模压高碳酚醛树脂基烧蚀复合材料制备与成型
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摘要
采用常规性能分析、傅里叶变换红外光谱分析、差示扫描量热分析、热重分析、凝胶渗透色谱分析等对模压高碳酚醛树脂进行表征,通过模压成型分别制备了碳纤维和高硅氧纤维增强模压高碳酚醛树脂复合材料,测试了不同成型压力下两种复合材料的力学性能和耐烧蚀性能,最后通过超声无损检测方法对复合材料密实度进行表征。结果表明,模压高碳酚醛树脂苯环上以邻位取代为主,其游离酚和游离醛含量较低,180℃的凝胶时间低于50 s,适用于较高温度下的快速模压成型工艺;该树脂分子量小,对纤维的浸润性好,适宜的固化温度为(190±5)℃,900℃的残炭率可达67.13%。随成型压力增加,碳纤维和高硅氧纤维增强复合材料的拉伸和弯曲性能均逐渐提高,但当成型压力大于45 MPa后,增加趋势变缓;当成型压力为45 MPa时,两种复合材料具有最好的耐烧蚀性能,其中碳纤维增强复合材料的线烧蚀率和质量烧蚀率分别为0.006 8 mm/s和0.055 9 g/s,高硅氧纤维增强复合材料的线烧蚀率和质量烧蚀率分别为0.116 4 mm/s和0.070 8 g/s。通过超声无损检测方法可以初步判断碳纤维增强复合材料的密实度。
High char-yield phenolic resin was analyzed by general performances analysis,FTIR,DSC,TG and GPC etc.. Carbon fiber and high silica fiber reinforced the resin based composites were prepared respectively through compression molding,the mechanical and ablation resistant properties of the two composites at different molding pressure were tested,finally the compactness of the two composites were analyzed by ultrasonic nondestructive testing(UNDT). The result show that,the substitution on benzene ring of the resin is mostly ortho-substituted,the free phenol content and free formaldehyde content are low,the gelation time at 180℃ is less than 50 s,which indicates that the resin can be used for the rapid compression molding at high temperature. The resin has low molecular weight and good soakage for fiber,its appropriate curing temperature is(190±5)℃ and the char-yield at 900℃can reach 67.13%. With the increase of molding pressure,the tensile and flexural properties of the two composites increase,but when the molding pressure is higher than 45 MPa,the increase trends become slow. When the molding pressure is 45 MPa,the ablation resistant properties of the two composites are best,the linear ablation rate and the mass ablation rate of the carbon fiber reinforced composite is 0.006 8 mm/s and 0.055 9 g/s respectively,those of high silica fiber reinforced composite is 0.116 4 mm/s and 0.070 8 g/s respectively. The compactness of the carbon fiber reinforced composite can be determined through UNDT preliminarily.
High char-yield phenolic resin was analyzed by general performances analysis,FTIR,DSC,TG and GPC etc.. Carbon fiber and high silica fiber reinforced the resin based composites were prepared respectively through compression molding,the mechanical and ablation resistant properties of the two composites at different molding pressure were tested,finally the compactness of the two composites were analyzed by ultrasonic nondestructive testing(UNDT). The result show that,the substitution on benzene ring of the resin is mostly ortho-substituted,the free phenol content and free formaldehyde content are low,the gelation time at 180℃ is less than 50 s,which indicates that the resin can be used for the rapid compression molding at high temperature. The resin has low molecular weight and good soakage for fiber,its appropriate curing temperature is(190±5)℃ and the char-yield at 900℃can reach 67.13%. With the increase of molding pressure,the tensile and flexural properties of the two composites increase,but when the molding pressure is higher than 45 MPa,the increase trends become slow. When the molding pressure is 45 MPa,the ablation resistant properties of the two composites are best,the linear ablation rate and the mass ablation rate of the carbon fiber reinforced composite is 0.006 8 mm/s and 0.055 9 g/s respectively,those of high silica fiber reinforced composite is 0.116 4 mm/s and 0.070 8 g/s respectively. The compactness of the carbon fiber reinforced composite can be determined through UNDT preliminarily.
引文
[1]周传文,彭影,陶飞,等.甲阶酚醛树脂的合成、表征及应用研究[J].铸造,2017,66(11):1 191–1 195.Zhou Chuanwen,Peng Ying,Tao Fei,et al.Synthesis,characterization and application of the initial phenolic resin[J].Foundry,2017,66(11):1 191–1 195.
[2]Zhong Y H,Jing X L,Wang S J,et al.Behavior investigation of phenolic hydroxyl groups during the pyrolysis of cured phenolic resin via molecular dynamics simulation[J].Polymer Degradation and Stability,2016,125:191–195.
[3]Tahen-Behrooz F,Maher M,Shokrieh M.Mechanical properties modification of a thin film phenolic resin filled with nano silica particles[J].Computational Materials Science,2015,96:91–97.
[4]Hirano K,Asami M.Phenolic resins–100 years of progress and their future[J].Reactive and Functional Polymers,2013,73(2):120–125.
[5]Asaro L,Manfredi L B,Pellice S,et al.Innovative ablative fire resistant composites based on phenolic resins modified with mesoporous silica particles[J].Polymer Degradation and Stability,2017,144:78–83.
[6]曾艳明,王海云,王敏,等.复合材料发动机衬管热压罐成型工艺研究[J].新技术新工艺,2017(1):82–84.Zeng Yanming,Wang Haiyun,Wang Min,et al.Study of the autoclave molding technology for composite engine liner[J].New Technology&New Process,2017(1):82–84.
[7]高延杰,李锦文,张清辉,等.尿素功能化石墨烯及其对酚醛树脂性能的影响[J].工程塑料应用,2015,42(12):30–34.Gao Yanjie,Li Jinwen,Zhang Qinghui,et al.Preparation of functionalized graphene with urea and its effects on the phenolic resin[J].Engineering Plastics Application,2015,42(12):30–34.
[8]林松竹,崔巍,贾若琨,等.高残炭硼酚醛树脂的制备[J].应用化学,2017,34(6):631–635.Lin Songzhu,Cui Wei,Jia Ruokun,et al.Prepration of high residual carbon boron phenolic resin[J].Chinese Journal of Applied Chemistry,2017,34(6):631–635.
[9]洪慎章.镁酚醛树脂在电子电器中的应用[J].橡塑技术与装备,2016,42(16):64–66.Hong Shenzhang.Application of magnesium boron phenolic resin in electronic appliance[J].China Rubber/Plastics Technology and Equipment,2016,42(16):64–66.
[10]刘国霞,王彩红,党艳秋,等.高温岩棉用水溶性钼酚醛树脂胶的研制[J].应用化工,2015,44(11):2 055–2 057.Liu Guoxia,Wang Caihong,Dang Yanqiu,et al.Preparation of high temperature rock wool with water-soluble molybdenum phenolic resin[J].Applied Chemical Industry,2015,44(11):2 055–2 057.
[11]吴轲,王汝敏,曹金芳.低压钡酚醛树脂改性苯并噁嗪树脂的研究[J].中国胶粘剂,2015,24(10):23–26.Wu Ke,Wang Rumin,Cao Jinfang.Study on the modification of benzoxazine resin by low pressure barium phenolic resin[J].China Adhesives,2015,24(10):23–26.
[12]陈鸯飞.高成炭率酚醛树脂的制备及其在C/C复合材料中的应用[D].长沙:湖南大学,2013.Chen Yangfei.Resarch on preparation of high char yield PF resin and its applications in C/C composite material[D].Changsha:Hunan University,2013.
[2]Zhong Y H,Jing X L,Wang S J,et al.Behavior investigation of phenolic hydroxyl groups during the pyrolysis of cured phenolic resin via molecular dynamics simulation[J].Polymer Degradation and Stability,2016,125:191–195.
[3]Tahen-Behrooz F,Maher M,Shokrieh M.Mechanical properties modification of a thin film phenolic resin filled with nano silica particles[J].Computational Materials Science,2015,96:91–97.
[4]Hirano K,Asami M.Phenolic resins–100 years of progress and their future[J].Reactive and Functional Polymers,2013,73(2):120–125.
[5]Asaro L,Manfredi L B,Pellice S,et al.Innovative ablative fire resistant composites based on phenolic resins modified with mesoporous silica particles[J].Polymer Degradation and Stability,2017,144:78–83.
[6]曾艳明,王海云,王敏,等.复合材料发动机衬管热压罐成型工艺研究[J].新技术新工艺,2017(1):82–84.Zeng Yanming,Wang Haiyun,Wang Min,et al.Study of the autoclave molding technology for composite engine liner[J].New Technology&New Process,2017(1):82–84.
[7]高延杰,李锦文,张清辉,等.尿素功能化石墨烯及其对酚醛树脂性能的影响[J].工程塑料应用,2015,42(12):30–34.Gao Yanjie,Li Jinwen,Zhang Qinghui,et al.Preparation of functionalized graphene with urea and its effects on the phenolic resin[J].Engineering Plastics Application,2015,42(12):30–34.
[8]林松竹,崔巍,贾若琨,等.高残炭硼酚醛树脂的制备[J].应用化学,2017,34(6):631–635.Lin Songzhu,Cui Wei,Jia Ruokun,et al.Prepration of high residual carbon boron phenolic resin[J].Chinese Journal of Applied Chemistry,2017,34(6):631–635.
[9]洪慎章.镁酚醛树脂在电子电器中的应用[J].橡塑技术与装备,2016,42(16):64–66.Hong Shenzhang.Application of magnesium boron phenolic resin in electronic appliance[J].China Rubber/Plastics Technology and Equipment,2016,42(16):64–66.
[10]刘国霞,王彩红,党艳秋,等.高温岩棉用水溶性钼酚醛树脂胶的研制[J].应用化工,2015,44(11):2 055–2 057.Liu Guoxia,Wang Caihong,Dang Yanqiu,et al.Preparation of high temperature rock wool with water-soluble molybdenum phenolic resin[J].Applied Chemical Industry,2015,44(11):2 055–2 057.
[11]吴轲,王汝敏,曹金芳.低压钡酚醛树脂改性苯并噁嗪树脂的研究[J].中国胶粘剂,2015,24(10):23–26.Wu Ke,Wang Rumin,Cao Jinfang.Study on the modification of benzoxazine resin by low pressure barium phenolic resin[J].China Adhesives,2015,24(10):23–26.
[12]陈鸯飞.高成炭率酚醛树脂的制备及其在C/C复合材料中的应用[D].长沙:湖南大学,2013.Chen Yangfei.Resarch on preparation of high char yield PF resin and its applications in C/C composite material[D].Changsha:Hunan University,2013.