炭黑补强异戊橡胶和天然橡胶性能之对比研究

用填充炭黑的异戊橡胶（IR）和天然橡胶（NR）分别研究其硫化特性、力学性能、热空气老化性能和动态力学性能。结果表明,异戊橡胶比天然橡胶的硫化速度慢,焦烧时间长。随着炭黑用量的增多,IR和NR的300％定伸应力增大,拉伸强度和拉断伸长率都下降,撕裂强度出现了峰值。炭黑用量增加到40份时,IR的拉伸强度下降最缓慢,耐老化性能最好;而NR随炭黑用量增加,其拉伸强度下降加快,耐老化性能变差。0℃时IR的损耗因子大于NR的损耗因子;60℃时,IR的损耗因子小于NR的损耗因子。     

碳纳米管炭黑天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶补强的理想填料。本文中我们采用两种不同牌号的碳纳米管(分别为Flotube 7000、9011)与炭黑N660作为实验原料,制备了碳纳米管/炭黑/天然橡胶复合材料,并对其性能进行了探讨。结果发现：碳纳米管的加入能明显提高复合材料的定伸应力,具有一维取向排列且长径比较大的Flotube 7000(以下简称7000)对力学性能的提高程度最大。且我们将碳纳米管7000、9011分别与炭黑N660并用,对于提高复合材料的导热性能并没有如我们预期的一样存在所谓的“叠加关系”甚至是“协同效应”,而是对于提高复合材料导热有着一定的“负协同效应”。     

甲基丙烯酸锌与炭黑共同补强天然橡胶的研究

在开放式炼胶机上,分别以直接添加和原位生成2种方法向天然橡胶(NR)基体中添加甲基丙烯酸锌(ZDMA),制备了2种类型的ZDMA与炭黑共同补强的NR硫化胶,X射线衍射(XRD)分析证实,成功制备了ZDMA。扫描电镜(SEM)研究表明,原位生成ZDMA硫化胶的断面比直接添加ZD-MA硫化胶的粗糙很多,表现出更强的界面结合力。力学性能研究表明,用ZDMA部分替代炭黑,可以有效提高硫化胶的力学性能。在相同添加量下,原位生成ZDMA硫化胶的力学性能优于直接填充ZD-MA硫化胶的。     

Carbon nanotubes/carbon black synergistic reinforced natural rubber composites

Abstract

Carbon black (CB) and carbon nanotubes (CNTs) filled natural rubber (NR) composites were prepared. In order to overcome the dispersion of CNTs in rubber matrix, the surface modification of CNTs with bis-(γ-triethoxysilylpropyl)-tetrasulphide (Si-69) was undertaken, and a two-step mixing process, i.e. the use of twin roll mill followed by mixing in a Haake Banbury mixer (TR-THM) was used. The structure and mechanical properties were investigated. The results show that the Si-69 treated CNTs (S-CNTs) were dispersed in the rubber matrix uniformly. Compared with CB/NR composites without CNTs, the S-CNTs/CB/NR composites have better mechanical properties. When the ratio of S-CNTs/CB/NR was 5 : 20 : 100, the tear strength was improved by ～60%, and the mechanical properties reached a maximum. Dynamical mechanical analysis (DMA) reveals that with increasing content of CNT, the elastic modulus of composites at room temperature increases, and the maximum loss tangent and the corresponding glass transition temperature of composites decrease.     

白炭黑补强异戊橡胶和天然橡胶性能的对比研究

采用白炭黑填充补强异戊橡胶(IR)和天然橡胶(NR),分别研究其硫化特性、机械力学性能、热空气老化性能和动态力学性能.结果表明:白炭黑补强的IR比NR硫化速度快,焦烧时间短,交联密度与NR接近;NR的机械力学性能优于IR;随着白炭黑用量增加,IR的耐老化能力逐渐增强,NR在白炭黑用量为20份时耐老化性能最好;在0℃时,IR的损耗因子大于NR的损耗因子,在60℃时,IR的损耗因子小于NR的损耗因子.     

Regenerated cellulose nanocomposites reinforced with exfoliated graphite nanosheets using BMIMCL ionic liquid

Green nanocomposites of regenerated cellulose/exfoliated graphite nanosheets films with low nanofiller loadings were prepared using environmentally benign 1-butyl-3-methylimidazolium chloride (BMIMCl) ionic liquid. X-ray diffraction revealed well developed intercalated nanocomposites. The tensile strength and Young's modulus of the prepared nanocomposites were increased by 97.5% and 172% respectively when 0.75 wt.% and 1 wt.% exfoliated graphite nanosheets were added. The results were validated using the Halpin–Tsai model. The exfoliated graphite nanosheets were unidirectionally aligned in the regenerated cellulose parallel to the surface of the nanocomposites as revealed by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). Also, the TEM and FESEM revealed uniform dispersion of the exfoliated graphite nanosheets and good interaction between the nanofillers and the matrix. The addition of the exfoliated graphite nanosheets enhanced the thermal stability and reduced the water absorption and diffusivity of the nanocomposites.     

Effect of carbon black on properties of rubber nanocomposites

Polymer based nanocomposites were prepared using brominated poly(isobutylene‐co‐paramethylstyrene) (BIMS) rubber and octadecyl amine modified montmorillonite nanoclay. The effect of nature and loading of carbon black on these nanocomposites and the control BIMS was investigated thoroughly using X‐ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), and mechanical properties. The addition of 4 parts of the modified nanoclay to 20 phr N550 carbon black filled samples increased the tensile strength by 53%. Out of the three different grades of carbon black (N330, N550, and N660), N550 showed the best effect of nanoclay. Optimum results were obtained with the 20 phr filler loading. For comparison, china clay and silica at the same loading were used. Fifty‐six and 46% improvements in tensile strength were achieved with 4 parts of nanoclay added to the silica and the china clay filled samples, respectively. N330 carbon black (20 parts) filled styrene butadiene rubber (SBR) based nanocomposite registered 20% higher tensile strength with 4 parts of the modified nanoclay. In all the above carbon black filled nanocomposites, the modulus was improved in the range of 30 to 125%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 443–451, 2005     

Comparison study of graphite nanosheets and carbon black as fillers for high density polyethylene

In this work, the properties of high density polyethylene (HDPE)/graphite nanosheets (GN) and HDPE/carbon black (CB) nanocomposites prepared by melt mixing were studied. GN‐filled HDPE nanocomposites exhibited very low percolation threshold (ca. 6 wt%) as compared with that of HDPE/CB (ca. 22 wt%). Moreover, the impact strength and processing properties of HDPE/GN nanocomposites were superior to those of HDPE/CB within a certain content of fillers. The large aspect ratio of GN plays an important role in reducing the percolation threshold of HDPE/GN nanocomposites. Furthermore, the tensile fracture morphology revealed the formation of continuous conducting networks after the content of GN reached the critical percolation threshold. Differential scanning calorimetry (DSC) analysis illustrated a decreasing degree of crystallinity of HDPE/GN nanocomposites, while the crystalline temperature varied slightly. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Safe amine based zinc dithiocarbamates for the vulcanization of carbon black reinforced natural rubber

Binary combination of three safe amine based synthesized zinc dithiocarbamates (ZDC), namely zinc (N‐benzyl piperazino) dithiocarbamate (ZBPDC), zinc (N‐ethyl piperazino) dithiocarbamate (ZEPDC), and zinc (N‐phenyl piperazino) dithiocarbamate (ZPPDC) with mercapto benzothiazole disulfide (MBTS) as an effective accelerator system for the vulcanization of carbon black (N330, N550, and N774) filled natural rubber (NR) composites are studied. A comparison between the safe amine based zinc dithiocarbamates with the unsafe zinc dimethyl dithiocarbamate (ZDMC) in the light of mechanical and aging resistance behavior, introduces the non carcinogenic rubber additives in the filled vulcanization of rubber. Both accelerator and filler have the major importance for improving the mechanical as well as aging resistance behavior of the resultant vulcanizate. Variation in the filler and also filler to oil ratio are done to optimize the mechanical properties. SEM studies of different types of filler with different amounts show that N330 at 30 phr loading composites forms more homogeneity and less aggregated structures. Natural rubber systems with N330 carbon black show the best results with respect to tensile strength, but after the aging N774 carbon black filled system indicates better retention in the tensile strength. ZPPDC‐MBTS accelerated vulcanizate shows the better age resistance behavior than ZDMC‐MBTS accelerated vulcanizate. From both the points of age resistance and mechanical properties, ZBPDC‐MBTS accelerator system is the suitable substitute for ZDMC‐MBTS accelerated system in the filled vulcanization of natural rubber composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39988.     

Effect of carbon nanotubes decorated with silver nanoparticles as hybrid filler on properties of natural rubber nanocomposites

Decoration of carbon nanotube (CNT) surfaces with silver nanoparticles (AgNPs) was performed using N,N-dimethylformamide reducing agent. The CNT-decorated with AgNP (CNT-AgNP) was then used to prepare natural rubber (NR) nanocomposites via latex mixing method. Cure characteristics, mechano-thermal relaxation, electrical conductivity, and thermal properties of the composites were investigated. It was found that the CNT-AgNP gave cure properties improved over plain NR compounds in terms of scorch time, degree of vulcanization, and activation energy. In addition, temperature scanning stress relaxation measurement revealed stronger network formation after incorporation of AgNP into the NR matrix due to the interaction among CNT and AgNP particles. This also provided high conductivity and low percolation threshold concentration for the CNT-AgNP filled NR, relative to plain CNT filled NR composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47281.     

工程轮胎胎面胶用黏土/炭黑/天然橡胶纳米复合材料的性能

在工程轮胎胎面胶配方中,用黏土替代部分高耐磨炭黑,利用机械共混工艺制备了黏土/炭黑/天然橡胶(NR)纳米复合材料,研究了复合材料的综合性能.结果表明,黏土的加入不会对胶料的硫化特性产生太大影响;少量黏土的加入增强了混炼胶的填料网络作用,改善了炭黑/NR硫化胶的物理机械性能,耐磨性能提高了15%～30%,降低了滚动阻力,提高了耐屈挠疲劳破坏性能,当黏土填充量为4份时,复合材料的综合性能最优.     

黏土/炭黑/天然橡胶纳米复合材料的抗裂纹增长和耐破坏性能

用多种预割口实验方法研究了黏土/炭黑/天然橡胶纳米复合材料在静态和动态情况下的抗裂纹增长和耐破坏性能.结果表明,少量纳米黏土的加入能够有效地增加裂纹尖端的钝化支化倾向,从而阻碍裂纹的增长,提高天然橡胶的耐破坏能力;用动态耐切割试验机研究抗崩花掉块性能的结果表明,少量纳米黏土的加入可以提高复合材料抗崩花掉块的能力,改善其...     

碳纳米管增强天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶的理想填料。本文分别采用四种不同牌号(分别为Flotube7000 9000 9011 9400)的碳纳米管为实验原料,制备了碳纳米管/天然橡胶复合材料,并对其性能进行了研究探讨。结果发现,碳纳米管的加入能显著提高复合材料的力学性能和热导率,具有一维取向排列且长径比较大的Flotube7000(以下简称7000)对力学性能的提高程度最大,Flotube7000以及经过酸处理的表面具有-OH、–COOH官能团的Flotube9011(以下简称9011)对导热性能提高程度最为明显。     

掺杂氧化钐的炭黑用量对粉末天然橡胶性能的影响

高耐磨炉黑(HAF)填充型粉末天然橡胶(NR)[P(NR/HAF)]硫化胶的缺点是300%定伸应力低,因此,采用Sm2O3掺杂HAF(HAF-Sm),用凝聚共沉法制备了掺杂Sm2O3的HAF填充型粉末天然橡胶(NR)[P(NR/HAF-Sm)],研究了其硫化胶的力学性能与Sm2O3及HAF用量之间的关系。结果表明:在炭黑用量为10~100份,当炭黑用量相同、Sm2O3的质量分数为HAF的3%时,其P(NR/HAF-Sm)硫化胶的300%定伸应力显著高于P(NR/HAF)硫化胶,而与块状NR(MNR)/HAF机械混炼胶料硫化胶的相近;其拉伸强度、100%定伸应力和撕裂强度明显高于P(NR/HAF)及MNR/HAF硫化胶。这说明适量的Sm2O3掺杂HAF可显著提高炭黑填充型粉末NR硫化胶的300%定伸应力及其他力学性能。     

甲基丙烯酸锌/炭黑增强氢化丁腈橡胶的性能

分别以炭黑、甲基丙烯酸锌(ZDMA)及两者并用为增强剂填充氢化丁腈橡胶(HNBR),研究了HNBR混炼胶的硫化特征,考察了增强剂种类、炭黑与ZDMA并用比、温度对HNBR硫化胶物理机械性能的影响,并评价了用ZDMA/炭黑增强HNBR制得的封隔器胶筒的高温高压密封性能.结果表明,相比炭黑,ZDMA增强HNBR混炼胶的焦烧...     

Crack growth resistance of natural rubber reinforced with carbon nanotubes

Carbon nanotubes (CNTs)/natural rubber (NR) composites are prepared through ultrasonically assisted latex mixing combined with a two-roll mixing process, and their crack growth behavior is examined to evaluate their fatigue properties. CNTs/NR shows a reinforcement of crack growth resistance compared to unfilled NR. The measurements of the tearing energy and the hysteresis loss show that CNTs/NR exhibits more energy dissipation than NR. Also, strain-induced crystallization (SIC) around the crack tip of CNTs/NR and NR composite was examined at different fatigue strains. CNTs positioned at the crack tip led to a crack branching at low fatigue strain, which is responsible for the improvement of the crack growth resistance of CNTs/NR. However, the inclusion of CNTs renders NR higher crystallinity and larger crystallization zones in front of the crack tip at high fatigue strains, which allows more energy dissipation during crack growth. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48447.     

Influence of modified natural rubber and structure of carbon black on properties of natural rubber compounds

Carbon black‐filled natural rubber composites were prepared using various types of natural rubber: unmodified natural rubber, epoxidized natural rubber with two levels of epoxy groups at 25 and 50 mol % [epoxidized natural rubber (ENR)‐25 and ENR‐50], and maleated natural rubber. Two types of carbon black (HAF and ECF) with different structure and surface area were used. The functional groups present in natural rubber and carbon black were characterized by FTIR and ¹H‐NMR. Furthermore, cure characteristics, mechanical, morphological, and electrical properties of composites and gum rubber compounds were investigated. It was found that the presence of polar functional groups in rubber molecules and the different structures of carbon black significantly affected the cure characteristics and mechanical properties. This is attributed to physical and chemical interactions between carbon black surfaces and rubber molecules. It was also found that natural rubber filled with ECF showed the highest Young's modulus and hardness, which is due to the high‐surface area and structure of the ECF causing an increase in the degree of entanglement between rubber chains and carbon black particles. Frequency dependency of the dielectric constant, loss tangent, and AC conductivity was also investigated. An increase in dielectric constant, loss tangent, and AC conductivity was observed in the ENR/ECF composites. High‐carbon black loading level caused network formation of these conductive particles, increasing the AC conductivity of the composites. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

Structure and properties of hollow carbon black and filled rubber nanocomposites

Abstract

Hollow carbon black (HCB) is introduced in this work. It has a special hollow structure, high specific surface area, high structure and high electric conductivity. Hollow carbon black is used to fill styrene–butadiene rubber (SBR). The bound rubber test results show that the bound rubber of SBR/HCB can be measured when the HCB content reaches 25 phr because a strong filler network is formed, which indicates good electric conductivity of SBR/HCB. In comparison, the bound rubber of SBR/N330 can not be measured even when the N330 content is 40 phr. The mechanical measurements show that HCB has very good reinforcing effect on SBR especially when the filler content is low. The electric conductivity and thermal conductivity increase with the increase in filler content. At the same filler content, the properties of SBR/HCB nanocomposites are better than those of SBR/N330 nanocomposites, which suggests that HCB has good application potential.     

Toughening of epoxy hybrid nanocomposites modified with silica nanoparticles and epoxidized natural rubber

Silica nanoparticles (SN) and epoxidized natural rubber (ENR) were used as binary component fillers in toughening diglycidyl ether of bisphenol A (DGEBA) cured cycloaliphatic polyamine. For a single component filler system, the addition of ENR resulted in significantly improved fracture toughness (K_IC) but reduction of glass transition temperature (T_g) and modulus of epoxy resins. On the other hand, the addition of SN resulted in a modest increase in toughness and T_g but significant improvement in modulus. Combining and balancing both fillers in hybrid ENR/SN/epoxy systems exhibited improvements in the Young’s modulus and T_g, and most importantly the K_IC, which can be explained by synergistic impact from the inherent characteristics associated with each filler. The highest K_IC was achieved with addition of small amounts of SN (5 wt.%) to the epoxy containing 5–7.5 wt.% ENR, where the K_IC was distinctly higher than with the epoxy containing ENR alone at the same total filler content. Evidence through scanning electron microscopy (SEM) and transmission optical microscopy (TOM) revealed that cavitation of rubber particles with matrix shear yielding and particle debonding with subsequent void growth of silica nanoparticles were the main toughening mechanisms for the toughness improvements for epoxy. The fracture toughness enhancement for hybrid nanocomposites involved an increase in damage zone size in epoxy matrix due to the presence of ENR and SN, which led to dissipating more energy near the crack-tip region.