利用高压水射流技术制备天然橡胶复合材料

首先利用超声空化作用将炭黑团聚体破碎、切割、分散在水中制得炭黑悬浮液,然后在高速射流场中,炭黑悬浮液被高速射流卷吸到天然胶乳中,在射流边界,由于二者存在极大的速度差,而形成一个湍流混合层,炭黑在湍流拉伸、剪切作用下微观分散到天然胶乳中.结果表明,与传统干法工艺相比,射流工艺可以使炭黑更均匀的分散到天然橡胶基体中.Payne效应结果表明射流工艺减弱了炭黑与炭黑之间的相互作用,增强了炭黑与橡胶之间的相互作用.同时射流工艺制备的复合材料硫化时间变短,硫化程度增加,硫化胶的撕裂强度提高了78%,回弹性提高了20%,DIN磨耗减小了33%.动态力学性能结果表明,射流工艺制备的复合材料在60℃左右具有更低的损耗因子.     

稀土化合物处理高耐磨炭黑填充粉末丁腈橡胶

以经稀土化合物处理的高耐磨炭黑和丁腈胶乳为原料,以凝聚共沉法制备粉末丁腈橡胶.研究了分散剂和稀土化合物对粉末胶颗粒粒径及其硫化胶性能的影响.结果表明,粉末胶颗粒粒径随分散剂用量的增加而减小,随La3+用量的增加而增大.La3+改善了硫化胶的性能,特别是扯断伸长率和拉伸强度.进一步分析得出,硫化胶性能得以改善的根本原因是La3+改善了炭黑粒子在橡胶基体中的分散均匀性及其与橡胶基体的黏结牢固性.     

亲水性炭黑-天然橡胶纳米复合材料的制备及性能

利用原位球磨法制备了聚苯乙烯磺酸钠表面修饰炭黑,粒径分析和离心沉降实验结果表明,改性炭黑在水中具有十分优异的分散稳定性。利用该改性炭黑通过胶乳混合法成功制备了亲水性炭黑-天然橡胶纳米复合材料。采用万能电子拉力机、扫描电子显微镜、结合橡胶含量分析和动态热机械分析等多种手段对该复合材料进行了测试和研究。结果表明,与未改性炭黑相比,改性炭黑在橡胶基体中的分散性明显改善,与基体的相互作用显著增强,材料的力学性能大幅提高,填料网络化程度明显减弱。     

稻壳基二氧化硅/碳复合材料的表面改性及对天然橡胶的影响

以稻壳基二氧化硅/碳复合材料(SiCB)作为天然橡胶(NR)的补强填料, 采用表面化学改性的方法将天然乳胶(NRL)接枝到SiCB表面, 改善其与NR基体的相容性. 研究了不同处理方法对接枝NRL效率的影响, 以及填料填入NR后对硫化橡胶力学性能的影响. 结果表明, 经过硝酸和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(γ-MPTMS)预处理, NRL能高效接枝在SiCB表面, 得到的样品SiCB_MR10比未处理的SiCB_P有更强的补强能力. 硫化胶NR/SiCB_MR10的拉伸强度、 300%定伸和撕裂强度较NR/SiCB_P分别提高了61.06%, 27.15%和15.90%, 与传统炭黑产品N774填充的硫化胶NR/N774的力学性能相近. 经过NRL接枝改性的SiCB_MR10具有替代商业炭黑的应用前景.     

原位接枝炭黑/天然橡胶复合材料的制备及性能

采用原位固相接枝方法,使在高温和强剪切作用下降解的天然橡胶接枝到炭黑表面.通过对接枝前后炭黑填充天然橡胶的性能对比发现,原位接枝炭黑不但能提高天然橡胶的硫化速度,还能提高拉伸强度,定伸应力和撕裂强度等;动态力学性能的测试结果表明接枝炭黑填充的天然橡胶中接枝炭黑网络化程度较低,这些结果主要归因于接枝炭黑在橡胶基体中分散性的改善及炭黑与橡胶之间作用力的增加.     

TBIR改性BIIR/NR共混物的结构与性能

研究了新型合成橡胶——高反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)对全钢轮胎气密层并用橡胶——溴化丁基橡胶(BIIR)/天然橡胶(NR)(质量比70/30)的改性作用,探讨了BIIR/NR/TBIR共混物的交联密度、填料分散性及力学性能,特别是并用硫化胶的气密性及屈挠疲劳性能等.结果表明,与无定型的BIIR和NR相比,结晶性TBIR的引入提高了炭黑填充的BIIR/NR/TBIR混炼胶的强度和模量,且随着TBIR用量的增大,混炼胶中TBIR的结晶熔融峰更明显,混炼胶的强度与模量显著提高.硫化特性结果表明,随着TBIR用量的增大,BIIR/NR/TBIR共混物的硫化速率略有提高,交联密度略有降低;TBIR用量为10~30份(生胶总质量的10%~30%)时,BIIR/NR/TBIR硫化胶在机械性能基本保持不变的情况下,耐热氧老化性能提高10%以上,耐一级屈挠疲劳性能提升2~5倍,气密性提高17%.炭黑分散结果表明,经过动态疲劳实验BIIR/NR硫化胶中炭黑聚集体的平均粒径增大至11.5μm,明显大于BIIR/NR/TBIR硫化胶中炭黑聚集体的平均粒径.对含TBIR硫化胶在周期性应力应变过程中的结构演变及对耐疲劳裂纹引发性能的影响机制进行了探讨,结果表明,TBIR可改性BIIR或者BIIR/NR制备高抗裂口引发的全钢轮胎气密层材料.     

高疲劳寿命氯丁橡胶基减振材料的结构与性能

以氯丁橡胶(CR)为基体材料, 将新型反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)引入传统CR减振基体中, 探讨TBIR在减振材料中的应用前景. 研究发现, 随着TBIR用量的增加, CR/TBIR混炼胶的强度及模量明显提升; CR/TBIR硫化胶的拉伸强度、 撕裂强度、 压缩永久变形、 动静刚度比及耐疲劳性能均得到改善, 特别是一级疲劳寿命提高了50%~400%(未填充体系)及40%~180%(填充体系), 六级疲劳寿命提高了60%~500%(未填充体系)及30%~120%(填充体系). 与未填充CR/TBIR硫化胶相比, 填充CR/TBIR硫化胶由于炭黑补强作用及填料-聚合物相互作用的引入, 屈挠疲劳寿命、 撕裂强度及拉伸性能均显著提高. 与填充CR硫化胶相比, 填充CR/TBIR质量比为90/10的并用胶能够在保持硫化胶的损耗因子基本不变的基础上, 实现综合性能的平衡提升.     

基于天甲橡胶的高性能生物基弹性体制备及性能研究

天甲橡胶(MGNR)是生物基高分子材料天然橡胶(NR)的一种改性产品,较高的门尼黏度导致MGNR作为橡胶制品主要成分的研究鲜见报道.本文将极性的MGNR与非极性的NR并用,NR分子链较高的柔顺性使MGNR的门尼黏度得到有效降低,改善了MGNR的加工性能.进而添加表面具有硅羟基的气相法白炭黑,一方面,白炭黑与MGNR、NR形成结合胶;另一方面,白炭黑表面的硅羟基与MGNR的侧链甲基丙烯酸甲酯形成较强的相互作用,白炭黑作为"桥梁"改善了MGNR与NR之间的相容性.随着白炭黑含量的提高,MGNR/NR(40/60)硫化胶的拉伸强度与断裂伸长率均逐渐增大.当白炭黑的填充量为10 phr时,硫化胶的拉伸强度为31.2 MPa,断裂伸长率为605%.相比于未填充白炭黑的硫化胶分别提高了42.4%和28.9%,相比于纯MGNR分别提高了55.2%和93.9%.     

稀土化合物改性炭黑/天然橡胶复合材料的制备与性能

用铕（Eu）、钬（Ho）、饵（Er）和镝（Dy）4种稀土（Ln）氧化物（Ln2O3）制备了稀土氢氧化物改性炭黑，然后加入天然胶乳（NRL），采用凝聚共沉法制备了粉末状的稀土改性炭黑，天然橡胶复合材料P[NR／HAF-Ln（OH）3]。研究了稀土种类和用量对P[NR／HAF-Ln（OH）3]的粒径分布及其硫化胶物理机械性能的影响。结果表明，稀土可以提高NRL与乳化炭黑构成的粉末体系的成粉率，当Ho，Er的用量为1．0％或Dy的用量为0．5％时均可使粒径小于0．9mm的产物达100％；稀土的存在可显著提高P[NR／HAF-Ln（OH）3]硫化胶的拉伸强度和撕裂强度，而Er和Dy还可明显降低硫化胶的永久变形；SEM分析表明，HAF-Dy（OH）3以团粒形态存在于NR基体中，团粒表面覆盖一层NR膜，团粒与NR构成的界面模糊，说明HAF-Dy（OH）3与NR基体结合紧密，这是P[NR／HAF-Ln（OH）3]具有较好物理机械性能的主要原因。     

炭黑结合橡胶对天然橡胶性能的影响

本文研究了天然橡胶(NR)与五种不同类型炭黑的结合橡胶对其混炼胶的应力-应变、流变性质等的影响。结果表明,NR与炭黑的结合橡胶量随炭黑结构和表面积增加而增加。结合橡胶的增加使NR在低剪切下的本体粘度、弹性恢复性和强度增加,塑性和粘着性降低;在高剪切下流动性变差,挤出物收缩则有所下降。此外,结合橡胶的增加也增加了硫化胶的交联度,因此模量、硬度和耐磨性提高,抗张强度和伸长率却有所下降。     

Preparation and mechanical properties of water-dispersible hyperbranched polymer grafted carbon black/natural rubber composites by latex blending method

In order to improve the mechanical properties of rubber-matrix composites, carboxyl-terminated hyperbranched poly (2-hydroxypropane-1,2,3-tricarboxylic acid) grafted carbon black (CB-g-CTHBP) was prepared, and it could be stably dispersed in water for up to 90 days. CB-g-CTHBP dispersion and natural rubber latex were blended to obtain NR/CB-g-CTHBP, and the effect of CB-g-CTHBP content on the mechanical properties of composites was discussed. The results show that the dispersibility and wettability of CB-g-CTHBP to composites are significantly improved after grafting hyperbranched polymer onto the surface. Compared with the composite filled with NR/CB, when the amount of filler is 30 phr, tensile strength, tear strength, and shore A hardness of NR/CB-g-CTHBP increase by 54.78%, 55.13%, and 20.96%, respectively. Moreover, CB-g-CTHBP could disperse more evenly in the natural rubber-matrix, and the interaction between CB-g-CTHBP and rubber-matrix could further enhance in the composite.     

Influence of heat treatment on electromagnetic properties of polyimide/carbon black composites

A kind of absorbing materials was prepared by hot pressing method using polyimide as matrix and carbon black (CB) as filler. The mechanical properties, the electromagnetic properties, and the thermal stability of polyimide/CB composites were studied. The results showed that the complex permittivity increased from 6.82 + 1.38i to 18.69 + 9.47i, whereas the flexural strength decreased from 108 MPa to 77 MPa, respectively, when the CB content increased from 2 wt% to 8 wt%. The reflection loss curves shifted to low frequency with increase of the thickness at the same content. The reflection loss below ?10 dB could be obtained in the X band with 6 wt% CB content and did not display significant difference before and after the heat treatment at 400°C for 5 h. When the content of CB was 8 wt%, the decomposition temperature (at 5% weight loss) increased approximately 42°C compared with pure polyimide matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

甲基丙烯酸全氟烷基代乙酯对天然橡胶乳液辐射改性研究

天然橡胶的性能与其组成中的C C双键有密切关系,由于C C双键的存在,为天然橡胶的改性提供了便利,大多数天然橡胶的改性方法,如氯化、氢氯化、环化、环氧化、接枝共聚等皆是建立在这一思路基础上的.White等[1]认为接枝天然橡胶的目的是提高天然橡胶的机械强度,赋予特殊的功能.作     

Synthesis and Characterization of Aramid Fiber‐Reinforced Polyimide/Carbon Black Composites and Their Use in a Supercapacitor

The aramid fabric (AF )‐reinforced polyimide (PI ) composites filled with carbon black (CB ) were fabricated by means of a thermal imidization and their mechanical, thermal and electrochemical behaviors were comparatively investigated. Experimental results showed that the tensile strength of composite increased with an increase of the CB , meanwhile, the addition of 5 wt% CB and AF increased the tensile modulus to 5682.0 MPa . The superior mechanical properties of the composites were attributed to the good dispersion and effective stress transfer between the polymer and CB , as evidenced by the results from X‐ray diffraction (XRD ) and morphological studies. Besides, the thermal‐nonoxidative stability of PI was significantly improved by the incorporation of CB and AF . Furthermore, the CB /AF /PI composite was employed as the supercapacitor electrode in the 6 mol/L KOH aqueous electrolyte solution, which exhibited a specific capacitance of 510 F•g⁻¹ at 10 mV •s⁻¹. It also exhibited excellent long‐term stability, and the energy density was stable with the increase in the power density. The super performance of the composite electrode is attributed to the synergistic effects of CB particles and organic polymer.     

Sulfur nanoparticles transform montmorillonite into an inorganic surfactant applicable in thermoplastics processing

We report on the modification of montmorillonite (MMT) with sulfur nanoparticles (S NPs) that yields a MMT/S nanocomposite exhibiting surfactant-like amphiphilic behavior at 80:20 MMT:S weight-to-weight ratio. The new material was successfully used as an inorganic surfactant for the dispergation of carbon black (CB) in High-Density Polyethylene (HDPE). Both the novel inorganic surfactants and the HDPE-based nanocomposite products were characterized rigorously by XRD, TGA-DSC, SEM, TEM, zeta potential measurement, static contact angle measurement, tensile strength analysis, particle charge measurement, and X-ray micro-computed tomography. It was found that the presence of 0.5 wt% MMT/S has no adverse effects on HDPE product quality. On the contrary, the MMT/S additive improves the homogeneity of the distribution of CB particles in the HDPE matrix, which is very important because of the UV stabilization properties of CB. The industrial relevance of this finding is that it demonstrates how the right composite of two cheap and readily available inorganic materials can improve the properties of one of the most widely used thermoplastics.     

Cytotoxicity and anticancer activity of natural rubber latex particles for cancer cells

To broaden the knowledge of cytotoxicity of natural rubber latex (NRL) nanoparticles we for the first time examined the latex biocompatibility in vitro against a panel of cancer cells (A549, A2780, and MDA-MB-231). Owing to fractionation of NRL nanoparticles by ultra-centrifuge, the effect of the non-rubber constituents (intermediate of 5.8 wt% and sediment of 0.2 wt%) on the cytotoxicity was clarified. For intermediate constituent, the half maximal inhibitory concentration (IC₅₀) values at 24 h was 1.05 mg/mL for A549 cells, which was one order of magnitude higher in toxicity as compared to that for A2780 (0.24 mg/mL) and MDA-MB-231 (0.36 mg/mL) cells. In addition, profound studies including cell cycle arrest abilities and apoptosis induction profiles against cancer cells were discussed in detail. It was found that the constituents exhibit some significant effect on the cell cycle arrest and trigger apoptosis for A2780 cells. This effective apoptosis induction profiles was more prominent in MDA-MB-231 cells incubated with NRL nanoparticles and sediment loading conditions. The percentage of apoptotic cells was ca. 6–8% of the total cells.     

Reduced percolation thresholds of immiscible conductive blends

The DC conductivity of polymer blends composed of poly(ethylene‐co‐vinyl acetate) (EVA) and high density polyethylene (HDPE), where a conductive carbon black (CB) had been preferentially blended into the HDPE, were investigated to establish the percolation characteristics. The blends exhibited reduced percolation thresholds and enhanced conductivities above that of the individually carbon filled HDPE and EVA. The percolation threshold of the EVA/HDPE/CB composites was between 3.6 and 4.2 wt % carbon black, where the volume resistivity changed by 8 orders of magnitude. This threshold is at a significantly lower carbon content than the individually filled HDPE or EVA. At a carbon black loading of 4.8 wt %, the EVA/HDPE/CB composite exhibits a volume resistivity which is approximately 14 and 11 orders of magnitude lower than the HDPE/CB and EVA/CB systems, respectively, at the same level of incorporated carbon black. The dielectric response of the ternary composites, at a temperature of 23°C and frequency of 1 kHz, exhibited an abrupt increase of ca. 252% at a carbon concentration of 4.8 wt %, suggesting that the percolation threshold is somewhat higher than the range predicted from DC conductivity measurements. Percolating composites with increasing levels of carbon black exhibit significantly greater relative permittivity and dielectric loss factors, with the composite containing 6 wt % of carbon black having a value of ϵ′ ≈ 79 and ϵ″ ≈ 14. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1899–1910, 1999