磺化石墨烯与纳米氧化铝改性聚甲醛复合材料的导热及摩擦学性能研究
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摘要
目的探究纳米氧化铝(αAl_2O_3)和磺化石墨烯(S-GNS)对聚甲醛(POM)复合材料导热性能和摩擦学性能的影响,分析两种填料的协同改性机理。方法以S-GNS、αAl_2O_3和POM为原料,通过静电自组装法制备S-GNS-αAl_2O_3复合体,采用模压成型法制备S-GNS-αAl_2O_3/POM复合材料。采用X射线衍射仪、红外光谱仪及扫描电子显微镜对S-GNS和S-GNS-αAl_2O_3复合体进行表征,并采用导热系数测试仪和摩擦磨损试验机对复合材料的导热系数、摩擦系数和磨损量进行测试。利用扫描电子显微镜观察复合材料的磨损表面形貌。结果αAl_2O_3和S-GNS协同改性能够有效改善POM的导热性能,当S-GNS-αAl_2O_3复合体含量为7%(质量分数,下同)时,S-GNS-αAl_2O_3/POM复合材料导热系数为0.2524 W/(m·K),比纯POM提高了25.3%,S-GNS起到传递热量和提高αAl_2O_3与POM界面相容性的作用。S-GNS的加入,提高了S-GNS-αAl_2O_3/POM复合材料的热稳定性,有效地减少了αAl_2O_3磨粒对基体的损伤;αAl_2O_3的加入则分担了载荷,提高了复合材料的耐磨性。随着S-GNS-αAl_2O_3复合体含量的增加,S-GNS-αAl_2O_3/POM复合材料的摩擦系数逐渐降低,磨损量也呈降低趋势,且磨损表面光滑,磨损机理为磨粒磨损和轻微的犁沟切削。结论S-GNS和αAl_2O_3在POM中能发挥协同作用,有效提高了POM复合材料的导热性能和摩擦学性能。
The work aims to explore effects of nano alumina(αAl_2O_3)and sulfonated graphene(S-GNS)on thermal conductivity and tribological properties of polyoxymethylene(POM)composites and analyze the synergistic modification mechanism ofαAl_2O_3 and S-GNS.S-GNS,αAl_2O_3 and POM were used as raw materials to prepare S-GNS-αAl_2O_3 complex by electrostatic self-assembly method,as well as S-GNS-αAl_2O_3/POM composites by compression molding.The S-GNS and S-GNS-αAl_2O_3complexes were characterized by XRD,FT-IR and SEM.At the same time,the thermal conductivity,friction coefficient and wear loss of composites were tested by friction and wear tester and thermal conductivity tester.The worn surface morphology of the composites was observed by SEM.The synergistic modification ofαAl_2O_3 and S-GNS could effectively improve the thermal conductivity of composites.When the content of S-GNS-αAl_2O_3 was 7%(mass fraction,the same below),the thermal conductivity of the composite was 0.2524 W/(m·K),which was 25.3%higher than that of pure POM.S-GNS played the role in transferring heat and improving the compatibility of interface betweenαAl_2O_3 and POM.The addition of S-GNS improved the thermal stability of S-GNS-αAl_2O_3/POM composite and effectively reduced the damage to the matrix byαAl_2O_3 abrasive particles.Meanwhile,the addition ofαAl_2O_3 shared the load and improved wear resistance of composites.With the increase of S-GNS-αAl_2O_3 content,the friction coefficient of S-GNS-αAl_2O_3/POM composite decreased gradually and the wear amount also decreased.Furthermore,the worn surface was very smooth,and the wear mechanism was abrasive wear and slight furrow cutting.S-GNS andαAl_2O_3 can play a synergistic role in POM composites,and effectively improve the thermal conductivity and tribological properties of POM composites.
The work aims to explore effects of nano alumina(αAl_2O_3)and sulfonated graphene(S-GNS)on thermal conductivity and tribological properties of polyoxymethylene(POM)composites and analyze the synergistic modification mechanism ofαAl_2O_3 and S-GNS.S-GNS,αAl_2O_3 and POM were used as raw materials to prepare S-GNS-αAl_2O_3 complex by electrostatic self-assembly method,as well as S-GNS-αAl_2O_3/POM composites by compression molding.The S-GNS and S-GNS-αAl_2O_3complexes were characterized by XRD,FT-IR and SEM.At the same time,the thermal conductivity,friction coefficient and wear loss of composites were tested by friction and wear tester and thermal conductivity tester.The worn surface morphology of the composites was observed by SEM.The synergistic modification ofαAl_2O_3 and S-GNS could effectively improve the thermal conductivity of composites.When the content of S-GNS-αAl_2O_3 was 7%(mass fraction,the same below),the thermal conductivity of the composite was 0.2524 W/(m·K),which was 25.3%higher than that of pure POM.S-GNS played the role in transferring heat and improving the compatibility of interface betweenαAl_2O_3 and POM.The addition of S-GNS improved the thermal stability of S-GNS-αAl_2O_3/POM composite and effectively reduced the damage to the matrix byαAl_2O_3 abrasive particles.Meanwhile,the addition ofαAl_2O_3 shared the load and improved wear resistance of composites.With the increase of S-GNS-αAl_2O_3 content,the friction coefficient of S-GNS-αAl_2O_3/POM composite decreased gradually and the wear amount also decreased.Furthermore,the worn surface was very smooth,and the wear mechanism was abrasive wear and slight furrow cutting.S-GNS andαAl_2O_3 can play a synergistic role in POM composites,and effectively improve the thermal conductivity and tribological properties of POM composites.
引文
[1]钱志强.聚甲醛的增强、耐磨及增韧改性技术的研究与开发[D].北京:北京化工大学, 2014.QIANZhi-qiang.Developmentandresearchofpolyoxymethylenecompositesonreinforcement,tougheningand wear-resistance modification[D]. Beijing:Beijing University of Chemical Technology, 2014.
[2]ZHANGBY,XUL,GUOZX,etal.Effectsofglass fiber on the properties of polyoxymethylene/thermoplastic polyurethane/multiwalled carbon nanotube composites[J].Polymer composites, 2017, 38(7):1319-1326.
[3]江玲玲.高导热POM/氧化铝复合材料的制备及性能[D].合肥:合肥工业大学, 2016.JIANGLing-ling.PreparingandpropertiesofhighthermalconductivityPOM/Al2O3composites[D].Hefei:Hefei University of Technology, 2016.
[4]马小丰,金旺,杨大志,等.碳纤维增强聚甲醛复合材料的制备及性能研究[J].工程塑料应用,2014,42(1):23-26.MA Xiao-feng, JIN Wang, YANG Da-zhi, et al. Study on preparationandpropertiesofcarbonfibersreinforced polyoxymethylenecomposites[J].Engineeringplastics application, 2014, 42(1):23-26.
[5]张臻,龙春光,尹妍,等.聚甲醛/泡沫铝合金互穿复合材料导热性能的研究[J].功能材料,2014,45(23):23029-23032.ZHANG Zhen, LONG Chun-guang, YIN Yan, et al. Study onheattransferperformanceofPOM/Aluminumalloy interpenetratingphasecomposites[J].Journaloffunctional materials, 2014, 45(23):23029-23032.
[6]江玲玲,冯艳,陈诚,等.高导热绝缘Al2O3/POM复合材料的制备与性能[J].塑料工业,2015,43(12):102-104.JIANGLing-ling,FENGYan,CHENCheng,etal.Preparationandpropertiesofhighthermallyconductive and electrical insulating Al2O3/POM composites[J]. China plastics industry, 2015, 43(12):102-104.
[7]HEJ,ZHANGL,LIC.ThermalconductivityandtribologicalpropertiesofPOM-Cucomposites[J].Polymer engineering&science, 2010, 50(11):2153-2159.
[8]WACHARAWICHANANT S, THONGYAI S, PHUTTHAPHAN A, et al. Effect of particle sizes of zinc oxide on mechanical,thermalandmorphologicalpropertiesof polyoxymethylene/zincoxidenanocomposites[J].Polymer testing, 2008, 27(8):971-976.
[9]邢新侠,甘志宏.改性纳米氧化铝悬浮体系制备工艺研究[J].表面技术, 2015, 44(4):104-108.XING Xin-xia, GAN Zhi-hong. Research on the preparationprocessofmodifiednano-Al2O3suspension[J].Surface technology, 2015, 44(4):104-108.
[10]FENG J, WANG X, GUO P, et al. Mechanical properties andwearresistanceofsulfonatedgraphene/waterborne polyurethanecompositespreparedbyinsitumethod[J].Polymers, 2018, 10(1):75.
[11]陈航,王继虎,温绍国,等.磺化石墨烯/天然橡胶复合材料的性能研究[J].高分子通报, 2017(6):32-38.CHENHang,WANGJi-hu,WENShao-guo,etal.The performance of natural rubber composites filled with sulfonatedgraphene[J].Chinesepolymerbulletin,2017(6):32-38.
[12]吴平,叶昕瑜,舒杨,等.磺化石墨烯在丙烯酸酯涂料中的性能研究[J].涂料工业, 2017, 47(3):67-71.WUPing,YEXin-yu,SHUYang,etal.Studyonperformanceofacrylatecoatingsfilledwithsulfonatedgraphene[J]. Paint&coatings industry, 2017, 47(3):67-71.
[13]HU C F, RONG J H, CUI J H, et al. Fabrication of agrapheneoxide-goldnanorodhybridmaterialbyelectrostaticself-assemblyforsurface-enhancedRamanscattering[J]. Carbon, 2013, 51:255-264.
[14]齐天娇,俞泽民,许志鹏,等.石墨烯增强铝基复合材料制备及力学性能研究[J].哈尔滨理工大学学报,2015, 20(3):61-65.QI Tian-jiao, YU Ze-min, XU Zhi-peng, et al. Preparation andmechanicalpropertiesofgraphenereinforcedaluminumcomposites[J].JournalofHarbinUniversityofScience and Technology, 2015, 20(3):61-65.
[15]SIY,SAMULSKIET.Synthesisofwatersolublegraphene[J]. Nano letters, 2008, 8(6):1679.
[16]周敏.氧化石墨烯的制备与表征[J].化工技术与开发,2017, 46(7):21-24.ZHOUMin.Preparationandcharacterizationofgraphene[J].Technology&developmentofchemicalindustry, 2017, 46(7):21-24.
[17]HUANGW,OUYANGX,LEELJ.High-performance nanopapersbasedonbenzenesulfonicfunctionalizedgraphenes[J]. ACS Nano, 2012, 6(11):10178.
[18]SHEN Y, CHEN B. Sulfonated graphene nanosheets as a superbadsorbentforvariousenvironmentalpollutantsin water[J].Environmentalscience&technology,2015,49(12):7364-7372.
[19]陈良勇,杨彬,刘丽华,等.磺化石墨烯的制备及其催化性能研究[J].广州化工, 2016, 44(5):110-113.CHENLiang-yong,YANGBin,LIULi-hua,etal.Synthesisofsulfonatedgrapheneoxidecatalystandits catalyticactivity[J].Guangzhouchemicalindustry,2016,44(5):110-113.
[20]阳杰,吉冬冬,田长安,等.氧化铝-氧化石墨烯复合材料制备及性能研究[J].应用化工, 2018(1):62-65.YANGJie,JIDong-dong,TIANChang-an,etal.Study onpreparationandpropertiesofaluminagraphiteoxide composites[J]. Applied chemical industry, 2018(1):62-65.
[21]胡洋洋,许崇海,肖光春,等.氧化铝/氧化石墨烯复合陶瓷的制备及性能[J].硅酸盐学报,2016,44(3):432-437.HU Yang-yang, XU Chong-hai, XIAO Guang-chun, et al.Preparationandpropertiesofalumina/graphemeoxide compositeceramic[J].Journalofthechinese ceramicsociety, 2016, 44(3):432-437.
[22]QIANR,YUJ,WUC,etal.Alumina-coatedgraphene sheet hybrids for electrically insulating polymer compositeswithhighthermalconductivity[J].RscAdvances,2013, 3(38):17373-17379.
[23]徐翔民,张豫徽,李宾杰,等.POM/GF-MWCNTs复合材料的制备及其性能研究[J].中国塑料,2016,30(4):76-82.XU Xiang-min, ZHANG Yu-hui, LI Bin-jie, et al. PreparationandperformanceofPOM/GF-MWCNTscomposites[J]. China plastic, 2016, 30(4):76-82.
[24]KIMKT,DAOTD,HANMJ,etal.Graphenecoated with alumina and its utilization as a thermal conductivity enhancerforaluminasphere/thermoplasticpolyurethane composite[J].Materialschemistry&physics,2015,153:291-300.
[25]符永宏,张航成,戴金跃,等.激光复合织构薄壁弯管模具成型试验[J].精密成形工程, 2017, 9(1):59-65.FU Yong-hong, ZHANG Hang-cheng, DAI Jin-yue, et al.Forming of thin-wall tube bending mould with composite lasertexturingsurface[J].Netshapeformingengineering,2017, 9(1):59-65.
[26]龙春光,申超,曹太山.石墨烯增强MC尼龙复合材料的力学和摩擦学性能[J].长沙理工大学学报(自然科学版), 2014(2):92-97.LONGChun-guang,SHENChao,CAOTai-shan.Mechanical and tribological properties of MC nylon composites reinforced by graphene[J]. Journal of Changsha University of Science and Technology(natural science), 2014(2):92-97.
[27]卞达.石墨烯增强耐磨减摩氧化铝陶瓷涂层基础研究[D].无锡:江南大学, 2017.BIANDa.Fundamentalresearchonthechemically bondedceramiccoatingsreinforcedbygraphene[D].Wuxi:Jiangnan University, 2017.
[28]莫品书,向定汉,方伟,等.纳米Al2O3填充LDPE/POM复合材料的力学和摩擦性能研究[J].润滑与密封,2012, 37(7):45-48.MOPin-shu,XIANGDing-han,FANGWei,etal.MechanicalandtribologicalpropertiesofLDPE/POMcompositesfilledwithnano-Al2O3[J].Lubricationengineering, 2012, 37(7):45-48.
[2]ZHANGBY,XUL,GUOZX,etal.Effectsofglass fiber on the properties of polyoxymethylene/thermoplastic polyurethane/multiwalled carbon nanotube composites[J].Polymer composites, 2017, 38(7):1319-1326.
[3]江玲玲.高导热POM/氧化铝复合材料的制备及性能[D].合肥:合肥工业大学, 2016.JIANGLing-ling.PreparingandpropertiesofhighthermalconductivityPOM/Al2O3composites[D].Hefei:Hefei University of Technology, 2016.
[4]马小丰,金旺,杨大志,等.碳纤维增强聚甲醛复合材料的制备及性能研究[J].工程塑料应用,2014,42(1):23-26.MA Xiao-feng, JIN Wang, YANG Da-zhi, et al. Study on preparationandpropertiesofcarbonfibersreinforced polyoxymethylenecomposites[J].Engineeringplastics application, 2014, 42(1):23-26.
[5]张臻,龙春光,尹妍,等.聚甲醛/泡沫铝合金互穿复合材料导热性能的研究[J].功能材料,2014,45(23):23029-23032.ZHANG Zhen, LONG Chun-guang, YIN Yan, et al. Study onheattransferperformanceofPOM/Aluminumalloy interpenetratingphasecomposites[J].Journaloffunctional materials, 2014, 45(23):23029-23032.
[6]江玲玲,冯艳,陈诚,等.高导热绝缘Al2O3/POM复合材料的制备与性能[J].塑料工业,2015,43(12):102-104.JIANGLing-ling,FENGYan,CHENCheng,etal.Preparationandpropertiesofhighthermallyconductive and electrical insulating Al2O3/POM composites[J]. China plastics industry, 2015, 43(12):102-104.
[7]HEJ,ZHANGL,LIC.ThermalconductivityandtribologicalpropertiesofPOM-Cucomposites[J].Polymer engineering&science, 2010, 50(11):2153-2159.
[8]WACHARAWICHANANT S, THONGYAI S, PHUTTHAPHAN A, et al. Effect of particle sizes of zinc oxide on mechanical,thermalandmorphologicalpropertiesof polyoxymethylene/zincoxidenanocomposites[J].Polymer testing, 2008, 27(8):971-976.
[9]邢新侠,甘志宏.改性纳米氧化铝悬浮体系制备工艺研究[J].表面技术, 2015, 44(4):104-108.XING Xin-xia, GAN Zhi-hong. Research on the preparationprocessofmodifiednano-Al2O3suspension[J].Surface technology, 2015, 44(4):104-108.
[10]FENG J, WANG X, GUO P, et al. Mechanical properties andwearresistanceofsulfonatedgraphene/waterborne polyurethanecompositespreparedbyinsitumethod[J].Polymers, 2018, 10(1):75.
[11]陈航,王继虎,温绍国,等.磺化石墨烯/天然橡胶复合材料的性能研究[J].高分子通报, 2017(6):32-38.CHENHang,WANGJi-hu,WENShao-guo,etal.The performance of natural rubber composites filled with sulfonatedgraphene[J].Chinesepolymerbulletin,2017(6):32-38.
[12]吴平,叶昕瑜,舒杨,等.磺化石墨烯在丙烯酸酯涂料中的性能研究[J].涂料工业, 2017, 47(3):67-71.WUPing,YEXin-yu,SHUYang,etal.Studyonperformanceofacrylatecoatingsfilledwithsulfonatedgraphene[J]. Paint&coatings industry, 2017, 47(3):67-71.
[13]HU C F, RONG J H, CUI J H, et al. Fabrication of agrapheneoxide-goldnanorodhybridmaterialbyelectrostaticself-assemblyforsurface-enhancedRamanscattering[J]. Carbon, 2013, 51:255-264.
[14]齐天娇,俞泽民,许志鹏,等.石墨烯增强铝基复合材料制备及力学性能研究[J].哈尔滨理工大学学报,2015, 20(3):61-65.QI Tian-jiao, YU Ze-min, XU Zhi-peng, et al. Preparation andmechanicalpropertiesofgraphenereinforcedaluminumcomposites[J].JournalofHarbinUniversityofScience and Technology, 2015, 20(3):61-65.
[15]SIY,SAMULSKIET.Synthesisofwatersolublegraphene[J]. Nano letters, 2008, 8(6):1679.
[16]周敏.氧化石墨烯的制备与表征[J].化工技术与开发,2017, 46(7):21-24.ZHOUMin.Preparationandcharacterizationofgraphene[J].Technology&developmentofchemicalindustry, 2017, 46(7):21-24.
[17]HUANGW,OUYANGX,LEELJ.High-performance nanopapersbasedonbenzenesulfonicfunctionalizedgraphenes[J]. ACS Nano, 2012, 6(11):10178.
[18]SHEN Y, CHEN B. Sulfonated graphene nanosheets as a superbadsorbentforvariousenvironmentalpollutantsin water[J].Environmentalscience&technology,2015,49(12):7364-7372.
[19]陈良勇,杨彬,刘丽华,等.磺化石墨烯的制备及其催化性能研究[J].广州化工, 2016, 44(5):110-113.CHENLiang-yong,YANGBin,LIULi-hua,etal.Synthesisofsulfonatedgrapheneoxidecatalystandits catalyticactivity[J].Guangzhouchemicalindustry,2016,44(5):110-113.
[20]阳杰,吉冬冬,田长安,等.氧化铝-氧化石墨烯复合材料制备及性能研究[J].应用化工, 2018(1):62-65.YANGJie,JIDong-dong,TIANChang-an,etal.Study onpreparationandpropertiesofaluminagraphiteoxide composites[J]. Applied chemical industry, 2018(1):62-65.
[21]胡洋洋,许崇海,肖光春,等.氧化铝/氧化石墨烯复合陶瓷的制备及性能[J].硅酸盐学报,2016,44(3):432-437.HU Yang-yang, XU Chong-hai, XIAO Guang-chun, et al.Preparationandpropertiesofalumina/graphemeoxide compositeceramic[J].Journalofthechinese ceramicsociety, 2016, 44(3):432-437.
[22]QIANR,YUJ,WUC,etal.Alumina-coatedgraphene sheet hybrids for electrically insulating polymer compositeswithhighthermalconductivity[J].RscAdvances,2013, 3(38):17373-17379.
[23]徐翔民,张豫徽,李宾杰,等.POM/GF-MWCNTs复合材料的制备及其性能研究[J].中国塑料,2016,30(4):76-82.XU Xiang-min, ZHANG Yu-hui, LI Bin-jie, et al. PreparationandperformanceofPOM/GF-MWCNTscomposites[J]. China plastic, 2016, 30(4):76-82.
[24]KIMKT,DAOTD,HANMJ,etal.Graphenecoated with alumina and its utilization as a thermal conductivity enhancerforaluminasphere/thermoplasticpolyurethane composite[J].Materialschemistry&physics,2015,153:291-300.
[25]符永宏,张航成,戴金跃,等.激光复合织构薄壁弯管模具成型试验[J].精密成形工程, 2017, 9(1):59-65.FU Yong-hong, ZHANG Hang-cheng, DAI Jin-yue, et al.Forming of thin-wall tube bending mould with composite lasertexturingsurface[J].Netshapeformingengineering,2017, 9(1):59-65.
[26]龙春光,申超,曹太山.石墨烯增强MC尼龙复合材料的力学和摩擦学性能[J].长沙理工大学学报(自然科学版), 2014(2):92-97.LONGChun-guang,SHENChao,CAOTai-shan.Mechanical and tribological properties of MC nylon composites reinforced by graphene[J]. Journal of Changsha University of Science and Technology(natural science), 2014(2):92-97.
[27]卞达.石墨烯增强耐磨减摩氧化铝陶瓷涂层基础研究[D].无锡:江南大学, 2017.BIANDa.Fundamentalresearchonthechemically bondedceramiccoatingsreinforcedbygraphene[D].Wuxi:Jiangnan University, 2017.
[28]莫品书,向定汉,方伟,等.纳米Al2O3填充LDPE/POM复合材料的力学和摩擦性能研究[J].润滑与密封,2012, 37(7):45-48.MOPin-shu,XIANGDing-han,FANGWei,etal.MechanicalandtribologicalpropertiesofLDPE/POMcompositesfilledwithnano-Al2O3[J].Lubricationengineering, 2012, 37(7):45-48.