesis[D ], Northw estern PolytechnicalU niversity (西北工业大学博士论文) [J ], 1999 [ 10 ] Dobiasova L. , Stary V. . Carbon[J ], 1999, 37 (2): 421_ 425 [ 11 ] Deutsch S. , Krieger K. A. . J. Phy. Chem. [J ], 1962, 66 (9): 1569_ 1573 [ 12 ] Hu Zijun, Huttinger K. J. . Carbon[J ], 2001, 39 (9): 1023_ 1032 [ 13 ] Ooya Sugirou, Sanada Yuuzou. T rarslated by Zhang M ing2Da (张名大) , YAN G Jun2Ying (杨俊英). Introduction to Carbonization Engineering (炭化工学基础) [M ], L anzhou: Gansu Culture Press, 1985 Fabr ication of CarbonöCarbon Composites by Chem ical L iquid-vapor ized Deposition with Toluene as Precursors WAN G L an2Ying, L I He2Jun 3 , LU Jin2Hua, BA I Rui2Cheng, GUO L ing2Jun, ZHAN G Xiu2L ian (Carbon2Carbon Com p osites M aterial Eng ineering and T echnolog y R esearch Center, N orthw estern P oly technical U niversity , X i′an 710072, China) Abstract Carbon2carbon compositesw ith a density of 1163 göcm 3w ere p repared by chem ical liquid vapor2 ized deposition w ith toluene as the p recursors and stratum carbon2cloth as the p reform at 950 ℃ in 9 hours. Itsm icrostructure, X2ray diffraction and m echanical p ropertiesw ere m easured. The results indicate that the homogeneousm aterials can be p repared by chem ical liquid vaporized deposition using toluene as the p recursors. The ingredient of the recovered toluene w as also analyzed w ith GCöM S. The possible m echa2 nism of initial pyrolysis and polym eric p rocess of toluene w as discussed. Keywords Carbon2carbon composites; Chem ical liquid2vaporized deposition; Toluene; Crack ing m echa2 nism (Ed. : D , I) No. 6 王兰英等: 以甲苯为前驱体化学液气相沉积法制备碳ö碳复合材料 1005