白炭黑的功能化改性及其改性橡胶基复合材料的制备与表征

利用沉淀法白炭黑生产工艺,在相同的条件下,选用不同质量分数的羟基羧酸酯作为改性剂进行湿法改性,研究了白炭黑/天然橡胶(NR)复合橡胶的力学性能、动态性能以及动态生热性能。结果表明:制备的白炭黑均为非晶态白炭黑,采用质量分数为6%的羟基羧酸酯改性的白炭黑,其分散性好,颗粒分布均匀,呈近球状,经羟基羧酸酯改性后的白炭黑有效的去除了部分亲水基团,改善了其在NR中的分散性。随着白炭黑用量的增加,分散性变差,损耗因子和动态温升均有所提高,Payne效应增大。当白炭黑用量达到临界值(白炭黑与NR质量比为40∶100)时,白炭黑/NR复合材料表现出较好的性能,改性白炭黑/NR复合材料比未改性白炭黑/NR复合材料的硬度、拉伸强度、断裂伸长率有所提高,而磨耗体积和动态生热则有所下降。动态力学性能测试结果表明,改性白炭黑与天然橡胶的质量比为40∶100时,改性白炭黑/NR复合材料的60℃滚动阻力损耗因子由0.123降到0.104。SEM结果表明,改性白炭黑在橡胶基体中的分散性优于未改性白炭黑,与NR基体界面结合的更加紧密。     

硅酸盐纳米纤维增强橡胶复合材料的结构与性能

利用天然针状硅酸盐——凹凸棒石(AT)的结构特点, 采用机械共混法并结合原位改性技术制备了一系列硅酸盐纳米纤维/橡胶复合材料, 研究了复合材料的结构与性能, 分析了针状硅酸盐良好增强效果的内在机制。借助硅烷偶联剂的原位改性和混合过程中的机械剪切力, AT微米聚集体被解离成长径比为10~30的纳米纤维分散在橡胶基体中, 纳米复合材料表现出短纤维/橡胶复合材料(SFRC)的应力-应变特性和明显的力学性能各向异性。而且, AT/橡胶纳米复合材料具有优良的高温模量和加工性能。AT的优良的增强效果来源于AT的纳米分散和良好的纤维-橡胶界面结合。      

粒径对Ni/硅橡胶复合材料压敏性及介电性质的影响

采用不同粒径的Ni粉与硅橡胶(110型)按质量比2.4∶1.0制成Ni/硅橡胶复合材料, 分别测量了其压敏导电性及介电性质, 并结合扫描电镜照片对其微观导电机制进行了分析。结果表明随着填料Ni粉粒径的减小, Ni/硅橡胶复合材料的直流电阻率对外加压强更加敏感: 在低压强下, 粒径为74、48和18 μm的样品的电阻率随压强的变化率分别为1.73×104、2.59×104和3.71×10 4 Ω·m/kPa。样品直流电阻率陡降的区域随粒径的减小向压强较小的方向移动, 显示出复合材料的渗流阈值与填充粒子的粒径有关: 粒径越小, 渗流阈值也越小。Ni/硅橡胶复合材料的交流电导率、介电常数、介电损耗均随填料Ni粉粒径的减小而变大: Ni粉粒径为18 μm的Ni/硅橡胶复合材料的电导率约为10-2 S·m-1, 比74 μm粒径样品的电导率(约10-7 S·m-1)提高了5个数量级; 对应的介电常数由约102提高到约103。改变填料Ni粉粒径可以有效地调节复合材料的弹性和压敏、电输运特性。      

纳米二氧化硅粒径对橡胶复合材料力学性能的影响

以不同粒径的纳米二氧化硅为填料加到天然橡胶中制备纳米二氧化硅/天然橡胶(NR)复合材料。研究了不同粒径纳米二氧化硅(15,30和80nm)对复合材料的力学性能、应力软化效应、Payne效应、动态热机械性能、压缩生热和损耗因子等基本特性的影响。结果表明,随着纳米二氧化硅粒径的增大,复合材料的抗拉强度变大,应力软化效应增大;同时,复合材料的Payne效应和损耗因子越低,其动态压缩温升越低。Payne效应分析及扫描电镜观察还表明,大粒径纳米二氧化硅在橡胶基体中易于分散均匀,粒子间聚集程度更小,而小粒径的则表现出较明显的团聚现象,粒子在橡胶基体中的分散性对复合材料力学性能有直接影响。     

玄武岩短纤维-芳纶浆粕/氯丁橡胶复合材料的制备与性能

以氯丁橡胶（CR）为基体,改性玄武岩短纤维（BSF）和芳纶浆粕（AP）作为增强相,制备了高强度、高模量的BSF-AP/CR复合材料,系统地研究了BSF和AP对BSF-AP/CR复合材料基本物理性能、动态力学性能和动刚度的影响。采用超声波辅助γ-氨丙基三乙氧基硅烷（KH550）对BSF进行了改性,通过FTIR测试显示KH550与BSF表面基团发生了反应。通过SEM观察发现,改性BSF与CR界面相容性较好,易于分散和取向,而AP锚固在CR基体中,取向度不如BSF高;随着BSF与AP质量比值减小,BSF-AP/CR复合材料的拉伸强度、拉断伸长率和屈挠性能降低,耐撕裂性能和耐磨性能变好。采用弹性体材料测试系统（MTS）测试复合材料的动刚度。结果表明,BSF与AP质量比越小,BSF-AP/CR复合材料的动刚度越大,说明AP对BSF-AP/CR复合材料动刚度贡献大。动态力学性能显示,AP用量越多,BSF-AP/CR复合材料的储能模量（G'）越高,Payne效应越明显,而阻尼因子越小,说明AP有良好的模量-滞后平衡效应。当BSF与AP质量比为10:10时,BSF-AP/CR复合材料的综合性能较好。      

Lignocellulosic fibre mediated rubber composites: An overview

The rising concern towards the reduction in the use of petroleum-based, non-renewable resources and the need for more versatile polymer-based composite materials have led to increasing interests on natural polymer composites filled with natural organic fillers, i.e. coming from renewable and biodegradable sources. This paper reviews wood flour and other lignocellulosic fibres filled rubber composites, including cellulosic rubber composites, cellulosic thermoplastic elastomers, nanocellulose based rubber nanocomposites, with the aims at providing the most state of the art information for directing further scientific research, possible commercialization and design of cellulosic rubber composites. It has been found that 1) the surface properties of natural cellulose, hence the compatibility and interface of the natural cellulose and matrix rubber/plastics, are crucial for the successful development of the composites, such, physical and chemical modification and additives have been widely attempted to improve the incompatibility and poor interfacial adhesion between the filler and matrix; 2) the curing characteristics, mechanical properties, thermal stability and morphologies of the composites are complex but closely related to not only the interfacial properties, but also the compositions (e.g. the concentration of cellulosic materials) and other processing parameters; 3) the nature of hydrophilic cellulosic and hydrophobic matrix rubber and/or plastics requires an accurate introduction of coupling agent, one end of its structure shall be compatible to hydrophilic and the other to hydrophobic. The reviews on the main paths and results of study on the advanced nanocellulose reinforced rubber nanocomposites and sandwiches indicate much potentials and needs for further in-depth studies.     

橡胶相尺度对亚微米或纳米橡胶颗粒填充环氧复合材料性能的影响

对比研究了由液体橡胶在环氧树脂中原位形成的亚微米橡胶/环氧复合材料和在环氧树脂中直接添加纳米橡胶颗粒形成的纳米橡胶/环氧复合材料的性能。研究表明：未固化混合物的黏度随着纳米橡胶相的加入逐渐增加,但随着亚微米橡胶相含量的增加而降低;橡胶/环氧复合材料的玻璃化转变温度随着纳米橡胶颗粒的加入逐渐增加,但随着亚微米橡胶相含量的增加而降低;两种橡胶相的添加均使复合材料的弹性模量降低,断裂延伸率增加;在较低含量时,纳米橡胶颗粒可以提高环氧的拉伸强度;两种橡胶填充的橡胶/环氧复合材料均显示出明显的增韧效果。微观形貌分析表明,两种橡胶均可以在应力作用下脱粘并促进裂纹尖端的塑性变形。     

Separation of matrix alloy and reinforcement from aluminum metal matrix composites scrap by salt flux addition

Separation of matrix alloy and reinforcements from pure Al-SiC_p composite scrap by salt flux addition has been theoretically predicted using interface free energies. Experiments performed confirm the theoretical prediction. Complete separation of matrix aluminum and reinforcement from metal matrix composites (MMCs) scrap has been achieved by addition of 2·05 wt% of equimolar mixture of NaCl-KCl salt flux with a metal and particle yield of 84 and 50%, respectively. By adding 5 wt% of NaF to equimolar mixture of NaCl-KCl, metal and particle yield improved to 91 and 73%, respectively. Reusability of both the matrix aluminum and the SiC separated from Al-SiC_p scraps has been analysed using XRD, SEM and DTA techniques. The matrix alloy separated from Al-SiC_p scraps can be used possibly as a low Si content Al-Si alloy. However, the interfacial reaction that occurred during the fabrication of the composites had degraded the SiC particles.     

超细绢云母/加成型液体硅橡胶复合材料的制备及性能

以天然绢云母矿物为原料,利用气流磨超细粉碎、乙烯基三乙氧基硅烷表面修饰处理对绢云母进行深加工,得到有机化的绢云母超细粉体,再采用溶液聚合方法制备出具有优良性能的超细绢云母/加成型液体硅橡胶复合材料。用SEM对其微观形貌进行了观察和分析,通过观察SEM可以发现经偶联剂表面修饰处理后超细绢云母在硅橡胶基体中分散均匀。当超细绢云母质量分数为8%时,复合材料的拉伸强度和邵氏硬度达到了1.25 MPa和61,分别比纯硅橡胶提高了197.62%和48.78%。TGA测试结果表明,超细绢云母可显著提高硅橡胶的热稳定性能。此外,用Kraus方程对超细绢云母与硅橡胶之间的相互作用进行了表征。      

石墨烯硅橡胶复合材料的性能研究

本文采用复配的石墨烯、碳纳米管和氧化铝为导热填料制备了具有导热功能的有机硅复合材料。研究了石墨烯、碳纳米管和氧化铝的复配比例对复合材料体积电阻率、导热系数、拉伸强度等性能的影响;同时,以Gr-C-4#样品为基础配方,采用硅烷偶联剂Si-G-1分别对石墨烯、碳纳米管及氧化铝进行改性,并用改性后的填料配制石墨烯硅橡胶复合材料Gr-C-Si-1#,对比样品Gr-C-4^#与Gr-C-Si-1^#的性能差异,分析了改性复配填料对复合材料性能的影响。采用石墨烯硅橡胶复合材料对电缆终端进行了封装,对封装好的电缆终端开展了100、150、200A电流下的温升实验,未出现局部过热,并测定水浸泡前后的电缆终端电阻,封装后的电缆终端电阻未出现明显上升,实验结果表明本材料可以在电缆终端或中间连接处进行灌封,可对封铅连接处的良好的保护作用,工程应用意义重大。     

Mechanical,rheological, morphological and water absorption properties of maleated polyethylene/hemp composites: Effect of ground tire rubber addition

Natural fibre composites were produced from maleated polyethylene (MAPE) and hemp fibres, while impact modification was performed via ground tire rubber (GTR) addition. Incorporation of hemp fibre increased significantly the tensile (strength and modulus) and flexural properties of the MAPE matrix. Impact strength however, decreased with increasing hemp content, but GTR addition led to a noticeable increase in impact strength (up to 50% at 10% GTR). Increase in hemp content produced also higher water uptake and longer saturation time. After ageing in water, the mechanical properties and thermal stability were unchanged for samples up to 30% hemp, but samples at higher concentrations showed some degradation.     

改性淀粉/丁苯橡胶复合材料的制备及性能研究

采用固相法制备了玉米淀粉接枝马来酸酐(MAH)和苯乙烯(St)的共聚物Starch-g-MAH-St(SMS)。采用机械共混法制备了接枝改性淀粉/丁苯橡胶(SMS/SBR)复合材料,研究了复合材料的力学性能、热空气老化性能、动态力学性能以及微观形态。结果表明,SMS/SBR复合材料的力学性能优于未改性淀粉/SBR复合材料和纯SBR。当苯乙烯和MAH单体用量都为原淀粉质量的10 %且SMS的用量为20 g/100 g SBR时,SMS/SBR复合材料的力学性能最佳。经100℃ 热空气老化48 h后,复合材料的拉伸强度仍可达10 MPa。与纯 SBR硫化胶相比,SMS/SBR复合材料的玻璃化转变温度(T_g)降低。微观形态分析显示,淀粉经改性后粒子尺寸减小,在SBR 中的分散性得到了改善,与SBR基体的相容性得到了提高。      

纳米石墨/天然橡胶复合材料的应力软化与动态性能

以不同尺寸的纳米石墨为原料,制备了纳米石墨/天然橡胶(NR)复合材料.研究不同尺寸(30、80、150 nm)的纳米石墨对复合材料的应力软化效应(Mullins效应)、Payne效应、动态生热和损耗因子的影响.结果表明:随着纳米石墨尺寸的增大,纳米填料对纳米石墨/NR复合材料体系的补强作用明显,应力软化效应增大、动态损耗因子增加,但Payne效应降低;纳米石墨/NR复合材料动态损耗因子越大,其动态生热越高;动态生热还与填料粒子网络形成紧密相关.SEM观察及Payne效应分析结果表明:采用不同尺寸的纳米石墨材料填充天然橡胶,大尺寸石墨在橡胶基体中易于分散均匀,片层的聚集程度小,而小尺寸纳米片层表现出较明显的团聚.     

碱式硫酸镁晶须/橡胶复合材料的制备

将超声分散后的硅烷偶联剂3-氨丙基三乙氧基硅烷改性碱式硫酸镁晶须（KH550-MgOS_W）分散液加入天然胶乳（NR）中,对其进行补强,制得绿色环保高性能的KH550-MgOS_W/NR复合材料。系统研究了KH550-MgOS_W/NR复合材料的力学性能、阻燃性能及热稳定性能。结果表明,用KH550改性后的MgOS_W与橡胶基体具有很好的相容性。KH550-MgOS_W/NR复合材料的力学性能、阻燃性能及热稳定性能均比纯胶有所提高。当KH550-MgOS_W与NR质量比为4%时,KH550-MgOS_W/NR复合材料的各项性能均达到最佳,300%定伸应力、拉伸强度、撕裂强度、断裂伸长率、交联密度比纯胶胶膜分别提高了25.0%、36.8%、37.3%、11.4%、44.2%,垂直燃烧等级由FV-1提高到了FV-0级,比纯胶的起始热降解温度（T₀）、最大热降解温度（T_p）和终止热降解温度（T_f）分别提高了6.2℃、5.2℃和4.1℃。     

Micromechanical analysis of fatigue cracks in cord–rubber composites

Analyses of two different types of cracks due to fatigue of cord–rubber composites is carried out using micromechanical two-dimensional (2D) and three-dimensional (3D) finite element analysis. The fracture parameter, tearing energy (TE)/J-integral that characterizes the severity of crack tip stresses in rubber composites, is computed from the finite element results of stresses and strains. The results obtained are validated with existing analytical methods in the literature. Numerical results of J-integral values are presented for two crack types, and crack sizes under transverse strain and shear strain loading conditions. The results presented illustrate that crack type, loading, and crack size have a strong effect on the values of J-integral. The results of the J-integral should help our understanding in estimating the severity of local failures in cord–rubber composites.     

碳纳米管/橡胶复合材料的界面性能:碳纳米管的比表面积的影响

橡胶大分子和无机纳米填料由于相互作用形成的界面是决定弹性体复合材料性能的重要因素.利用原子力显微镜的峰值力定量纳米力学映射模式(AFM-QNM)建立了碳纳米管/溶聚丁苯橡胶(CNT/SSBR)复合材料的界面纳米力学性能和界面厚度的定量表征方法,研究揭示了CNT的比表面积对CNT/SSBR复合材料的界面纳米力学性能和界面...     

受阻酚AO-60/丁腈橡胶-环氧化天然橡胶-天然橡胶复合材料的制备及其阻尼性能

选用受阻酚AO-60/丁腈橡胶（NBR）（质量比40:100）作为阻尼相,环氧化天然橡胶（ENR）作为相容剂,制备了AO-60/NBR-ENR-天然橡胶（NR）复合材料。研究发现,复合材料的微观结构呈"海岛结构",当质量比NR/NBR为60:40和50:50时,体系中出现双连续相结构。复合材料呈现两个玻璃化转变温度,分别出现在-60℃附近和-10℃附近;随着AO-60/NBR质量比的增加,在-20~40℃温度范围内复合材料的有效阻尼温域从0℃拓宽到35.9℃,且损耗因子随应变增大有小幅提升。复合材料在低应变下呈现低应力,表现出高柔性,同时其在较高应变下存在应力突变点,表现出较高的拉伸强度和扯断伸长率。      

Multiaxial fatigue of rubber: Part I: equivalence criteria and theoretical aspects

This paper investigates commonly used approaches for fatigue crack nucleation analysis in rubber, including maximum principal strain (or stretch), strain energy density and octahedral shear strain criteria. The ability of these traditional equivalence criteria, as well as a recent equivalence criterion (the cracking energy density) to predict multiaxial fatigue behaviour is explored. Theoretical considerations are also introduced relating to the applicability of various fatigue life analysis approaches. These include the scalar nature of traditional equivalence criteria, robustness of the criteria investigated for a wide range of multiaxial loadings, effects of crack closure and applications to non‐proportional multiaxial loadings. It is shown that the notion of a stress or strain amplitude tensor used for the analysis of multiaxial loading in metals is not appropriate in the analysis of rubber due to nonlinearity associated with finite strains and near incompressibility. Taken together, these considerations illustrate that traditional criteria are not sufficiently consistent or complete to permit confident analysis of arbitrary multiaxial loading histories, and that an analysis approach specific to the failure plane is needed. Of the three traditional criteria, maximum principal strain is shown to match most closely to the cracking energy density criterion, in terms of a failure locus in principal stretch space.     

纳米功能化石墨烯/室温硫化硅橡胶复合材料的制备与表征

用KH-550对氧化石墨进行改性, 再对其进行还原, 获得功能化石墨烯(FG), 未经干燥的FG经超声处理后可以稳定分散在质量比9∶1的丙酮/水混合液中; 在高速搅拌和超声分散条件下, 将FG分散液分散到室温硫化(RTV)硅橡胶中, 固化后得到纳米FG(nano-FG)/RTV硅橡胶复合材料。采用FTIR、TEM、SEM、XRD和DSC分析了FG及复合材料的结构和形貌。结果表明: KH-550连接到石墨烯片层表面上, 使其片层起皱、折叠, 部分发生了剥离, 层间距增大到3.46 ; FG经过超声处理后剥离成透明至半透明的片层; nano-FG/RTV硅橡胶复合材料的断面结构为褶皱结构, 不同于纯硅橡胶, 也未出现微观相分离; 与硅橡胶相比, 复合材料的T_g、T_m和结晶度均有所提高。复合材料的力学性能测试结果表明, nano-FG对RTV硅橡胶具有明显的补强效果, 当nano-FG质量分数为0.5 %时, nano-FG/RTV硅橡胶复合材料的拉伸强度比纯RTV硅橡胶提高了一倍多, 达到了0.43 MPa; 断裂伸长率也提高了52%, 达到了265%。      

改性纳米SiO2/硅橡胶复合材料的制备及性能

为提高纳米SiO₂在硅橡胶（SR）基体中的分散性及两相间的界面结合力,设计以羟基硅油（HSO）和γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）为纳米SiO₂的表面封端改性剂,并将改性SiO₂与双组份加成型液体SR复合得到改性纳米SiO₂/SR复合材料。通过一系列表征手段对改性纳米SiO₂的形貌结构及其在乙醇中的分散性等进行分析,研究了改性纳米SiO₂对纳米SiO₂/SR复合材料的断面形貌、力学性能及热稳定性的影响。结果表明:KH570成功接枝到纳米SiO₂表面并与SR基体间形成化学键。当HSO协同KH570改性纳米SiO₂时,可有效改善纳米SiO₂在SR基体中的分散性能及纳米SiO₂与SR两相间的界面结合性能,并显著提高纳米SiO₂/SR复合材料的力学性能和热稳定性。将SiO₂∶HSO∶KH570以质量比为2.0∶0.2∶0.6处理的改性纳米SiO₂粒子,得到的改性纳米SiO₂/SR复合材料起始热分解温度提高了230℃。当SiO₂∶HSO∶KH570质量比为2.0∶0.2∶0.45时,改性纳米SiO₂/SR复合材料的拉伸强度和断裂伸长率分别提高了约1倍。