酚醛气凝胶/碳纤维复合材料的结构调控及性能研究

doi:10.11949/j.issn.0438-1157.20180650

摘要/Abstract

摘要：

以酚醛树脂为前体、碳纤维针刺预制体为增强体，采用溶胶-凝胶、常压干燥方法制备得到纳米孔酚醛气凝胶/碳纤维复合材料。在不改变材料密度的条件下，通过调节固化剂的用量来调控酚醛气凝胶的纳米颗粒尺寸及孔隙结构，改变气凝胶颗粒在碳纤维针刺预制体中的填充状态，制备出不同微观结构的复合材料。研究表明：随着固化剂用量的减少，气凝胶的颗粒粒径逐渐变小，平均孔径在230 nm~5μm范围内可调；与碳纤维复合后，随着气凝胶颗粒的减小，复合材料的力学性能逐渐提升、热导率逐渐降低、烧蚀性能明显提高。优化后的PAC复合材料具有极低的密度（0.27 g·cm^-3）、高弯曲强度（8.9 MPa）、较低的热导率（0.065 W·m^-1·K^-1）；在2000℃、30 s的中等热流烧蚀条件下，质量烧蚀率为0.0081 g·s^-1、线烧蚀率为0.0204 mm·s^-1。通过调控材料的纳米结构，能够有效地提升材料的力学、隔热以及烧蚀性能，满足高性能热防护应用需求。

关键词: 复合材料, 纳米结构, 粒子, 热防护, 酚醛气凝胶

Abstract:

Phenolic aerogel/carbon fiber composites with different microstructures have been prepared by sol-gel polymerization of phenolic resin and curing agent. The particle size and pore size of phenolic aerogel in the composites were controlled by changing the amount of curing agent. It was found that the particle size of the aerogels could be decreased from 368 nm to 54 nm with the decrease of the curing agent amount, corresponding to the decrease of average pore size from 5 μm to 230 nm. Furthermore, the properties of composites were strongly depended on the microstructure of aerogel, in which the mechanical strength and ablation property increased while the thermal conductivity decreased with nanoparticle size decreasing. The composites with the minimized particle size had a low density of 0.27 g·cm^-3, a high bending strength of 8.9 MPa and a low room-temperature thermal conductivity of 0.065 W·m^-1·K^-1. Under the oxyacetylene ablation conditions of 2000℃ for 30 s, its mass/linear ablation rate were 0.0081 g·s^-1 and 0.0204 mm·s^-1, respectively. By regulating the nanostructure of material, it can effectively improve the mechanics, heat insulation and ablation performance of the material to meet the needs of high performance thermal protection applications.

Key words: composites, nanostructure, particle, thermal protection, phenolic aerogels

中图分类号:

TB332

董金鑫, 朱召贤, 姚鸿俊, 龙东辉. 酚醛气凝胶/碳纤维复合材料的结构调控及性能研究[J]. 化工学报, 2018, 69(11): 4896-4901.

DONG Jinxin, ZHU Zhaoxian, YAO Hongjun, LONG Donghui. Structural control and properties of phenolic aerogel/carbon fiber composites[J]. CIESC Journal, 2018, 69(11): 4896-4901.

参考文献 31

[1]	PEKALA R W, MAYER S T, POCO J F, et al. Structure and performance of carbon aerogel electrodes[C]//MRS Proceedings, 1994, 349:79.
[2]	LOY D A, JAMISON G M, BAUGHER B M, et al. Alkylene-bridged polysilsesquioxane aerogels:highly porous hybrid organic-inorganic materials[J]. Journal of Non-Crystalline Solids, 1995, 186(2):44-53.
[3]	DESPETIS F, BARRAL K, KOCON L, et al. Effect of aging on mechanical properties of resorcinol-formaldehyde gels[J]. Journal of Sol-Gel Science and Technology, 2000, 19(1/2/3):829-831.
[4]	PEREZ-CABALLERO F, PEIKOLAINEN A L, KOEL M. Preparation of nanostructured carbon materials/nanostruktuurse susinikaerogeeli valmistamine[J]. Proceedings of the Estonian Academy of Sciences, 2008, 57(57-1):48-53.
[5]	ROJAS-CERVANTES M L. Some strategies to lower the production cost of carbon gels[J]. Journal of Materials Science, 2015, 50(3):1017-1040.
[6]	PEKALA R W. Organic aerogels from the polycondensation of resorcinol with formaldehyde[J]. Journal of Materials Science, 1989, 24(9):3221-3227.
[7]	PEKALA R W. Melamine-formaldehyde aerogels:US5086085[P]. 1992.
[8]	ARDUINI, GIRI, GIANNONE. "Prepidil versus propess":induzione farmacologica del travaglio di parto con dinoprostone[J]. Minerva Ginecologica, 2008, 60(2):127-133.
[9]	LU X, ARDUINI-SCHUSTER M C, KUHN J, et al. Thermal conductivity of monolithic organic aerogels[J]. Science, 1992, 255(5047):971-972.
[10]	TAN C, FUNG B M, NEWMAN J K, et al. Organic aerogels with very high impact strength[J]. Advanced Materials, 2010, 13(9):644-646.
[11]	CHEN M, LI Z, LI J, et al. The extraction of uranium using graphene aerogel loading organic solution[J]. Talanta, 2017, 166:284-291.
[12]	WEI X, QU C, LIANG Z, et al. High-performance energy storage and conversion materials derived from a single metal-organic framework/graphene aerogel composite[J]. Nano Letters, 2017, 17(5):2788-2792.
[13]	WU D, FU R. Requirements of organic gels for a successful ambient pressure drying preparation of carbon aerogels[J]. Journal of Porous Materials, 2008, 15(1):29-34.
[14]	MIRZAEIAN M, HALL P J. The control of porosity at nano scale in resorcinol formaldehyde carbon aerogels[J]. Journal of Materials Science, 2009, 44(10):2705-2713.
[15]	蒋伟阳, 张波, 周斌等. 间苯二酚-甲醛有机气凝胶的结构控制研究[J]. 材料科学与工艺, 1996, 14(2):69-75. JIANG W Y, ZHANG B, ZHOU B, et al. Study on structure controlling of RF aerogels[J].Material Science & Technology, 1996, 14(2):69-75.
[16]	李文翠, 郭树才, 王振林. 老化过程参数对新型纳米材料有机气凝胶特性影响研究[J]. 材料科学与工程学报, 2000, 18(2):25-27. LI W C, GUO S C, WANG Z L. Effect of aging process parameter on properties of organic aerogels[J]. Materials Science & Engineering, 2000, 18(2):25-27.
[17]	YOUNG K S, HO Y D, WOO L J, et al. Synthesis and characterization of resorcinol-formaldehyde organic aerogel[J]. Journal of Chemical Engineering of Japan, 2001, 34(2):216-220.
[18]	YIN R, CHENG H, HONG C, et al. Synthesis and characterization of novel phenolic resin/silicone hybrid aerogel composites with enhanced thermal, mechanical and ablative properties[J]. Composites Part A Applied Science & Manufacturing, 2017, 101:500-510.
[19]	KASCHMITTER J L, MAYER S T, PEKALA R W. Process for producing carbon foams for energy storage devices:US5789338[P]. 1998.
[20]	PEKALA R W, FARMER J C, ALVISO C T, et al. Carbon aerogels for electrochemical applications[J]. Journal of Non-Crystalline Solids, 1998, 225(1):74-80.
[21]	YAMAMOTO T, ENDO A, OHMORI T, et al. Porous properties of carbon gel microspheres as adsorbents for gas separation[J]. Carbon, 2004, 42(8/9):1671-1676.
[22]	HAJI S, ERKEY C. Removal of dibenzothiophene from model diesel by adsorption on carbon aerogels for fuel cell applications[J]. Industrial & Engineering Chemistry Research, 2003, 42(26):6933-6937.
[23]	MAHATA N, SILVA A R, PEREIRA M F, et al. Anchoring of a[Mn(salen)Cl] complex onto mesoporous carbon xerogels[J]. Journal of Colloid & Interface Science, 2007, 311(1):152-8.
[24]	JOB N, MARIE J, LAMBERT S, et al. Carbon xerogels as catalyst supports for PEM fuel cell cathode[J]. Energy Conversion & Management, 2008, 49(9):2461-24702.
[25]	TRAN H K, JOHNSON C E, HSU M T, et al. PICA forebody heatshield qualification for the stardust discovery class mission[R]. NASA, 1996.
[26]	TRAN H, JOHNSON C, HSU M T, et al. Qualification of the forebody heatshield of the stardust's sample return capsule[C]//Thermophysics Conference. 2006:125-138.
[27]	MILOS F S, CHEN Y K, GOKCEN T. Nonequilibrium ablation of phenolic impregnated carbon ablator[J]. Journal of Spacecraft Rockets, 2012, 49(5):894-904.
[28]	MILOS F S, CHEN Y K. Ablation and thermal response property model validation for phenolic impregnated carbon ablator[J]. Journal of Spacecraft & Rockets, 2009, 47(5):786-805.
[29]	OLYNICK D, CHEN Y K, TAUBER M, et al. Forebody TPS sizing with radiation and ablation for the stardust sample return capsule[C]//Thermophysics Conference. 2013.
[30]	贾献峰, 刘旭华, 乔文明, 等. 酚醛浸渍碳烧蚀体(PICA)的制备、结构及性能[J]. 宇航材料工艺, 2016, 46(1):77-80. JIA X F, LIU X H, QIAO W M, et al. Preparation and properties of phenolic of phenolic impregnated carbon ablator[J].Aerospace Materials & Technology, 2016, 46(1):77-80.
[31]	贾献峰, 王际童, 龙东辉, 等. PICA-X的制备及其炭化前后性能研究[J]. 宇航材料工艺, 2016, 46(6):46-49. JIA X F, WANG J T, LONG D H, et al. Preparation and properties of PICA-X before and after carbonization[J]. Aerospace Materials & Technology, 2016, 46(6):46-49.