|
|
- 2018
功能化石墨烯-SiO2协同增强增韧聚丙烯复合材料的制备与性能
|
Abstract:
先采用溶胶-凝胶法制备了氧化石墨烯（GO）-SiO2杂化材料，再与聚丙烯（PP）进行熔融共混制备了GO-SiO2/PP复合材料。分别采用FTIR、XRD、XPS、DSC、SEM、动态热机械分析（DMA）、拉伸及冲击等测试手段对填料及GO-SiO2/PP复合材料的结构与性能进行了表征。FTIR和XPS分析表明，GO已经成功获得功能化。力学性能测试结果证实，GO-SiO2对PP基体具有良好的强韧化协同改性作用，且优于SiO2/PP及GO/PP复合材料体系。固定GO-SiO2中GO与SiO2的质量比为1∶1，当填料GO-SiO2的质量分数为0.1wt%时，GO-SiO2/PP复合材料的拉伸强度和冲击强度分别为38.9 MPa和7.6 kJ/m2，与纯PP基体相比分别提高了29.4%和66.3%。DSC测试表明，GO-SiO2/PP复合材料中PP的熔融温度和结晶温度分别为167.4℃和111.7℃，与纯PP相比分别提高了4.7℃和5.2℃。DMA测试表明，GO-SiO2的加入使GO-SiO2/PP复合材料的储能模量增大，损耗模量峰向更高温度移动。SEM观察表明，当加入少量的GO-SiO2时，填料能均匀的分散在基体中，但GO-SiO2过多时，则容易形成团聚。 Graphene oxide-SiO2 (GO-SiO2) hybrid materials were firstly synthesized by using sol-gel method, and then GO-SiO2/polypropylene (PP) composites were prepared through melting blending. The structures and properties of fillers and GO-SiO2/PP composites were characterized and investigated by using FTIR, XRD, XPS, DSC, SEM, dynamic thermo-mechanical analysis (DMA), tensile and impact tests. The results show GO has been chemically functionalized. The mechanical property tests verify that GO-SiO2 has good synergistic effect on strengthening and toughening of PP matrix, and the mechanical properties of GO-SiO2/PP composites are superior to those of SiO2/PP and GO/PP composites. When the mass ratio of GO/SiO2 is 1:1 and the GO-SiO2 mass fraction is 0.1wt%, the tensile strength and impact strength of GO-SiO2/PP composites are 38.9 MPa and 7.6 kJ/m2, respectively, which increase by 29.4% and 66.3% compared with those of PP matrix. DSC tests show that the melting and crystallization temperature of PP in the GO-SiO2/PP composites are 167.4℃ and 111.7℃, which increase by 4.7℃ and 5.2℃, respectively, compared with those of the pure PP. DMA tests show that the incorporation of GO-SiO2 results in increasing of storage modulus and the shifts of loss modulus peaks to higher temperature. SEM observations show that when the addition of a small amount of GO-SiO2, the filler can be evenly dispersed in the matrix, but aggregation appears at higher GO-SiO2 mass fraction. 四川省教育厅科研项目（17ZB0422）；国家级大学生创新创业训练计划项目（201710623098；201510623033）；四川省高校重点实验室开放研究基金（SZjj2017-066；SZjj2015-086）；西华大学“师资支持计划”基金（02020597）
| [1] | 李振中, 李东红, 温变英. 无机纳米粒子填充改性聚合物的研究进展[J]. 塑料, 2001, 30(1):44-48. LI Z Z, LI D H, WEN B Y. Recent development of polymer filled by inorganic nano-particle[J]. Plastics, 2001, 30(1):44-48(in Chinese). |
| [2] | 陈平, 于祺, 路春. 纤维增强聚合物基复合材料的界面研究进展[J]. 纤维复合材料, 2005, 22(1):53-59. CHEN P, YU Q, LU C. Advance in the study of interface of fiber reinforced polymer matrix composites[J]. Fiber Composites, 2005, 22(1):53-59(in Chinese). |
| [3] | 张肇英, 黄玉惠, 廖兵, 等. 环氧树脂水基化化学改性的研究[J]. 广州化学, 2000, 25(2):7-11. ZHANG Z Y, HUANG Y H, LIAO B, et al. Waterborne epoxy resin by chemical modification[J]. Guangzhou Chemistry, 2000, 25(2):7-11(in Chinese). |
| [4] | 李爱元, 徐国财, 邢宏龙. 纳米粉体表面改性技术及应用[J]. 化工新型材料, 2002, 30(10):25-28. LI A Y, XU G C, XING H L. Technology and application of nano powder's surface modify[J]. New Chemical Materials, 2002, 30(10):25-28(in Chinese). |
| [5] | BOTAS C, áLVAREZ P, BLANCO P, et al. Graphene materials with different structures prepared from the same graphite by the Hummers and Brodie methods[J]. Carbon, 2013, 65:156-164. |
| [6] | LI Y, GAO W, CI L, et al. Catalytic performance of Pt nanoparticles on reduced graphene oxide for methanol electro-oxidation[J]. Carbon, 2010, 48(4):1124-1130. |
| [7] | QIU J, LAI C, WANG Y, et al. Resilient mesoporous TiO2/graphene nanocomposite for high rate performance lithium-ion batteries[J]. Chemical Engineering Journal, 2014, 256:247-254. |
| [8] | 李金焕, 王瑞海, 王堂洋, 等. 石墨烯/氰酸脂-环氧树脂复合材料的制备和性能[J]. 复合材料学报, 2014, 31(5):1154-1159. LI J H, WANG R H, WANG T Y, et al. Preparation and properties of graphene/cyanate esterresin-epoxy resin composites[J]. Acta Materiae Compositae Sinica, 2014, 31(5):1154-1159(in Chinese). |
| [9] | 周醒, 夏元梦, 蔺海兰, 等. 纳米SiO2功能化改性石墨烯/热塑性聚氨酯复合材料的制备与性能[J]. 复合材料学报, 2017, 34(4):699-707. ZHOU X, XIA Y M, LIN H L, et al. Preparation and paoperties of nano SiO2 functionally modified graphene/thermoplastic polyurethane composites[J]. Acta Materiae Compositae Sinica, 2017, 34(4):699-707(in Chinese). |
| [10] | 蔺海兰, 朱庆兰, 卞军, 等. 共混型石墨烯-nano SiO2/TPU复合材料的制备与性能[J]. 复合材料学报, 2016, 33(7):1382-1389. LIN H L, ZHU Q L, BIAN J, et al. Preparation and properties of blended graphene oside-nano SiO2/TPU composites[J]. Acta Materiae Compositae Sinica, 2016, 33(7):1382-1389(in Chinese). |
| [11] | 余宗学, 马瑜, 何毅, 等. TiO2-GO的制备及TiO2-GO/环氧树脂涂层的抗腐蚀性能[J]. 复合材料学报, 2015, 32(4):1017-1024. YU Z X, MA Y, HE Y, et al. Preparation of TiO2-GO and anti-corrosion performances of TiO2-GO/epoxy coatings[J]. Acta Materiae Compositae Sinica, 2015, 32(4):1017-1024(in Chinese). |
| [12] | MA Y, DI H, YU Z, et al. Fabrication of silica-decorated graphene oxide nanohybrids and the properties of composite epoxy coatings research[J]. Applied Surface Science, 2016, 360:936-945. |
| [13] | ZHANG S, DU Z, LI G. Layer-by-layer fabrication of chemical-bonded graphene coating for solid-phase microextraction[J]. Analytical Chemistry, 2011, 83(19):7531-7541. |
| [14] | 王正君, 周醒, 肖文强, 等. PP/石墨微片复合材料的制备和性能[J]. 材料研究学报, 2017, 31(4):291-299. WANG Z J, ZHOU X, XIAO W Q, et al. Preparation and properties of composites PP/graphite sheets[J]. Chinese Journal of Materials Research, 2017, 31(4):291-299(in Chinese). |
| [15] | BIAN J, WANG Z J, LIN H L, et al. Thermal and mechanical properties of polypropylene nanocomposites reinforced with nano-SiO2 functionalized graphene oxide[J]. Composites Part A:Applied Science and Manufacturing, 2017, 97:120-127. |
| [16] | 张强, 朱光明, 付东升, 等. 聚丙烯共混增韧改性的研究进展[J]. 现代塑料加工应用, 2003, 15(3):58-61. ZHANG Q, ZHU G M, FU D S, et al. Recent Advances of modification of toughening PP[J]. Modern Plastics Processing and Applications, 2003, 15(3):58-61(in Chinese). |
| [17] | 李琛, 晏石林, 杨亚运, 等. 氧化石墨烯/呋喃树脂复合材料的制备及其性能[J]. 复合材料学报, 2017, 34(2):278-283. LI C, YAN S L, YANG Y Y, et al. Preparation and properties of graphene oxide/furan resin composites[J]. Acta Materiae Compositae Sinica, 2017, 34(2):278-283(in Chinese). |
| [18] | 周宏, 朴明昕, 李芹, 等. 氧化石墨烯纳米片/环氧树脂复合材料的制备与性能[J]. 复合材料报, 2015, 32(5):1309-1315. ZHOU H, PIAO M X, LI Q, et al. Preparation and properties of graphene oxide nanosheets/expoxy composites[J]. Acta Materiae Compositae Sinica, 2015, 32(5):1309-1315(in Chinese). |
| [19] | 王正君, 周醒, 孙坤程, 等. GO/SiO2/PP复合材料的制备与性能研究[J]. 弹性体, 2015, 25(6):7-10. WANG Z J, ZHOU X, SUN K C, et al. Preparation and properties of graphene/silica/PP composites[J]. China Elastomerics, 2015, 25(6):7-10(in Chinese). |
| [20] | LIN Y, JIN J, SONG M. Preparation and characterisation of covalent polymer functionalized graphene oxide[J]. Journal of Materials Chemistry, 2011, 21(10):3455-3461. |
| [21] | KOU L, GAO C. Making silica nanoparticle-covered graphene oxide nanohybrids as general building blocks for large-area superhydrophilic coatings[J]. Nanoscale, 2011, 3(2):519-528. |
| [22] | LEE C, WEI X, KYSAR J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene[J]. Science, 2008, 321(5887):385-388. |
| [23] | 谢桂兰, 张平, 龚曙光, 等. 增强增韧聚合物基复合材料宏细观应力集中的分析与研究[J]. 工程力学, 2005, 22(3):228-234. XIE G L, ZHANG P, GONG S G, et al. Macro-micro stress concentration analysys of strengthened and toughened polymer-matrix composites[J]. Engineering Mechanics, 2005, 22(3):228-234(in Chinese). |
| [24] | 麦堪成, 汪克风, 曾汉民. PP中成核剂的异相成核作用的热稳定性[J]. 合成树脂及塑料, 2001, 18(5):1-3. MAI K C, WANG K F, ZENG H M. Study on thermal stability of heterogeneous nucleation of the nucleated poly-propylene[J]. China Synthetic Resin and Plastics, 2001, 18(5):1-3(in Chinese). |
| [25] | KASHIWAGI T, GRULKE E, HILDING J, et al. Thermal degradation and flammability properties of poly(propylene)/carbon nanotube composites[J]. Macromolecular Rapid Communications, 2002, 23(13):761-765. |
