乙烯-醋酸乙烯酯共聚物增强硅橡胶复合材料的黏弹阻尼性能
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摘要
在密炼机中将醋酸乙烯基(VA)含量为18%(质量比)的乙烯-醋酸乙烯酯共聚物(EVA)与硅橡胶(SR)共混,再在开炼过程中加入橡胶其他组分混合得到EVA/SR混炼胶,硫化形成EVA/SR宽温域黏弹阻尼复合材料。采用毛细管流变仪、橡胶加工分析仪(RPA)、动态力学热分析仪(DMA)和DSC研究了EVA含量对EVA/SR复合材料的力学性能、加工性能、阻尼性能和热性能的影响。结果表明:加入较多EVA可更明显地改善SR的硬度和模量及撕裂强度,并使其拉伸强度和断裂伸长率仍然较高,保持在SR使用要求范围内。EVA/SR混炼胶剪切变稀,增大剪切应变幅值显示明显的Payne效应,用Kraus模型可分析EVA含量和硫化的影响。EVA分散于白炭黑填充的SR化学交联网络中形成多重结构;SR降低了EVA的结晶温度,添加EVA起到了增强和增黏SR的作用。纯SR损耗因子大于0.1的温度范围为-42～-28℃;对于EVA∶SR质量比为40∶100的EVA/SR复合材料,其最大损耗因子从0.125提高到0.18,有效阻尼温域为-23～37℃。这明显拓宽了SR有效阻尼温域,可应用于较高温度减震降噪工程。
Ethylene vinyl acetate(EVA)with 18%(mass ratio)of vinyl acetate was blended with silicone rubber(SR)in the mixer,then the other rubber components were added in the roll-milling to prepare un-vulcanized EVA/SR rubber composites,then they were vulcanized to produce EVA/SR viscoelastic damping composites with wider effective temperature range.The effects of different contents of EVA on the mechanical properties,processability,damping characteristics and thermal properties of EVA/SR composites were studied by capillary rheometer,rubber processing analyzer(RPA),DMA and DSC.The results show that adding more EVA can significantly improve the hardness and modulus and tear strength of SR.Meanwhile,the tensile strength and elongation at break are still high remaining within the range of SR application requirements,and EVA/SR is sheared thinner.The compound exhibits distinct Payne effect in strain scanning by increasing its amplitude.The effects of EVA content and vulcanization can be analyzed by Kraus model.EVA micro-cluster is dispersed in chemically crosslink network SR together filled withsilica forming multiple structures.SR decreases the crystallization temperature of EVA.EVA plays a significant role in reinforcing and increasing the viscosity of SR.For pure SR,the temperature range is-42～-28℃ when the loss factor is greater than 0.1.In contrast,for 100∶40(mass ratio)EVA/SR,the effective damping temperature range is-23～37℃corresponding to the maximum loss factor of 0.18 in comparison of 0.125 for pure SR.This obviously widens the effective damping temperature range rendering the shock-absorbing and de-noising applications at higher temperature.
Ethylene vinyl acetate(EVA)with 18%(mass ratio)of vinyl acetate was blended with silicone rubber(SR)in the mixer,then the other rubber components were added in the roll-milling to prepare un-vulcanized EVA/SR rubber composites,then they were vulcanized to produce EVA/SR viscoelastic damping composites with wider effective temperature range.The effects of different contents of EVA on the mechanical properties,processability,damping characteristics and thermal properties of EVA/SR composites were studied by capillary rheometer,rubber processing analyzer(RPA),DMA and DSC.The results show that adding more EVA can significantly improve the hardness and modulus and tear strength of SR.Meanwhile,the tensile strength and elongation at break are still high remaining within the range of SR application requirements,and EVA/SR is sheared thinner.The compound exhibits distinct Payne effect in strain scanning by increasing its amplitude.The effects of EVA content and vulcanization can be analyzed by Kraus model.EVA micro-cluster is dispersed in chemically crosslink network SR together filled withsilica forming multiple structures.SR decreases the crystallization temperature of EVA.EVA plays a significant role in reinforcing and increasing the viscosity of SR.For pure SR,the temperature range is-42～-28℃ when the loss factor is greater than 0.1.In contrast,for 100∶40(mass ratio)EVA/SR,the effective damping temperature range is-23～37℃corresponding to the maximum loss factor of 0.18 in comparison of 0.125 for pure SR.This obviously widens the effective damping temperature range rendering the shock-absorbing and de-noising applications at higher temperature.
引文
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[2]黄艳华,石扬,薛磊,等.航空硅橡胶材料研究及应用进展[J].航空材料学报,2016,36(3):79-91.HUNG Y H,SHI Y,XUE L,et al.Progress in research and application of aeronautical silicone rubber materials[J].Journal of Aeronautical Materials,2016,36(3):79-91(in Chinese).
[3]黄瑞丽,卢珣,龙娟,等.EPDM/ENR宽温域阻尼材料的制备及阻尼机理[J].高分子材料科学与工程,2016,32(10):119-124.HUANG R L,LU L,LONG J,et al.Preparation and damping mechanism of EPDM/ENR wide temperature domain damping materials[J].Polymer Materials Science and Engineering,2016,32(10):119-124(in Chinese).
[4]时姣,王克俭,刘杰,等.天然橡胶与其环氧化物(NR-ENR)并用胶基复合材料的黏弹阻尼性能[J].复合材料报,2018,35(3):537-544.SHI J,WANG K J,LIU J,et al.Viscoelastic damping properties of natural rubber and its epoxide(NR-ENR)in combination with matrix composites[J].Acta Materiae Compositae Sinica,2018,35(3):537-544(in Chinese).
[5] ZANG L,CHEN D,CAI Z,et al.Preparation and damping properties of an organic-inorganic hybrid material based on nitrile rubber[J].Composites Part B:Engineering,2018,137:217-224.
[6] YAHYAEI H,EBRAHIMI M,TAHAMI H V,et al.Toughening mechanisms of rubber modified thin film epoxy resins Part 2:Study of abrasion,thermal and corrosion resistance[J].Progress in Organic Coatings,2017,113:136-142.
[7] ZHANG C,PAL K,BYEON J U,et al.A study on mechanical and thermal properties of silicone rubber/EPDM damping materials[J].Journal of Applied Polymer Science,2011,119(5):2737-2741.
[8] BERAHMAN R,RAIATI M,MAZIDI M M,et al.Preparation and characterization of vulcanized silicone rubber/halloysite nanotube nanocomposites:Effect of matrix hardness and HNT content[J].Materials&Design,2016,104:333-345.
[9] CAI Y J,ZHANG C C,WU L L,et al.Mechanical damping properties of silicone rubber prepared by nano-SiO2and AGEmodified polysiloxane blends[J].Advanced Materials Research,2011,337:41-45.
[10]卢珣,李涛,陶刚,等.改性硅橡胶宽温域阻尼材料研究[J].哈尔滨工程大学学报,2016,37(1):92-97.LU X,LI T,TAO G,et al.Modified silicone rubber damping materials with wide temperature range[J].Journal of Harbin Engineering University,2016,37(1):92-97(in Chinese).
[11] ZHANG G,WANG F,DAI J,et al.Effect of functionalization of graphene nanoplatelets on the mechanical and thermal properties of silicone rubber composites[J].Materials,2016,9(2):92.
[12] YOUSEFZADE O,HEMMATI F,GARMABI H,et al.Thermal be havior and electrical conductivity of ethylene vinyl acetatecopolymer/expandedgraphitenanocomposites:Effects of nanofiller size and loading[J].Journal of Vinyl&Additive Technology,2016,22(1):51-60.
[13] CHEN X M,ZHONG H,JIA L Q,et al.Effect of the content of EVA on the dispersing status and properties of polyesteramide/EVA blend[J].International Journal of Adhesion&Adhesives,2001,21(3):221-226.
[14] LIANG Y X,GUO P,REN B Y,et al.Effects of preparation process of MQ silicone resin on reinforcement of RTV silicone rubber[J].Journal of South China University of Technology,2013,41(2):123-128.
[15] TAN X,ZHAO Y,SHANG M,et al.Supramolecular reinforcement of styrene-butadiene rubber composites[J].Polymer,2017,122:242-248.
[16] ZHANG Z,HE X,WANG X,et al.Reinforcement of the mechanical properties in nitrile rubber by adding graphene oxide/silicon dioxide hybrid nanoparticles[J].Journal of Applied Polymer Science,2017,135(14):46091.
[17]张祥福,张隐西.不同VA含量EVA/硅橡胶共混物的性能[J].弹性体,1991(2):28-32.ZHANG X F,ZHANG Y X.VEG/silicone rubber blends with different VA content[J].Elastomers,1991(2):28-32(in Chinese).
[18]程青民,丁国芳,罗世凯,等.EVA对硅橡胶混胶的共混改性研究[J].材料导报,2010,24(s1):415-417.CHENG Q M,DING G F,LUO S K,et al.EVA’s blending modification of silicone rubber blends[J].Materials Bulletin,2010,24(s1):415-417(in Chinese).
[19] STARK W,JAUNICH M.Investigation of ethylene/vinyl acetate copolymer(EVA)by thermal analysis DSC and DMA[J].Polymer Testing,2011,30(2):236-242.
[20]中国国家标准化管理委员会.硫化橡胶或热塑性橡胶拉伸应力应变性能的测定:GB/T 528—2009[S].北京:中国标准出版社,2009.Standardization Administration of the People’s Republic of China.Rubber,vulcanized or thermoplastic:Determination of tensile stress-strain properties:GB/T 528—2009[S].Beijing:China Standards Press,2009(in Chinese).
[21]中国国家标准化管理委员会.硫化橡胶或热塑性橡胶撕裂强度的测定(裤形、直角形和新月形试样):GB/T 529—2008[S].北京:中国标准出版社,2008.Standardization Administration of the People’s Republic of China.Rubber vulcanized or thermoplastic:Determination of tear strength(Trouser,angle and crescent test pieces):GB/T 529—2008[S].Beijing:China Standards Press,2008(in Chinese).
[22]中国国家标准化管理委员会.硫化橡胶或热塑性橡胶压入硬度试验方法第1部分:邵氏硬度计法(邵尔硬度):GB/T531.1—2008[S].北京:中国标准出版社,2008.Standardization Administration of the People’s Republic of China.Rubber vulcanized or thermoplastic:Determination of indentation hardness Part 1:Duromerer method(Shore hardness):GB/T 531.1—2008[S].Beijing:China Standards Press,2008(in Chinese).
[23] YANG R,SONG Y,ZHENG Q.Payne effect of silica-filled styrene-butadiene rubber[J].Polymer,2017,116:304-313.
[24] PAN Y,ZHONG Z.A viscoelastic constitutive modeling of rubber-like materials with the Payne effect[J].Applied Mathematical Modelling,2017,50:2621-2632.