补强填料对EVM-GMA/XNBR并用胶性能的影响

研究了不同用量的两种填料(炭黑、白炭黑)对EVM-GMA/XNBR并用胶的加工性能、力学性能、Payne效应、DIN磨耗的影响,并进行了微观结构的分析。结果表明,炭黑和白炭黑作为EVM-GMA/XNBR并用胶的补强填料能够缩短工艺正硫化时间,提高硫化效率;同时使复合材料的机械性能和耐磨性能提高。当炭黑做补强填料时,复合材料的压缩永久变形较小,炭黑的用量为40份时,复合材料的综合性能最好。     

炭黑/白炭黑复合填料网络在天然橡胶屈挠疲劳过程中的作用分析

通过改变填料体系中炭黑/白炭黑的用量比,制备出具有不同填料网络结构的硫化胶,通过胶料的硫化特性、交联密度、结合胶含量、Payne效应、损耗特性对填料网络结构进行表征并建立填料网络结构模型,最后通过各种性能测试考察了填料网络对橡胶动静态力学性能和屈挠疲劳性能的影响,建立了复合填料网络结构和屈挠疲劳性能的相关性。结果表明,白炭黑-白炭黑相互作用强于炭黑-炭黑相互作用,但白炭黑与橡胶基体的结合作用差;复合填料网络在屈挠疲劳过程中产生的内耗小,白炭黑/炭黑质量比为20/20时,硫化胶的疲劳性能最好。     

硅藻土/白炭黑复合填料补强天然橡胶复合材料的性能研究

以硅藻土和白炭黑作为复合填料填充天然橡胶（NR）,研究硅藻土用量对硅藻土/白炭黑复合填料补强天然橡胶（DCNR）复合材料性能的影响。结果表明：随着硅藻土用量的增大,DCNR复合材料的t10和t90先增大后减小;硅藻土用量较小时,可提高DCNR复合材料的邵尔A型硬度;硅藻土用量过大,易产生明显的团聚,从而降低硅藻土/白炭黑复合填料对NR基体的补强效果,使得DCNR复合材料的综合物理性能下降。     

白炭黑/炭黑混合填料对氟橡胶/硅橡胶共混胶性能的影响

采用沉淀白炭黑和高耐磨炭黑作为氟橡胶/硅橡胶共混胶的填料.研究以不同质量比混合的沉淀白炭黑和高耐磨炭黑对氟橡胶/硅橡胶共混胶的硫化特性、门尼粘度、力学性能、耐热老化性能和耐油性能的影响,并通过RPA分析表征填料-填料的相互作用,采用SEM表征白炭黑/炭黑混合填料在氟橡胶/硅橡胶共混胶中的分散性.结果表明,随着混合填料中白炭黑所占比例的增大,氟橡胶/硅橡胶共混胶的硫化转矩升高,焦烧时间(t10)缩短,正硫化时间(t90)延长,门尼粘度增大.氟橡胶/硅橡胶共混胶的力学性能,耐热老化性能和耐油性能都随着混合填料中白炭黑用量增多而提高.RPA分析表明,全部采用白炭黑补强的共混胶Payne效应最明显,炭黑补强的共混胶Payne效应最弱.SEM分析表明,白炭黑在共混胶中分布比炭黑更加均匀,填料聚集体粒径较小.     

环氧化杜仲橡胶的制备及其在丁苯橡胶/白炭黑复合材料中的应用

以杜仲橡胶(EUG)的石油醚溶液为原料、过氧乙酸为环氧化试剂,通过乳液法工艺对EUG进行环氧化改性制备了环氧化EUG(EEUG),采用核磁共振波谱对EEUG进行了表征,研究了EEUG用量对丁苯橡胶/白炭黑复合材料加工性能、微观形态、物理机械性能和动态力学性能的影响。结果表明,用EEUG改性丁苯橡胶/白炭黑复合体系时,可以明显改善白炭黑在丁苯橡胶基体中的分散情况,降低白炭黑引起的延迟硫化效应,减轻Payne效应,提高其硫化胶的力学性能、耐磨性能及压缩疲劳性能;改性后的丁苯橡胶/白炭黑硫化胶的动态力学性能明显提高,其储能模量增大,滞后损失减少;但是当EEUG用量较大时改性效果不佳。     

环氧化杜仲胶改性丁苯橡胶/白炭黑复合材料的制备与性能

研究了环氧化杜仲胶(EEUG)作为改性剂对丁苯橡胶(SBR)/白炭黑复合材料的性能及白炭黑分散性的影响,并与偶联剂KH-550和大分子界面改性剂三元乙丙橡胶接枝马来酸酐(EPDM-gMMH)作改性剂制备的复合材料进行了对比。结果表明,EEUG、EPDM-g-MMH和KH-550均能降低白炭黑引起的硫化延迟效应,减轻填料聚集导致的Payne效应,提高SBR/白炭黑复合材料的力学性能及耐磨性,改善压缩疲劳性能;采用EEUG改性的SBR/白炭黑复合材料具有更加优异的力学性能、耐磨性及动态力学性能。     

喷雾法黏土/白炭黑复合填料增强溶聚丁苯橡胶/顺丁橡胶复合材料的结构与性能

通过喷雾干燥工艺制备了黏土/白炭黑复合填料,用其等质量替代部分白炭黑,以共同增强溶聚丁苯橡胶/顺丁橡胶复合材料。考察了填料在复合材料基质中的分散状态,研究了黏土用量不同的填料所增强溶聚丁苯橡胶/顺丁橡胶混炼胶的硫化特性和加工性能,比较了其硫化胶的力学性能、动态黏弹性能、抗湿滑性、耐磨性及耐屈挠性等。结果表明,喷雾干燥工艺可使黏土剥离,以纳米片层的状态分散于溶聚丁苯橡胶/顺丁橡胶复合材料中。用喷雾法制备的黏土/白炭黑复合填料可导致溶聚丁苯橡胶/顺丁橡胶混炼胶的硫化时间延长。溶聚丁苯橡胶/顺丁橡胶硫化胶的力学性能随增强填料中黏土用量的增加而先提高后降低;抗湿滑性,特别是耐屈挠性在加入黏土后得到比较明显的改善;滚动阻力和生热增大,耐磨性随黏土用量的增加而逐渐降低。     

白炭黑/溶聚丁苯橡胶复合材料的填料网络结构与动态黏弹性能

用橡胶加工分析仪研究了白炭黑用量和偶联剂Si 69原位改性对白炭黑/溶聚丁苯橡胶复合材料中填料网络结构与动态黏弹性能的影响.结果表明,白炭黑用量为30份(质量,下同)时网络结构尚未形成,不能测定结合胶;填充了50份和 70份的白炭黑复合材料的结合胶含量较低,其网络结构的结点类型以刚性结点为主,混炼胶和硫化胶的Payne效应明显.混炼胶的温度扫描结果表明,随白炭黑用量增加,复合材料中填料的聚集程度加剧.经Si 69原位改性后,复合材料的结合胶含量大大提高,网络结构的结点类型以柔性结点为主,混炼胶和硫化胶的Payne效应明显减弱.在10.04%的大应变下进行频率扫描时,经Si 69原位改性硫化胶的储能模量和损耗因子随频率的增大而增大,且明显低于未改性者.     

硅烷偶联剂对白炭黑与CM/SBR的填料网络及动态性能的影响

采用偶联剂Si-69对白炭黑进行改性。实验表明,随着偶联剂Si-69用量的增多,填料在胶料中的分散性提高,使CM/SBR(氯化聚乙烯/丁苯橡胶)共混胶的力学性能提高,硫化胶的耐老化性能提高,Si-69的加入使白炭黑与橡胶基质的相容性提高,Payne效应减弱。     

用硫化仪数学分析法确定白炭黑在丁苯橡胶中最佳填充量

以谷氨酸二硫代氨基甲酸镧(La-GDTC)改性白炭黑(Si O2)填充丁苯橡胶(SBR),采用硫化仪数学分析法确定了Si O2最佳用量,通过橡胶加工分析仪分析了填料网络结构的形成,研究了SBR/La-GDTC/Si O2复合材料的拉伸性能。结果表明,采用硫化仪数学分析法确定Si O2最佳用量为40份;当Si O2用量不超过40份时,SBR/La-GDTC/Si O2复合材料的Payne效应不明显,当Si O2用量为50份时,复合材料出现了明显的Payne效应;随着Si O2用量的增加,SBR/La-GDTC/Si O2复合材料的拉伸强度先升高后下降,当Si O2用量为40份时达到最大值(28.03 MPa),表明采用硫化仪数学分析法可以快捷、准确确定在橡胶复合材料中无机填料的最佳用量。     

改性纳米二氧化硅的制备及其在溶聚丁苯橡胶/顺丁橡胶并用胶中的应用

摘要：以γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)为修饰剂,采用液相原位表面修饰技术,制备了可分散性纳米二氧化硅,并将这种改性后的纳米二氧化硅应用到溶聚丁苯橡胶/顺丁橡胶体系,对其进行力学性能、磨耗性能、流变性能测试,考察了修饰剂的不同用量对复合材料上述性能的影响。傅里叶红外光谱表明,KH570已经成功通过化学键键合在二氧化硅表面,扫描电镜显示其团聚减弱,分散性提高。橡胶纳米复合材料的力学性能有所改善,在修饰量为25-50mmol/kg时性能最佳;耐磨性能明显提高,尤其是修饰量为50mmol/kg时,磨耗体积最少,降低了33.85%;明显降低了Payne效应,减弱了二氧化硅的团聚,提高了其在橡胶基体中的分散性。     

不同种类低共熔溶剂对白炭黑填充丁苯橡胶物理机械性能的影响

以低共熔溶剂（DES）为白炭黑的改性剂,通过与双[3-（三乙氧基硅）丙基]四硫化物（TESPT）并用进行原位反应改善白炭黑在丁苯橡胶中的分散性,研究了不同种类DES对白炭黑/丁苯橡胶复合材料硫化特性、加工性能、物理机械性能和微观形貌的影响。结果表明,氯化胆碱/尿素与TESPT并用可以明显改善白炭黑在丁苯橡胶中的分散性,使Payne效应减弱,并提升白炭黑/丁苯橡胶硫化胶的力学性能和压缩疲劳性能;氯化胆碱/乙二酸与TESPT并用对提高白炭黑与丁苯橡胶界面结合力效果显著,所得白炭黑/丁苯橡胶复合材料的耐磨性能优异;而当DES用量较大时改性效果不佳。     

NR/SiO_2复合体系结合胶及动态力学性能研究

研究了白炭黑用量和Si69原位改性对NR/SiO2复合体系结合胶含量及其与动态力学性能之间关系的影响。结果表明,随着白炭黑用量的增大,2种复合体系(NR/SiO2/Si69和NR/SiO2)结合胶含量均呈现先增大后减小的趋势。当白炭黑用量达到临界值时,复合体系结合胶含量最大,此时Payne效应开始显现。当白炭黑用量超过临界值时,复合体系结合胶含量减小,形成完善的填料网络结构,出现明显的Payne效应。与NR/SiO2复合体系相比,NR/SiO2/Si69复合体系结合胶含量大大提高,白炭黑用量的临界值也相应提高,Payne效应减弱。     

环氧化天然杜仲橡胶在丁苯橡胶/白炭黑复合体系中的应用

本文主要研究了环氧化天然杜仲橡胶的应用对丁苯橡胶/白炭黑复合体系物理机械性能的影响,并与传统白炭黑分散剂进行分析比较。结果表明,白炭黑分散剂B-52、FS-79和环氧化天然杜仲橡胶均能改善白炭黑引起的硫化延迟,减轻填料聚集导致的Payne效应;与白炭黑分散剂B-52、FS-79相比,环氧化天然杜仲橡胶改性丁苯橡胶(SBR)/白炭黑硫化胶的力学性能更高、耐磨性更好、压缩温升适中,且具有更好的动态力学性能。     

Improved dispersion and physico-mechanical properties of rubber/silica composites through new silane grafting

3-Octanoylthio-1-propyltriethoxysilane (a new silane) grafted styrene butadiene rubber/ silica composites were prepared in the present work, where grafting weight percentage of the base rubber (0%, 2%, 4%, and 6%) and filler content of the composites (0, 5, 15, 35, and 50 phr) were varied to investigate dispersion of the filler in the rubber. A detailed quantitative study of morphology-physical property relationship of the composites using dispersion degree parameter was carried out. Pronounced improvement of dispersion was observed with increasing grafting weight percentage of the base rubber. A mechanism of polymer to filler interaction was shown by Fourier transform infrared spectroscopy. The dispersion rate constant from the torque-time curve increased with the grafting percentage. Bound rubber content and Payne effect measurement indicated improved rubber-filler interaction for the grafted rubber compound. A relation between low strain modulus of the composites and grafting percentage was proposed. The nanoindentation studies gave further insight into the results. Other physico-mechanical properties at different grafting weight percentages at particular filler loading (50 phr) and at different filler loadings at a particular grafting weight percentage (4%) were evaluated. The improved mechanical and dynamic mechanical properties with increasing grafting weight percentage are an indication that this methodology could be used in green tire application.     

改性剂种类对白炭黑补强阻尼硅橡胶性能的影响

以阻尼硅橡胶母胶、气相法白炭黑、改性剂为原料,制成了热硫化阻尼硅橡胶。研究了羟基硅油、六甲基环三硅氮烷、乙烯基三乙氧基硅烷(A-151)、γ-氨丙基三乙氧基硅烷(KH 550)、γ-环氧丙氧基丙基三甲氧基硅烷(KH 560)及其并用对阻尼硅橡胶硫化性能、分散性能、力学性能和黏弹性能的影响。结果表明,硅烷偶联剂类改性剂能显著加快混炼胶的硫化速度、缩短硫化时间;羟基硅油、六甲基环三硅氮烷和KH 560作改性剂时白炭黑的分散效果良好,而采用A 151作改性剂时白炭黑填料网络的Payne效应较明显,但在宽温域(-120~100℃)范围内具有温度稳定性;不同改性剂并用对改善白炭黑分散性没有明显的协同作用;改性剂种类对硫化胶的力学性能影响不大;六甲基环三硅氮烷与KH 560并用时,硅橡胶的阻尼性能最高。     

Comparative role of Interface in reinforcing mechanisms of Nano silica modified by Silanes and liquid rubber in SBR composites

The objective of the present study is to discuss the role of silica-rubber interfacial interactions on vulcanization kinetics, morphology, mechanical and viscoelastic behavior of silica filled styrene butadiene rubber (SBR) composites. Three types of modifiers, namely mono- and bi-functional silanes as well as hydroxyl-terminated poly butadiene (HTPB) liquid rubber were grafted to silica surface, and composites prepared by these fillers were characterized. Results showed that modified silica, especially grafted by bi-functional silane and liquid rubber, accelerated vulcanization reactions, while pristine silica slowed down vulcanization kinetics of SBR. Morphological studies indicated that all modifications improved dispersion of silica, but HTPB-grafted silica was dispersed to a greater extent in SBR. The observed differences in mechanical and dynamic-mechanical properties of vulcanizates were correlated to the significant differences in silica-rubber and silica-silica interactions. Type of interfacial interactions, i.e. rigid covalent bonds in the bi-functional silane, flexible polymeric bonds in the liquid rubber, and weak energetic bonds in the mono-functional silane, could explain the observed differences. Although all modifications reduced filler networking, rigid covalent bonding by bi-functional silane significantly improved mechanical properties and stabilized the filler network. The mono-functional silane lacks these mechanisms. The soft and flexible interphase of HTPB could create bonds and transfer stresses between the rubber matrix and silica to some extent, however it could not improve the mechanical properties and reduce the Payne effect as much as the bi-functional silane did.     

混炼方式对螺旋纳米碳纤维增强天然橡胶复合材料力学性能的影响

采用干法和湿法两种混炼工艺制备了螺旋纳米碳纤维(HCNFs)/炭黑(CB)/天然橡胶(NR)复合材料,通过扫描电镜、拉伸试验机和应变扫描仪分别对所制备复合材料的界面形貌、力学性能和Payne效应进行了测试分析,考察了混炼方式对复合材料宏观力学性能及Payne效应的影响。结果表明,与纯CB填料相比,在干湿两种混炼方式下,添加适量的HCNFs(1～6份)能提高HCNFs/CB/NR复合材料的300%定伸应力、扯断伸长率、拉伸强度和硬度。与干法混炼相比,湿法混炼能明显增强HCNFs/CB/NR复合材料的Payne效应,并提升在HCNFs高添加量(2～6份)条件下的拉伸强度和扯断伸长率,这主要源于湿法混炼能够有效改善HCNFs在橡胶基质中的分散性。     

Structure–property relationships of silica/silane formulations in natural rubber,isoprene rubber and styrene–butadiene rubber composites

The mechanical performance of natural rubber (NR), synthetic poly-isoprene rubber (IR), and styrene–butadiene rubber (SBR) composites filled with various silica/silane systems is investigated. The results are analyzed by referring to micro-mechanical material parameters, which quantify the morphological and structural properties of the polymer and filler network. These are obtained from fits with the dynamic flocculation model (DFM) describing the strongly nonlinear quasi-static stress–strain response of filler-reinforced elastomers as found from multihysteresis measurements of the investigated compounds. We focus on the reinforcement mechanisms of silica compounds with coupling and covering silane, respectively. The fitted material parameters give hints that the coupling silane provides a strong chemical polymer–filler coupling, which is accompanied by improved strength of filler–filler bonds for all three rubbers types. This may result also from the chemical coupling of short chains bridging adjacent silica particles. It implies larger stress values for the coupling silane and, in the case of NR and IR, a more pronounced “Payne effect” compared to the covering silane. In contrast, for SBR, the coupling silane delivers a lower Payne effect, which is explained by differences in the compatibility between rubber type and silane-grafted silica surface. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48435.     

The combination of montmorillonite and silica in styrene–butadiene rubber/polybutadiene rubber tread compounds

Montmorillonite and silica were used as fillers combined with Si69 as their coupling agent in styrene–butadiene rubber/polybutadiene rubber tread compounds to evaluate their interaction and influences on structure and properties of nanocomposites. Microstructure, filler dispersion, curing properties, and tire performance of the compounded rubber were investigated with the aid of X‐ray diffraction, transmission electron microscopy, rheometer, and dynamic‐mechanical analysis, respectively. The results showed that montmorillonite could react with coupling agent and their reaction rate was higher than silica/Si69. The dispersion and exfoliation was promoted by the existence of silica. Fully exfoliated montmorillonite were formed when the montmorillonite/silica ratio was 14 or lower, and the as‐prepared rubber compounds displayed well‐balanced properties. Additionally, coupling agent also influenced the curing kinetics, dynamic, and mechanical properties of the tread compounds. But the structure was not affected by the usage amount of Si69. POLYM. COMPOS., 38:918–926, 2017. © 2015 Society of Plastics Engineers