用红外光谱法研究橡胶/炭黑的界面相互作用

用红外光谱法(FI-IR)研究了橡胶微观结构、炭黑表面基团对橡胶/炭黑的界面相互作用的影响。研究表明,炭黑加入后各分子基团的振动均发生红移。炭黑与富电子的分子链相互作用大,即天然橡胶(NR)>丁基橡胶(BR)>丁苯橡胶(SBR)>丁腈橡胶(NBR);对侧基的影响小于对主链的影响。极性基团丙烯腈含量(ACN)增加,除ν(C≡N)外碳链上的其它基团均发生蓝移,且支链上双键基团所受影响最大。炭黑加入后,减弱了ACN含量增加对链段间作用力的影响,随ACN含量增加各基团蓝移较纯胶的小。门尼黏度仅影响δCH2的振动峰位。     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料动态力学性能的影响

分别采用γ-胺丙基三乙氧基硅烷(KH550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)及双-[γ-(三乙氧基硅)丙基]-二硫化物(Si75)湿法改性白炭黑,将改性后的白炭黑、丁苯橡胶(SBR)制成母炼胶,制备出白炭黑(SiO_2)/丁苯橡胶(SBR)复合材料。利用结合胶含量、橡胶加工分析仪、扫描电镜等方法研究了白炭黑与橡胶基体间的相互作用效果及填料在橡胶基体中的分散性,用压缩疲劳生热、动态力学性能分析和滞后损耗测试研究了白炭黑与橡胶基体的作用效果对丁苯橡胶/白炭黑复合材料生热的影响。结果表明,改性后白炭黑与橡胶基体间的相互作用力增大,分散性明显提高,随橡胶-填料相互作用增大,SiO_2/SBR生热明显降低,其中KH550在硫化过程产生化学反应接枝于橡胶大分子,其改性后的白炭黑与丁苯橡胶相互作用力最大,KH550-SiO_2/SBR生热最低。     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料动态力学性能的影响EI北大核心CSCD

分别采用γ-胺丙基三乙氧基硅烷(KH550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)及双-[γ-(三乙氧基硅)丙基]-二硫化物(Si75)湿法改性白炭黑,将改性后的白炭黑、丁苯橡胶(SBR)制成母炼胶,制备出白炭黑(SiO_2)/丁苯橡胶(SBR)复合材料。利用结合胶含量、橡胶加工分析仪、扫描电镜等方法研究了白炭黑与橡胶基体间的相互作用效果及填料在橡胶基体中的分散性,用压缩疲劳生热、动态力学性能分析和滞后损耗测试研究了白炭黑与橡胶基体的作用效果对丁苯橡胶/白炭黑复合材料生热的影响。结果表明,改性后白炭黑与橡胶基体间的相互作用力增大,分散性明显提高,随橡胶-填料相互作用增大,SiO_2/SBR生热明显降低,其中KH550在硫化过程产生化学反应接枝于橡胶大分子,其改性后的白炭黑与丁苯橡胶相互作用力最大,KH550-SiO_2/SBR生热最低。     

混炼工艺对SBR/BR/CB共混硫化胶性能的影响

为了研究混炼工艺对最终硫化胶性能的影响,利用HAAKE转矩流变仪对不同配比的丁苯橡胶/顺丁橡胶/炭黑进行混炼,混炼采用两种不同的混炼顺序——一种是炭黑首先与丁苯橡胶(SBR)混炼,然后加入顺丁橡胶(BR)混炼;另一种是BR与炭黑混炼之后再加入SBR进行混炼。对制得共混物进行结合胶含量、拉伸以及动态力学性能测试。结果显示,在相同配比下,炭黑首先跟份数多的富相橡胶混炼可以得到较多的结合胶,有利于体系的补强;动态力学测试结果表明硫化胶的粘弹特性受第一段混炼所用橡胶的影响较大,炭黑与柔顺性较好的BR先混炼,共混体系工艺相容性较好。     

混炼工艺对SBR/BR/CB共混硫化胶性能的影响EI北大核心

为了研究混炼工艺对最终硫化胶性能的影响,利用HAAKE转矩流变仪对不同配比的丁苯橡胶/顺丁橡胶/炭黑进行混炼,混炼采用两种不同的混炼顺序——一种是炭黑首先与丁苯橡胶(SBR)混炼,然后加入顺丁橡胶(BR)混炼;另一种是BR与炭黑混炼之后再加入SBR进行混炼。对制得共混物进行结合胶含量、拉伸以及动态力学性能测试。结果显示,在相同配比下,炭黑首先跟份数多的富相橡胶混炼可以得到较多的结合胶,有利于体系的补强;动态力学测试结果表明硫化胶的粘弹特性受第一段混炼所用橡胶的影响较大,炭黑与柔顺性较好的BR先混炼,共混体系工艺相容性较好。     

实用型磁敏橡胶的制备和力学性能

以NR/SBR并用胶为基体制备磁敏橡胶,研究了偶联剂修饰羰基铁粉和不同羰基铁粉、炭黑N660及软化剂橡胶油B-15的含量对其物理、力学性能以及磁流变性能的影响。结果表明:以NR/SBR并用胶为基体,使用适量硅烷偶联KH-570修饰的羰基铁粉(含量为300 Phr)(以纯橡胶或生胶重量为100 Phr的相对量单位,下同)、炭黑N660(含量为40 Phr)和软化剂橡胶油B-15(含量为15 Phr)制备的磁敏橡胶,具有最佳的物理与力学性能和磁流变效应。这是合理结构偶联剂修饰、炭黑增强、软化剂增韧等效应综合作用的结果。     

芳纶短纤维对氢化丁腈橡胶复合材料性能的影响

选用芳纶短切纤维(DCF)和芳纶浆粕(PPTA)2种芳纶短纤维分别补强炭黑N220填充、过氧化物硫化的氢化丁腈(HNBR)胶料,力求制备出高强度、高模量的HNBR复合材料,比较了芳纶短纤维的类型和用量对氢化丁腈胶料性能的影响。实验结果表明,随着DCF用量的增加,HNBR/CB体系的门尼黏度增加,但PPTA对HNBR/CB体系的门尼黏度几乎没有影响;芳纶短切纤维DCF填充的HNBR/CB体系比芳纶浆粕PPTA填充的HNBR/CB体系具有更明显的填料网络;DCF填充的HNBR/CB体系具有更高的硬度、拉伸强度以及撕裂强度。     

多壁碳纳米管填充丁苯橡胶复合材料的研究

采用浓硝酸(HNO3)氧化处理后的多壁碳纳米管(MWNTs)与丁苯橡胶(SBR)及其他配合剂在开炼机上进行混炼加工制备MWNTs／橡胶复合材料，并与炭黑补强橡胶体系进行对比，进而研究了MWNTs／橡胶复合材料的物理性能，并初步探讨了该材料微观结构与性能之间的关系。结果表明：随着MWNTs质量百分含量的增加，橡胶复合材料的力学性能也随之增高；MWNTs／橡胶复合材料的抗撕裂强度(25．9kN／m)、硬度(58)、磨耗(0．22mL/1．61km)性能较炭黑／橡胶体系要好。由MWNTs补强的橡胶对开发具有低滚动滞后性和抗疲劳损失的轮胎胎面胶将有很大的实用潜力。     

挤出法乙丙橡胶/蒙脱土纳米复合材料制备和表征

采用一种新型的有机土蒙脱土(OMM T),通过熔融挤出法制备出了具有优异性能的乙丙橡胶/OMM T复合材料,并与炭黑补强体系进行了对比。透射电子显微镜考察表明,所制备的乙丙橡胶/OMM T纳米复合材料为剥离型结构;力学性能测试结果表明,当有机土含量仅为3份时,复合材料硫化胶的扯断强度是纯胶体系的5.2倍,比同量的高耐磨炭黑增强体系的硫化胶也提高了284%,与加入15份高耐磨炭黑的硫化胶相当;有机土体系撕裂强度也明显高于炭黑体系。还利用门尼黏度测试表征了材料的加工性能。     

高岭土杂化填料填充丁苯橡胶复合材料的热稳定及燃烧性能

将改性高岭土(MK)、炭黑(CB)、白炭黑(PS)填充丁苯橡胶制备了一系列橡胶复合材料,分析了高岭土填充份数、填料类型、填料配合对丁苯橡胶热稳定性及阻燃性能的影响。结果表明:高岭土对丁苯橡胶热稳定性能的增强作用显著,与炭黑相当,略优于白炭黑;与炭黑配合填充时,复合材料的热分解高峰得到有效延迟。复合材料的燃烧氧指数随着高岭土填充量的增大而增大,其阻燃作用与白炭黑相当,略逊于炭黑。高岭土与白炭黑配合填充时的氧指数优于两者单独填充。     

超声分散制备天然橡胶/丁苯橡胶/炭黑/碳纳米管纳米复合材料

通过超声分散制备了分散均匀的碳纳米管(CNTs)/天然橡胶母料,利用母料制备了天然橡胶(NR)/丁苯橡胶(SBR)/炭黑(CB)/碳纳米管复合材料。通过比较常规搅拌、双辊混炼和超声分散三种方法对碳纳米管的分散及对复合材料性能的影响,表明超声分散能实现碳纳米管在基体中均匀分散,CNTs和CB的协同作用提高了复合材料的力学性能,当CB/CNTs之比为37/3时力学性能最高,与未加CNTs增强的体系相比,拉伸强度提高了6.4%。当CNTs含量为7phr,与未加CNTs的体系相比,压缩模量提高了20%。     

Preparation and properties of powder styrene-butadiene rubber composites filled with carbon black and carbon nanotubes

Carbon nanotubes (CNTs) and carbon black (CB) filled powder styrene-butadiene rubber (SBR) composites were prepared by spray drying of the suspension of CNTs and CB in SBR latex. The powders were sphere like and fine with uniform diameters of 10-15 μm. Experimental results showed that the introduction of CNTs into the matrix was beneficial to improve the security of the vulcanization of the rubber composites, and the dynamic and basic mechanical properties of the CNTs/SBR composites were better than those of CB/SBR and neat SBR composites. Observations on the microstructure of the composites indicated that CNTs were well dispersed in the matrix. Morphology of the fracture confirmed that the bonding between CNTs and rubber matrix was strong and load can be transferred to CNTs efficiently during the mechanical property tests. Moreover, the powder SBR composites containing well-dispersed CNTs could be perfect candidate as additives for other polymers.     

导电炭黑填充硅橡胶的电阻温度系数

以炭黑(CB3100)为导电相,硅橡胶为基质制备导电复合材料。研究导电橡胶中炭黑质量分数对电阻温度系数的影响,并用填料对电阻温度系数的影响。以隧道效应理论为基础,给出了导电炭黑填充橡胶的电阻温度系数计算模型,结合实验得到温度对导电炭黑/硅橡胶电阻温度系数的影响主要体现在对其电阻率的影响;基体的体积热膨胀提高复合材料的电阻率,提高了正电阻温度系数;炭黑粒子间的隧道效应降低复合材料的电阻率,增强了负电阻温度系数;在炭黑/硅橡胶中加入少量碳纳米管,利用碳纳米管和炭黑的协同补强效应,使复合材料的导电性和稳定性提高。     

A novel assembled carbon black/carbon nanotubes (CB/MWCNT) nano-structured composite for pressure-sensitive conductive silicon rubber (SR)

In this paper, a novel “grape string” carbon black/multi-wall carbon nanotubes (CB/MWCNT) structure was obtained by electro-static assembly method to enhance the resistance stability of the carbon material filled silicone rubber (SR). Carbon black (CB) and multi-wall carbon nanotubes (MWCNT) were surface modified by sulfonic dodecyl benzene sodium and cetyltrimethylammonium bromide to provide negatively charge and positively charge, respectively. Electric conductive sheet of CB/MWCNT/SR composite was obtained by mixing and vulcanizing. The assembly effect and dispersion state of the composites were analyzed by transmission electron microscopy and scanning electron microscopy. The electrical conductivity and dynamic pressure-resistance characteristic of CB/MWCNT/SR with different doping ratio and dosage were tested. The results show that the proper weight ratio 3:2 of CB:MWCNT for electrostatic assembly can cause the stable “grape string” nano-structure. The conductivity and pressure-resistance characteristic are superior when the volume fraction of “grape string” nano-composites reaches 22%, which will provided with less filler fraction and better stress sensitivity, compared with single component carbon black filler.     

Effect of expanded graphite and modified graphite flakes on the physical and thermo-mechanical properties of styrene butadiene rubber/polybutadiene rubber (SBR/BR) blends

The aim of the present research work is to develop expanded graphite (EG) and isocyanate modified graphite nanoplatelets (i-MG) filled SBR/BR blends, which can substitute natural rubber (NR) in some application areas. The present study investigated the effect of i-MG on the physical, mechanical and thermo-mechanical properties of polybutadiene rubber (BR), styrene butadiene rubber (SBR) and SBR/BR blends in the presence of carbon black (CB). Graphite sheets were modified to enhance its dispersion in the rubber matrices, which resulting in an improvement in the overall physical and mechanical properties of the rubber vulcanizates. Compounds based on 50:50 of BR and SBR with ∼3 wt% nanofillers with CB were fabricated by melt mixing. The morphology of the filled rubber blends was investigated by wide angle X-ray diffraction (WAXD) and high resolution transmission electron microscopic (HR-TEM) analyses. The intercalated and delaminated structures of the nanofiller loaded rubber blends were observed. Scanning electron microscopic (SEM) analysis of the cryo-fractured surfaces of the rubber compounds showed more rough and tortuous pathway of the fractured surfaces compared to the fractured surfaces of the only CB loaded rubber composites. Filled rubber compounds exhibit increase in the ΔS (torque difference) value, reduced scorch and cure time compared to their respective controls. Dynamic mechanical thermal analysis (DMTA) of the filled rubber compounds shows an increase in the storage modulus compared to the controls. Isocyanate modified graphite nanoplatelets (i-MG) containing rubber compounds in the presence of CB showed an increase in the mechanical, dynamic mechanical, hardness, abrasion resistance and thermal properties compared to the alone CB filled rubber vulcanizates.     

过硫酸铵改性炭黑通过胶乳混合法补强天然橡胶胶乳

用过硫酸铵水溶液改性炭黑,制备亲水性的炭黑悬浮液。通过红外光谱仪和热失重表征改性后炭黑表面含氧基团的变化。利用激光粒度分析仪、紫外可见分光光度计观察炭黑水溶液的分散性和分散稳定性,改性前后粒径由155.7nm降到114.2 nm。采用胶乳共混法制备改性炭黑/天然橡胶胶乳复合材料的性能明显增强,拉伸强度提高14.5%,撕裂强度提高56.5%。通过扫描电镜(SEM)观察发现,改性后的炭黑在橡胶基体中粒径小且分散均匀,与基体的界面结合力增强,炭黑的补强效果得到提高。     

稻壳源白炭黑/炭黑并用对天然橡胶协同补强作用研究

通过扫描电镜观察了稻壳源白炭黑(RHS)在天然橡胶(NR)交联体系中的分散,显示RHS作为刚性补强粒子微观呈纳米尺度均匀分布,这是补强作用的基础。依据非平衡态分子动力学原理,探究了RHS纳米粒子与炭黑(CB)对NR的协同补强作用机理。通过研究双相填料(RHS/CB)对NR协同补强作用,不同的RHS/CB比例对协同补强作用影响较大,适宜的用量比不仅提高物理力学性能,同时改善动态力学性能。     

Effect of filler dispersion degree on the Joule heating stimulated recovery behaviour of nanocomposites

Composites based on highly branched ethylene-1-octene copolymer (EOC) and carbon black (CB) with different dispersion degree of CB were prepared. The method of the online measured electrical conductance/resistance was used to monitor the change of the electrical conductance/resistance of the composites during the preparation processes, i.e. mixing and cross-linking. It was found that the kinetics of thermally stimulated shape-memory recovery of CB filled EOC is strongly influenced by the filler dispersion degree, which actually affects the heat transfer in the composites. Using a special arrangement of experiments the Joule heating stimulated shape-memory behaviour was quantified. CB dispersion degree and related electrical resistivity determine the extent of the Joule heating stimulated shape-memory behaviour. Composite collected at the maximum in the online measured conductance–time characteristics showed the best shape-memory effect owing to the highest electrical conductivity in the solid state. The CB filled EOC showed a negative thermal coefficient of resistivity (NTC) effect, which accelerates the temperature increase and shape-memory recovery of the composites when applying a voltage.     

Effect of corn powder as filler in radial passenger tyre tread compound

The present context of technological scenario, requirement of developing low rolling resistance passenger radial tyres with naturally occurring environmental friendly materials is inevitable. Several studies have been reported by using silica filler in place of carbon black for improving the rolling resistance property. In the present study, an attempt has been made to investigate the effect of biodegradable Indian corn powder in tyre tread compound as filler. The effect of corn powder in gum and filled compound of both natural rubber (NR) and styrene butadiene rubber (SBR) based compound has been studied. It was found that corn powder of 200-mesh size increased thermal stability of NR compound and acted as a non-reinforcing filler. It also affected the fatigue properties and abrasion loss when the carbon black was partially replaced with corn powder. However, an improvement in the temperature build up (TBU) and tan δ at 60 °C (a representative of rolling resistance property of tyre) was observed.