高碳酚醛树脂及其复合材料的炭化性能演变
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摘要
碳纤维增强酚醛树脂基复合材料是制备C/C复合材料的前驱体,但是目前所应用的酚醛树脂残炭率较低,浸渍炭化周期过长,工艺成本过高,限制了C/C复合材料在民用领域的大规模应用。因此,研究新型的高碳酚醛树脂及其作为基体的复合材料在炭化过程中的性能演变情况,可以有效促进酚醛树脂在C/C复合材料生产中的应用。本文探究了高碳酚醛树脂及其复合材料的炭化性能,研究了高碳酚醛树脂的结构、固化、耐热性,对高碳酚醛树脂及其碳纤维增强复合材料的炭化后性能进行了研究。研究结果表明:高碳酚醛树脂具有较普通酚醛树脂更高的残炭率;当炭化温度过高时,会出现无规则的非晶态的碳颗粒,影响材料的有序性、显气孔率等。在1000℃下炭化,会得到较为优异的孔隙率,利于后续制备工艺的进行。
As one of the precursors for the preparation of C/C composites,carbon fiber reinforced phenolic resin matrix composites have been widely used in almost every aspect of modern industry nowadays. Studying the carbonization performance of a novel high-carbon phenolic resin and its composites can effectively promote the production and application C/C composites. We investigated the carbonization properties of high carbon phenolic resin and its composites under different temperatures. It shows that high carbon phenolic resin has the same structure as normal phenolic resin. At 199 ℃,the solidification of high carbon phenolic resin can reach the fastest rate. TGA test result shows that this resin has higher carbon residue rate at 1000 ℃ in N2. The carbonization properties of this resin and its carbon fiber reinforced composites were also studied. The results show that high carbon phenolic resin has a higher residual carbon ratio than the ordinary phenolic resin. Only when the temperature exceeds 1000 ℃,the carbonization process of this resin can be fully carried out. However,when the carbonization temperature is too high,the decomposed same carbon particles will deposit into larger one. Of course,these particles contains only a very small amount of graphite grains,and most of them are amorphous and irregular. Similarly,when it comes to its composites,the large particles produced at higher temperatures will influence the contents of apparent and closed porosities in composites. When the composites are carbonized under 1000 ℃,they can obtain the best apparent porosities. This is benefit for their subsequent processes.
As one of the precursors for the preparation of C/C composites,carbon fiber reinforced phenolic resin matrix composites have been widely used in almost every aspect of modern industry nowadays. Studying the carbonization performance of a novel high-carbon phenolic resin and its composites can effectively promote the production and application C/C composites. We investigated the carbonization properties of high carbon phenolic resin and its composites under different temperatures. It shows that high carbon phenolic resin has the same structure as normal phenolic resin. At 199 ℃,the solidification of high carbon phenolic resin can reach the fastest rate. TGA test result shows that this resin has higher carbon residue rate at 1000 ℃ in N2. The carbonization properties of this resin and its carbon fiber reinforced composites were also studied. The results show that high carbon phenolic resin has a higher residual carbon ratio than the ordinary phenolic resin. Only when the temperature exceeds 1000 ℃,the carbonization process of this resin can be fully carried out. However,when the carbonization temperature is too high,the decomposed same carbon particles will deposit into larger one. Of course,these particles contains only a very small amount of graphite grains,and most of them are amorphous and irregular. Similarly,when it comes to its composites,the large particles produced at higher temperatures will influence the contents of apparent and closed porosities in composites. When the composites are carbonized under 1000 ℃,they can obtain the best apparent porosities. This is benefit for their subsequent processes.
引文
[1]赵华,贺辛亥,王宽喜.酚醛树脂及其复合材料研究现状[J].科技信息,2009(21):48-49.
[2]朱永茂,刘勇,殷荣忠,等.酚醛树脂及其复合材料发展动向[J].玻璃纤维,2005(3):35-43.
[3]薛斌,张兴林.酚醛树脂的现代应用及发展趋势[J].热固性树脂,2007,22(4):47-50.
[4]张衍,王井岗,刘育建,等.新型高残碳酚醛树脂的性能研究[J].宇航材料工艺,2003,33(5):35-39.
[5]Xu P,Jing X. High carbon yield thermoset resin based on phenolic resin,hyperbranched polyborate,and paraformaldehyde[J]. Polymers for Advanced Technologies,2011,22(12):2592-2595.
[6]陈鸯飞,陈智琴,肖绍懿,等.酚醛树脂热降解过程中的结构变化[J].热固性树脂,2008,23(4):4-8.
[7]冀克俭,张银生.酚醛树脂固化过程的红外光谱分析[J].分析测试学报,1993(2):53-56.
[8] Matsumoto A,Hasegawa K,Fukuda A,et al. Study on modified phenolic resin. I. Modification with homopolymer prepared from phydroxyphenylmaleimide[J]. Journal of Applied Polymer Science,2010,43(2):365-372.
[9]李淑君,陶毓博,李坚,等.用TG-DSC-FTIR联用技术研究酚醛树脂的热解行为[J].东北林业大学学报,2007,35(6):56-58.
[10]张衍,刘育建,王井岗,等.甲醇和丙酮对酚醛树脂热解过程和成炭性能的影响[J].固体火箭技术,2008,31(1):83-86.
[11]钱崇梁,周桂芝,黄启忠. XRD测定炭素材料的石墨化度[J].中南大学学报(自然科学版),2001,32(3):285-288.
[12]Kawashima Y,Katagiri G. Evidence for nonplanar atomic arrangement in graphite obtained by Raman spectroscopy[J]. Physical Review B,2002,66(10):351-363.
[13]Tamor M A,Vassell W C. Raman"fingerprinting"of amorphous carbon films[J]. Journal of Applied Physics,1994,76(6):3823-3830.
[14]黄彪,陈学榕,江茂生,等.不同炭化条件下炭化物的结构与性能表征[J].光谱学与光谱分析,2006,26(3):455-459.
[15]Nakamizo M,Kammereck R. 61. Laser Raman studies on carbons[J]. Carbon,1973,12(3):259-267.
[16]卫建军,宋进仁,刘朗.粘结剂含量对短炭纤维增强炭基复合材料性能的影响[J].炭素技术,1997(4):25-27.
[2]朱永茂,刘勇,殷荣忠,等.酚醛树脂及其复合材料发展动向[J].玻璃纤维,2005(3):35-43.
[3]薛斌,张兴林.酚醛树脂的现代应用及发展趋势[J].热固性树脂,2007,22(4):47-50.
[4]张衍,王井岗,刘育建,等.新型高残碳酚醛树脂的性能研究[J].宇航材料工艺,2003,33(5):35-39.
[5]Xu P,Jing X. High carbon yield thermoset resin based on phenolic resin,hyperbranched polyborate,and paraformaldehyde[J]. Polymers for Advanced Technologies,2011,22(12):2592-2595.
[6]陈鸯飞,陈智琴,肖绍懿,等.酚醛树脂热降解过程中的结构变化[J].热固性树脂,2008,23(4):4-8.
[7]冀克俭,张银生.酚醛树脂固化过程的红外光谱分析[J].分析测试学报,1993(2):53-56.
[8] Matsumoto A,Hasegawa K,Fukuda A,et al. Study on modified phenolic resin. I. Modification with homopolymer prepared from phydroxyphenylmaleimide[J]. Journal of Applied Polymer Science,2010,43(2):365-372.
[9]李淑君,陶毓博,李坚,等.用TG-DSC-FTIR联用技术研究酚醛树脂的热解行为[J].东北林业大学学报,2007,35(6):56-58.
[10]张衍,刘育建,王井岗,等.甲醇和丙酮对酚醛树脂热解过程和成炭性能的影响[J].固体火箭技术,2008,31(1):83-86.
[11]钱崇梁,周桂芝,黄启忠. XRD测定炭素材料的石墨化度[J].中南大学学报(自然科学版),2001,32(3):285-288.
[12]Kawashima Y,Katagiri G. Evidence for nonplanar atomic arrangement in graphite obtained by Raman spectroscopy[J]. Physical Review B,2002,66(10):351-363.
[13]Tamor M A,Vassell W C. Raman"fingerprinting"of amorphous carbon films[J]. Journal of Applied Physics,1994,76(6):3823-3830.
[14]黄彪,陈学榕,江茂生,等.不同炭化条件下炭化物的结构与性能表征[J].光谱学与光谱分析,2006,26(3):455-459.
[15]Nakamizo M,Kammereck R. 61. Laser Raman studies on carbons[J]. Carbon,1973,12(3):259-267.
[16]卫建军,宋进仁,刘朗.粘结剂含量对短炭纤维增强炭基复合材料性能的影响[J].炭素技术,1997(4):25-27.