Synthesis and characterizations of modified expanded graphite/emulsion styrene butadiene rubber nanocomposites: Mechanical,dynamic mechanical and morphological properties

The present research work demonstrated the reinforcing effect of expanded graphite (EG) and modified EG (MEG) with and without carbon black (CB) on the physical, mechanical and thermo-mechanical properties of emulsion polymerized styrene butadiene rubber (SBR) vulcanizates. In separate batches, EG and MEG flakes with and without CB were incorporated into the SBR by melt blending. The microstructures of the nanocomposites were precisely characterized by wide angle X-ray diffraction (WAXD) analysis and high resolution transmission electron microscope (HR-TEM). EG and MEG filled SBR compounds showed improvement in the curing features, mechanical, thermal and dynamic mechanical properties than their respective controls.     

Development of expanded graphite filled natural rubber vulcanizates in presence and absence of carbon black: Mechanical,thermal and morphological properties

As nanosized expanded graphite (EG) reveals a similar layered structure like organoclay and also it has a high expansion ratio so rubber chains can easily be intercalated into the gallery space. To improve the dispersion of EG in the rubber matrices, primarily the surface modification of the expanded graphite have been done and then the modified expanded graphite (MEG)/polar compatibilizer [epoxidized natural rubber (ENR)] master batch have been prepared by solution mixing method in the laboratory. After that the MEG/ENR master batch have been mixed with bulk natural rubber (NR) in presence and absence of carbon black (CB) in a laboratory scale open two roll mixing mill. Wide angle X-ray diffraction (WAXD) and high resolution transmission electron microscopic (HR-TEM) analysis of the nanocomposites revealed that MEG was intercalated and as well as delaminated in the NR matrix. Scanning electron microscope (SEM) images of the nanocomposites showed very rough surface than the pure NR matrix. In presence of expanded graphite the crack paths are channelized and coincide in one point suggesting the effect of plate like expanded graphite to acts as a barrier. We have got improved mechanical, thermal and dynamic mechanical properties for the MEG and MEG/CB loaded NR compounds compared to EG and EG/CB loaded NR compounds.     

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。     

碳纳米管/丁苯橡胶复合材料的电学性能

采用喷雾干燥法可制备不同配比的碳纳米管（Carbon nanotubes,CNTs）/粉末丁苯橡胶复合材料,观察CNTs在橡胶基体中的分散情况,检测复合材料的导电性能及介电性能,并进行了简要的理论分析。结果表明:CNTs在橡胶基体中获得了充分均匀的分散,有利于CNTs改性补强作用的发挥。与纯胶样品及填充炭黑（Carbon black,CB）样品相比, 填充CNTs样品在8~18GHz下具有较高的介电常数及低介电损耗。随着CNTs加入量的增加,CNTs/粉末丁苯橡胶复合材料的电导率逐渐升高,当CNTs加入量为60phr（per hundred rubber）时,与纯胶样品及添加60phr CB样品相比,电导率提高近10个数量级;复合材料内部导电同时存在隧道导电机制和渗逾导电机制。采用喷雾干燥法制备的CNTs/粉末丁苯橡胶复合材料,将是一种综合性能良好的新型纳米复合材料,有望在抗静电橡胶、电磁屏蔽及介电材料等领域获得应用。      

Investigations on the addition of styrene butadiene rubber in natural rubber and dichlorocarbene modified styrene butadiene rubber blends

This paper focuses on the use of styrene butadiene rubber (SBR) as a viscosity modifier in novel blends of natural rubber (NR) and dichlorocarbene modified styrene butadiene rubber (DCSBR). The processing characteristics, vulcanisation kinetics, stress-strain behaviour, mechanical properties and low temperature transition of the blends have been examined in order to analyse the influence of SBR in the blends. The change in cross-link density values from stress strain behaviour and equilibrium swelling data has been correlated with the technological properties of the blends. The excellent mechanical properties and the increased cross-link density in blends in the presence of 5—10 phr of styrene butadiene rubber reveals the viscosity modifying action of SBR in NR/DCSBR blends. The variation in viscosities of these blends with the addition of SBR is reflected in the DSC thermograms. The resulting blends show very high resistance to thermal ageing as compared to those without SBR.     

Modified phosphate pigments as high performance reinforcing materials for rubber vulcanizates

This study is focusing on the synthesis of novel modified micronized phosphate pigments as reinforcing materials for the vulcanizates of styrene-butadiene rubber (SBR), natural rubber (NR) and their blends. The metal phenyl phosphate pigments were prepared via co-precipitation process from the reaction of equimolar ratios of the disodium phenyl phosphate solution and the water soluble salts of the investigated metals. The white prepared phosphate pigments were introduced in the rubber formulations to replace carbon black the highly common and commercial reinforcing material in rubber vulcanizates. The rheometric characteristics, physico-mechanical properties in addition to the accelerated aging properties of the rubber vulcanizates were investigated, discussed and interpreted in the light of previous studies. The results showed that, phenyl phosphate pigments exercised a great effect on the rheological characteristics (scorch time, cure time…etc.), and achieved high performance and pronounced mechanical properties. The stress and strain at yield and at rupture of the loaded rubber with modified phosphates are better than that loaded with carbon black and Hisil e.g. tensile strength data were (20.0–23.4), 18.01 MPa and 15.05 for rubber blend vulcanizates loaded with 30 phr of modified phosphate pigments, carbon black and Hisil, respectively.     

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.     

Blends of ultrasonically devulcanized tire-curing bladder and butyl rubber

The devulcanization of the butyl rubber based tire-curing bladder was carried out with a grooved barrel ultrasonic extruder. The devulcanized rubber was blended at different ratios with the carbon black filled virgin butyl rubber and cured. The rheological and mechanical properties, as well as gel fraction and crosslink density of the revulcanized rubber and vulcanizates of blends have been measured. The blend of ground tire-curing bladder and carbon black filled butyl rubber has also been prepared for comparison purpose. Compared to the blend containing the ground rubber, compounding of the blends containing the devulcanized bladder were easier and their vulcanizates had smoother surface. In addition, the vulcanizates containing devulcanized tire-curing bladder and virgin rubber showed substantially improved mechanical properties than the vulcanizate of the devulcanized rubber alone.     

Gamma irradiation aging of NBR/CSM rubber nanocomposites

The effect of gamma-irradiation on the acrylonitrile butadiene/chlorosulphonated polyethylene rubber blends (NBR/CSM) based nanocomposites containing carbon black (CB) and silica filler (Si) were investigated by TG-DTG and ATR-FTIR techniques. The silica (with primary particle size of 22 nm) was added in content of 0, 10, 20 and 30 phr and carbon black (with primary particle size 40–48 nm) was added in content of 30 phr and rubber blend compounds were prepared. The obtained elastomeric materials were aging to different γ-irradiation doses (100, 200 and 400 kGy). The cure and mechanical properties of obtained nanocomposites were determined. Incorporating 20 phr of silica to the control NBR/CSM rubber blends containing 30 phr CB resulted 152% increase in tensile strength, 116%, in elongation at break and 142% modulus at 100% elongation, according to synergistic effect between the fillers. FTIR measurements of aged samples estimated the formation of alcohols, ethers and small amounts of lactones, anhydrides, esters and carboxylic acids after exposure to lower doses of γ-radiation (100 kGy). On the basis of the obtained spectra the formation of shorter polyene sequences and aromatic rings in aged elastomeric samples are assumed. The results show that 30 phr of carbon black (CB) and 20 phr of silica are needed for the best gamma aging resistance of NBR/CSM rubber nanocomposites. The result of radiation exposure is decrease in mechanical properties. The dose at which ultimate mechanical properties decreased was at 200 kGy. TG-DTG measurements estimated decrease in thermal stability of gamma-irradiated NBR/CSM rubber blend based nanocomposites. Silica reinforced NBR/CSM rubber blend had better radiation resistant than carbon black. Rough and heterogeneity of fracture surfaces has been observed for NBR/CSM rubber blends filled with silica. More uniform morphology of fracture surfaces according to high polymer–filler interaction and low filler–filler interaction has been observed for CB/Si filled NBR/CSM rubber blend.     

研磨溶液对改性石墨矿表面性质及微观结构的影响

使用行星式球磨机对石墨矿粉(G)进行湿法球磨改性,以硅烷偶联剂Si-69为改性剂,考察了球磨溶液对石墨矿粉微观结构和表面性质的影响,然后将改性石墨矿粉填充到丁苯橡胶中,考察了改性石墨/丁苯胶复合材料的力学性能及微观结构.结果表明,球磨溶液不同,改性石墨矿粉的微观结构和表面性质有所不同.以异丙醇为球磨溶液的改性石墨矿粉(...     

改性累托石粉体的制备及其填充橡胶复合材料的结构与性能

利用喷雾干燥法制备了硅烷偶联剂KH550改性的累托石粉体, 考察了喷嘴进口温度对制备的累托石粉体表面性质、结构及形貌的影响。将累托石粉体分别加入到丁苯橡胶(SBR)、天然橡胶(NR)和丁腈橡胶(NBR)中, 通过熔融共混法制备了改性累托石/橡胶复合材料, 研究了累托石在橡胶基体中的分散状态及其对基体的增强效果。结果表明: 随着进气温度的提高, 与累托石复合的KH550的量也随之增加; KH550分子插层进入累托石层间, 阻碍了片层的再聚集, 片层堆砌更加无序蓬松; 改性累托石在SBR中出现了局部团聚现象, 在NBR中分散较均匀, 而在NR中分散状态最好; 与相应的纯橡胶相比, 改性累托石填充的SBR和NBR基复合材料的各项力学性能均有所提高, 而其填充的NR基复合材料的定伸应力提高, 拉伸强度和撕裂强度基本不变, 断裂伸长率有所下降。     

氧化石墨烯/天然橡胶-丁腈橡胶复合材料的制备与性能

为研究氧化石墨烯（GO）对共混橡胶的补强改性作用,首先,通过改进的Hummers方法制备了GO,并通过乳液共混法制备了GO/天然橡胶（NR）-丁腈橡胶（NBR）复合材料;然后,采用SEM、FTIR、XRD、溶胀测试和力学性能测试表征了GO、NR-NBR硫化胶和GO/NR-NBR复合材料的微观形态、结构和力学性能。结果表明:所得GO含有大量的含氧官能团,氧化效果较好;橡胶基体中GO分散均匀,且GO/NR-NBR复合材料的拉伸断面粗糙程度显著增加;GO的填充可以提高复合材料的表观交联密度;GO/NR-NBR复合材料的力学性能随着GO含量的增加而改善,当GO含量为3.0wt%时,GO/NR-NBR复合材料的拉伸强度、100%定伸应力和邵氏A硬度分别提高了53.3%、67.3%和10.5%,断裂伸长率降低了9.6%。      

Effects of particle size and structure of carbon blacks on the abrasion of filled elastomer compounds

The effects of the particle size and structure of various carbon blacks on friction and abrasion behavior of filled natural rubber (NR), styrene–butadiene rubber (SBR) and polybutadiene (BR) compounds were investigated using a modified blade abrader. The effect of particle size and structure on abrasion resistance should be considered for the optimum design of desired wear properties. Characteristic parameters were introduced from the particle size and the structure of carbon blacks, with a linear relationship between the Young’s modulus and these characteristic parameters. The frictional coefficient depended not only on the particle size, but also on the structure of carbon black. The rates of abrasion were decreased with increasing surface area and developing structure of carbon blacks. Abrasion rates of the compounds were found to be proportional to a power n of the applied frictional work input. It was also observed that BR compounds caused much slower wear than NR and SBR compounds. The worn surfaces of the rubber compounds filled with carbon black having smaller particle size and a more developed structure showed narrower spaced ridges and better abrasion resistance. It means that smaller particle size and better structure development of carbon black resulted in improved abrasion resistance.     

Mechanical performance of styrene-butadiene-rubber filled with carbon nanoparticles prepared by mechanical mixing

Reinforcement of styrene-butadiene-rubber (SBR) was investigated using two different carbon blacks (CBs) with similar particle sizes, including highly structured CB and conventional CB, as well as multi-walled carbon nanotube (MWCNT) prepared by mechanical mixing. The attempts were made to examine reinforcing mechanism of these two different classes of carbon nanoparticles. Scanning electron microscopy and electrical conductivity measurement were used to investigate morphology. Tensile, cyclic tensile and stress relaxation analyses were performed. A modified Halpin-Tsai model based on the concept of an equivalent composite particle, consisting of rubber bound, occluded rubber and nanoparticle, was proposed. It was found that properties of CB filled SBR are significantly dominated by rubber shell and occluded rubber in which molecular mobility is strictly restricted. At low strains, these rubber constituents can contribute in hydrodynamic effects, leading to higher elastic modulus. However, at higher strains, they contribute in stress hardening resulting in higher elongation at break and higher tensile strength. These elastomeric regions can also influence stress relaxation behaviors of CB filled rubber. For SBR/MWCNT, the extremely great inherent mechanical properties of nanotube along with its big aspect ratio were postulated to be responsible for the reinforcement while their interfacial interaction was not so efficient.     

Mechanical and tribological properties of acrylonitrile–butadiene rubber filled with graphite and carbon black

In this work, acrylonitrile–butadiene rubber (NBR)/expanded graphite (EG)/carbon black (CB) micro- and nanocomposites were prepared by two different methods, and the resulting mechanical and tribological properties were compared with those of NBR/CB composites. Meanwhile, the effects of graphite dispersion and loading content, as well as the applied load and sliding velocity on the tribological behavior of the above composites under dry friction condition were also evaluated. The worn surfaces were analyzed by scanning electron microscopy (SEM) to disclose wear mechanism. As expected, the better the dispersion of graphite, the more remarkable enhancement on tensile and dynamic mechanical properties, and the greater reduction in the coefficient of friction (COF) and specific wear rate (W_s). It was found that a small amount of EG could effectively decrease COF and W_s of NBR/CB composites because of the formation of graphite lubricant films. The COF and W_s of NBR/CB/EG composites show a decreasing trend with a rise in applied load and sliding velocity. NBR/CB/EG nanocomposite always shows a stable wearing process with relatively low COF and W_s. It is thought that well-dispersed graphite nano-sheets were beneficial to the formation of a fine and durable lubricant film.     

纳米石墨片-羧基丁腈橡胶复合材料结构形态与电性能

利用电子束辐照法制备纳米石墨片(GnPs)-羧基丁腈橡胶(XNBR)复合材料,研究辐射剂量对胶乳共混体系稳定性的影响,并对GnPs-XNBR复合材料的交联度、热稳定性、电性能及其形貌予以表征。结果表明:辐照后GnPs-XNBR复合材料的交联度、热稳定性和体积电阻率提高,而共混乳液的稳定性显著降低。辐照强化了乳胶粒子与石墨片之间的界面结合,形成胶乳粒子包覆石墨片的核-壳结构,进而提高石墨片在基体中分散均匀性,并使GnPs-XNBR复合材料的热稳定性和介电常数提高,导电性和介电损耗降低。     

Use of rice husks as potential filler in styrene butadiene rubber/linear low density polyethylene blends in the presence of maleic anhydride

In the present study, rice husks filled styrene butadiene rubber (SBR)/linear low density polyethylene (LLDPE) 50/50 blends with a compatibilizer, maleic anhydride (MAH) were prepared using a brabender plasti-corder. Virgin SBR/LLDPE blend was also prepared. The physico-mechanical as well as dielectric properties were investigated. Increasing MAH concentrations in SBR/LLDPE blends resulted in an increase in the tensile strength, elongation at break and hardness. After a certain concentration (2.5 phr), a reduction in these properties was found. On the other hand an increase in the dielectric properties as well as in the mass swell in both toluene and oil with MAH was noticed. After certain concentration of rice husk filler (25 phr) an abrupt increase in permittivity ε′ and dielectric loss ε″ was obtained. These results are supported by the mechanical properties measurements. The scanning electron microscopy (SEM) indicates that the presence of MAH increases the interfacial interaction between SBR/LLDPE blends on one hand and also rice husk filler and the blend on the other hand.     

Rubber composites based on graphene nanoplatelets,expanded graphite,carbon nanotubes and their combination: A comparative study

Solution styrene butadiene rubber (S-SBR) composites reinforced with graphene nanoplatelets (GnPs), expanded graphite (EG), and multiwalled carbon nanotubes (MWCNTs) were prepared and the electrical and various mechanical properties were compared to understand the specific dispersion and reinforcement behaviours of these nanostructured fillers. The electrical resistivity of the rubber composite gradually decreased with the increase of filler amount in the composite. The electrical percolation behaviour was found to be started at 15 phr (parts per hundred rubber) for GnP and 20 phr for EG filled systems, whereas a sharp drop was found at 5 phr for MWCNT based composites. At a particular filler loading, dynamic mechanical analysis and tensile test showed a significant improvement of the mechanical properties of the composites comprised of MWCNT followed by GnP and then EG. The high aspect ratio of MWCNT enabled to form a network at low filler loading and, consequently, a good reinforcement effect was observed. To investigate the effect of hybrid fillers, MWCNT (up to 5 phr) were added in a selected composition of EG based compounds. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties.     

丁苯胶/甲基丙烯酸锌/气相法白炭黑纳米复合材料

制备了三相纳米复合材料SBR／ZDMA／气相法白炭黑。采用了两种气相法白炭黑,U—fumed silica是一种未改性的气相法白炭黑,M—fumed silica是一种采用硅烷偶联剂Si69表面改性的气相法白炭黑。主要研究了气相法白炭黑和ZDMA之间的协同补强效应。研究结果显示,单独添加同样份数的改性气相法白炭黑和未改性气相法白炭黑对硫化胶物理机械性能的影响不同,改性气相法白炭黑的效果明显优于未改性气相法白炭黑。单独添加气相法白炭黑,体系的物理机械性能仍然维持在较低值。当同时添加气相法白炭黑和ZDMA时,会观察到明显的协同补强效应。交联密度和丙酮抽出试验表明对气相法白炭黑进行表面改性和在体系中添加ZDMA均会减弱气相法白炭黑表面羟基的影响。扫描电镜显示改性后气相法白炭黑在SBR中的分散性得到提高。在体系中添加ZDMA会提高气相法白炭黑的分散性。     

Morphology/behaviour relationship of nanocomposites based on natural rubber/epoxidized natural rubber blends

In order to analyze the effect of an epoxidized natural rubber (ENR) and filler treatment on the morphology and behavior of natural rubber (NR) nanocomposites, blends of these polymers have been prepared. The nature and extent of the clay dispersions in the filled samples were evaluated by X-ray diffraction. In the presence of ENR, an exfoliated structure was obtained which suggests that enough rubbery polymer was incorporated into the interlayer spacing. The effect of clay in rubber compounds was analyzed through rheological, mechanical and swelling characterization. A sensible improvement in the nanocomposite properties was observed by the addition of organoclay. It has been deduced that the properties of the compounds strongly depend on the extent of the silicate nanolayers dispersion into the rubber matrices as well as on the organoclay type and elastomer compatibility.