ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2015,Vol.31>> Issue(6)>> 1179-1185     doi: 10.3866/PKU.WHXB201504146         中文摘要
Polyimide Aerogels Crosslinked with Chemically Modified Graphene Oxide
LIANG Yi, LU Yun, YAO Wei-Shang, ZHANG Xue-Tong
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China
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Polyimide (PI) aerogels, which are generally crosslinked using expensive chemical crosslinking agents, are novel porous materials with high strength, high heat resistance, high porosity, and low density. Graphene oxide (GO) is a functional nanofiller that has aroused wide interest in recent years. The reported PI/ GO composites have mostly been in the form of fibers and films. In this study, PI/GO composite aerogels were obtained using chemically modified graphene oxide (m-GO) as the crosslinking agent, instead of traditional ones such as 1,3,5-triaminophenoxybenzene (TAB), by reaction with 4,4'-oxydianiline (ODA) and 3,3',4,4'- biphenyltetracarboxylic dianhydride (BPDA). The chemical modification of GO was achieved by reacting GO with excess ODA using a hydrothermal method. The microstructures of the PI/m-GO aerogels were investigated using scanning electron microscopy (SEM). Nitrogen sorption tests, thermogravimetric analysis, and a hot-wire method were used to investigate the effects of m-GO on the pore properties, thermal stabilities, and thermal conductivities, respectively, of the resulting aerogels. The results show that the PI/m-GO aerogels are highly porous, thermally stable, and heat insulating. Compression tests showed that the PI aerogel prepared using 0.6% (mass fraction, w) m-GO instead of 1.8% (w) TAB as the crosslinking agent had a higher specific Young's modulus [Young's modulus/density (ρ)] and specific yield strength (yield strength/ρ), and less shrinkage.

Keywords: Polyimide aerogel   Graphene oxide   Crosslinking   Mechanical property   Shrinkage ratio  
Received: 2014-12-30 Accepted: 2015-04-13 Publication Date (Web): 2015-04-14
Corresponding Authors: LU Yun, ZHANG Xue-Tong Email:;

Fund: The project was supported by the National Natural Science Foundation of China (21373024) and Innovation Program of the Beijing Institute of Technology, China.

Cite this article: LIANG Yi, LU Yun, YAO Wei-Shang, ZHANG Xue-Tong. Polyimide Aerogels Crosslinked with Chemically Modified Graphene Oxide[J]. Acta Phys. -Chim. Sin., 2015,31 (6): 1179-1185.    doi: 10.3866/PKU.WHXB201504146

(1) Kistler, S. S. Nature 1931, 127, 741.
(2) Tamon, H.; Ishizaka, H.; Mikami, M.; Okazaki, M. Carbon 1997, 35 (6), 791. doi: 10.1016/S0008-6223(97)00024-9
(3) Wang, Z.; Dai, Z.; Wu, J.; Zhao, N.; Xu, J. Adv. Mater. 2013, 25 (32), 4494. doi: 10.1002/adma.v25.32
(4) Xu, Z. J.; Ji, T.; Zhao, L.; Wang, W. Y.; Yang, C. Y.; Gan, L. H. Acta Phys. -Chim. Sin. 2012, 28 (2), 361. [徐子颉, 吉涛, 赵蕾, 王玮衍, 杨春艳, 甘礼华. 物理化学学报, 2012, 28 (2), 361.] doi: 10.3866/PKU.WHXB201112063
(5) Guo, X. Z.; Yan, L. Q.; Yang, H.; Li, J.; Li, C. Y.; Cai, X. B. Acta Phys. -Chim. Sin. 2011, 27 (10), 2478. [郭兴忠, 颜立清, 杨辉, 李建, 李超宇, 蔡晓波. 物理化学学报, 2011, 27 (10), 2478.] doi: 10.3866/PKU.WHXB20110925
(6) Xu, W.W.; Du, A.; Tang, J.; Chen, K.; Zou, L. P.; Zhang, Z. H.; Shen, J.; Zhou, B. Acta Phys. -Chim. Sin. 2012, 28 (12), 2958. [许维维, 杜艾, 唐俊, 陈珂, 邹丽萍, 张志华, 沈军, 周斌. 物理化学学报, 2012, 28 (12), 2958.] doi: 10.3866/PKU.WHXB201209282
(7) Rhine, W.; Wang, J.; Begag, R. Production of Polyimide Aerogel for Carbon Aerogel, Involves Contacting Diamine and Aromatic Dianhydride Monomers in Solvent, Contacting Resulting Poly(amic acid) with Dehydrating Agent, and Drying Resulting Polyimide Gel. U. S. Patent 2004/0132845 A1, 2004-07-08.
(8) Guo, H.; Meador, M. A. B.; McCorkle, L.; Quade, D. J.; Guo, J.; Hamilton, B.; Cakmak, M.; Sprowl, G. ACS Appl. Mater. Interfaces 2011, 3 (2), 546. doi: 10.1021/am101123h
(9) Guo, H.; Meador, M. A. B.; McCorkle, L.; Quade, D. J.; Guo, J.; Hamilton, B.; Cakmak, M. ACS Appl. Mater. Interfaces 2012, 4
(10), 5422. doi: 10.1021/am301347a
(10) Meador, M. A. B.; Malow, E. J.; Silva, R.; Wright, S.; Quade, D.; Vivod, S. L.; Guo, H.; Guo, J.; Cakmak, M. ACS Appl. Mater. Interfaces 2012, 4 (2), 536. doi: 10.1021/am2014635
(11) Meador, M. A. B.; Wright, S.; Sandberq, A.; Nquyen, B. N.; Vankeuls, F.W.; Mueller, C. H.; Rodríguez-Solís, R.; Miranda, F. A. ACS Appl. Mater. Interfaces 2012, 4 (11), 6346. doi: 10.1021/am301985s
(12) Novoselov, K. S.; Jiang, D.; Schedin, F.; Booth, T. J.; Khotkevich, V. V.; Morozov, S. V.; Geim, A. K. Proceedings of the National Academy of Sciences 2005, 102 (30), 10451. doi: 10.1073/pnas.0502848102
(13) Mkhoyan, K. A.; Contryman, A.W.; Silcox, J.; Stewart, D. A.; Eda, G.; Mattevi, C.; Miller, S.; Chhowalla, M. Nano Lett. 2009, 9 (3), 1058. doi: 10.1021/nl8034256
(14) Shi, H.; Li, Y.; Guo, T. J. Appl. Polym. Sci. 2013, 128 (5), 3163. doi: 10.1002/app.v128.5
(15) Dong, J.; Yin, C.; Zhao, X.; Li, Y.; Zhang, Q. Polymer 2013, 54 (23), 6415. doi: 10.1016/j.polymer.2013.09.035
(16) Huang, T.; Xin, Y. S.; Li, T. S.; Nutt, S.; Su, C.; Chen, H. M.; Liu, P.; Lai, Z. L. ACS Appl. Mater. Interfaces 2013, 5 (11), 4878. doi: 10.1021/am400635x
(17) Park, O. K.; Hwang, J. Y.; Goh, M.; Lee, J. H.; Ku, B. C.; You, N. H. Macromolecules 2013, 46 (9), 3505. doi: 10.1021/ma400185j
(18) Liao, W. H.; Yang, S. Y.; Wang, J. Y.; Tien, H.W.; Hsiao, S. T.; Wang, Y. S.; Li, S. M.; Ma, C. C. M.; Wu, Y. F. ACS Appl. Mater. Interfaces 2013, 5 (3), 869. doi: 10.1021/am302494c
(19) Yoonessi, M.; Shi, Y.; Scheiman, D. A.; Lebron-Colon, M.; Tigelaar, D. M.; Weiss, R. A.; Meador, M. A. ACS Nano 2012, 6 (9), 7644.
(20) Zhang, X.; Sui, Z.; Xu, B.; Yue, S.; Luo, Y.; Zhan, W.; Liu, B. J. Mater. Chem. 2011, 21 (18), 6494. doi: 10.1039/c1jm10239g
(21) Ghani, M. A. A.; Abdallah, D.; Kazmaier, P. M.; Keoshkerian, B.; Buncel, E. Can. J. Chem. 2004, 82 (9), 1403. doi: 10.1139/v04-106
(22) Wang, G. Q. Water Resources Protection 2007, 23 (4), 85. [王国贤. 水资源保护, 2007, 23 (4), 85.]
(23) Chen, H.; Yin, J. 1, 3, 5-Tri (4-amino phenoxy) Benzene and Preparation Method Thereof. CN Patent 1405145 A, 2003-03-26. [陈焕, 印杰. 1, 3, 5-三(4-氨基苯氧基)苯及其制备方法: 中国, CN 1405145 A [P]. 2003-03-26.]
(24) Chidambareswarapattar, C.; Larimore, Z.; Sotiriou-Leventis, C.; Mang, J. T.; Leventis, N. J. Mater. Chem. 2010, 20 (43), 9666. doi: 10.1039/c0jm01844a
(25) Wu, W.; Wang, K.; Zhan, M, S. Ind. Eng. Chem. Res. 2012, 51 (39), 12821. doi: 10.1021/ie301622s
(26) Leventis, N.; Sotiriou-Leventis, C.; Mohite, D. P.; Larimore, Z. J.; Mang, J. T.; Churu, G.; Lu, H. Chem. Mate. 2011, 23 (8), 2250. doi: 10.1021/cm200323e
(27) Yang, S.; Feng, X.; Müllen, K. Adv. Mater. 2011, 23 (31), 3575. doi: 10.1002/adma.201101599

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2. JIAO Jin-Zhen, LI Shi-Hui, HUANG Bi-Chun.Preparation of Manganese Oxides Supported on Graphene Catalysts and Their Activity in Low-Temperature NH3-SCR[J]. Acta Phys. -Chim. Sin., 2015,31(7): 1383-1390
3. XU Jing, YANG De-Zhi, LIAO Xiao-Zhen, HE Yu-Shi, MA Zi-Feng.Electrochemical Performances of Reduced Graphene Oxide/Titanium Dioxide Composites for Sodium-Ion Batteries[J]. Acta Phys. -Chim. Sin., 2015,31(5): 913-919
4. LI Wen-You, HE Yun-Qiu, LI Yi-Ming.Photoelectric Properties of Graphene Oxide Film Prepared with the Electrochemical Method Using Varying Levels of Reduction[J]. Acta Phys. -Chim. Sin., 2015,31(3): 457-466
5. YANG Jun-Li, WU Cong-Ling, LI Yuan-Hao, LI Wan-Li, MIAO Yan-Qin, GUO Kun-Peng, LIU Hui-Hui, WANG Hua, WU Yong-An.Effect of Graphene Oxide Doped PEDOT:PSS as a Hole Injection Layer on the Luminescence Performance of Organic Light-Emitting Diodes[J]. Acta Phys. -Chim. Sin., 2015,31(2): 377-383
6. LU Jian-Jian, YING Zong-Rong, LIU Xin-Dong, ZHAO Shuang-Sheng.Preparation of Cross-Linked Porous Carbon Nanofiber Networks by Electrospinning Method and Their Electrochemical Capacitive Behaviors[J]. Acta Phys. -Chim. Sin., 2015,31(11): 2099-2108
7. MA Hui-Ling, ZHANG Long, ZHANG You-Wei, LIU Di, SUN Chao, ZENG Xin-Miao, ZHAI Mao-Lin.γ-Ray Induced Reduction of Graphene Oxide in Aqueous Solution[J]. Acta Phys. -Chim. Sin., 2015,31(10): 2016-2022
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9. WANG Jian-De, PENG Tong-Jiang, XIAN Hai-Yang, SUN Hong-Juan.Preparation and Supercapacitive Performance of Three-Dimensional Reduced Graphene Oxide/Polyaniline Composite[J]. Acta Phys. -Chim. Sin., 2015,31(1): 90-98
10. WANG Li, MA Jun-Hong.Synthesis and Electrocatalytic Properties of Pt Nanoparticles on Nitrogen-Doped Reduced Graphene Oxide for Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1267-1273
11. YANG Yu-Wen, FENG Gang, LU Zhang-Hui, HU Na, ZHANG Fei, CHEN Xiang-Shu.In situ Synthesis of Reduced Graphene Oxide Supported Co Nanoparticles as Efficient Catalysts for Hydrogen Generation from NH3BH3[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1180-1186
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13. NAN Guang-Hua, WANG Jian-Ping, WANG Yan, WANG He, LI Wei, ZHANG Xing-Xiang.Preparation and Properties of Nanoencapsulated Phase Change Materials Containing Polyaniline[J]. Acta Phys. -Chim. Sin., 2014,30(2): 338-344
14. SUN Yan-Bo, YANG Bin, AN Zhe, YU Chun-Lei, XUE Yao-Hong, LIU Hong.Multiscale Simulation Strategy for Preparing Polyurethane[J]. Acta Phys. -Chim. Sin., 2014,30(11): 2035-2042
15. LIU De-Zhi, HOU Xi-Xin, ZHU Xiu-Ling, WANG Rui, JING Jian, CUI Yue.Preparation and Physicochemical Property of Self-Crosslinked Poly(phthalazinone ether ketone) Anion-Exchange Membranes[J]. Acta Phys. -Chim. Sin., 2013,29(12): 2573-2578
16. LI Le, HE Yun-Qiu, CHU Xiao-Fei, LI Yi-Ming, SUN Fang-Fang, HUANG He-Zhou.Hydrothermal Synthesis of Partially Reduced Graphene Oxide-K2Mn4O8 Nanocomposites as Supercapacitors[J]. Acta Phys. -Chim. Sin., 2013,29(08): 1681-1690
17. SHI Qin, MEN Chun-Yan, LI Juan.Preparation and Electrochemical Capacitance Properties of Graphene Oxide/Polypyrrole Intercalation Composite[J]. Acta Phys. -Chim. Sin., 2013,29(08): 1691-1697
18. LONG Mei, CONG Ye, LI Xuan-Ke, CUI Zheng-Wei, DONG Zhi-Jun, YUAN Guan-Ming.Hydrothermal Synthesis and Photocatalytic Activity of Partially Reduced Graphene Oxide/TiO2 Composite[J]. Acta Phys. -Chim. Sin., 2013,29(06): 1344-1350
19. XU Jing, ZHU Yong-Fa.Elimination of Bisphenol A from Water via Graphene Oxide Adsorption[J]. Acta Phys. -Chim. Sin., 2013,29(04): 829-836
20. XU Gui-Yin, DING Bing, NIE Ping, LUO Hong-Jun, ZHANG Xiao-Gang.Preparation and Electrochemical Performance of Carbon Nanotubes/ Graphene Oxide/Sulfur Complex Cathode Material[J]. Acta Phys. -Chim. Sin., 2013,29(03): 546-552
21. LIU Na, YI Cheng-Lin, SUN Jian-Hua, WANG Juan-Qin, LIU Xiao-Ya.Structure and Emulsification Performance of Amphiphilic Copolymer Self-Assembled Micelles[J]. Acta Phys. -Chim. Sin., 2013,29(02): 327-334
22. ZUO Xiang, CAI Feng, LIU Xiao-Min, YANG Hui, SHEN Xiao-Dong.Synthesis and Characterization of a Novel Physically Cross-Linked Gel Polymer Electrolyte[J]. Acta Phys. -Chim. Sin., 2013,29(01): 64-72
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25. ZHANG Xiao, YANG Rong, WANG Chen, HENG Cheng-Lin.Cell Biocompatibility of Functionalized Graphene Oxide[J]. Acta Phys. -Chim. Sin., 2012,28(06): 1520-1524
26. LIU Ling-Ling, DING Lei, XU Li, QIAO Jin-Li, SHENG Jia-Wei.Synthesis and Properties of Chemically Cross-Linked Poly(vinyl alcohol) Modified Quaterized Hydroxyethylcellulose Ethoxylate as Novel Alkaline Anion-Exchange Membrane[J]. Acta Phys. -Chim. Sin., 2011,27(11): 2665-2670
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30. WANG Shi-Wei, GAO Bao-Jiao, GAO Xue-Chao, WANG Ling.Phase Transfer Catalytic Activity of Immobilized Dibenzo-18-Crown-6 for Butyl Benzoate Synthesis[J]. Acta Phys. -Chim. Sin., 2010,26(04): 927-932
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32. ZHANG Jian, GAO Bao-Jiao, LU Jin-Hua.Chelation Adsorption Behavior of a Salicylic Acid-Type Chelate Resin for Fe(III) Ions[J]. Acta Phys. -Chim. Sin., 2009,25(03): 532-538
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