Styrene–butadiene rubber/cellulose II/clay nanocomposites prepared by cocoagulation—mechanical properties

In this work, nanocomposites of styrene butadiene rubber (SBR), cellulose II, and clay were prepared by cocoagulation of SBR latex, cellulose xanthate, and clay aqueous suspension mixtures. The incorporated amount of cellulose II was 15 phr, and the clay varied from 0 to 7 phr. The influence of cellulose II and clay was investigated by rheometric, mechanical, physicochemical, and morphological properties. From the analysis of transmission electron microscopy (TEM), dispersion in nanometric scale (below 100nm) of the cellulosic and mineral components throughout the elastomeric matrix was observed. XRD analysis suggested that fully exfoliated structure could be obtained by this method when low loading of silicate layers (up to 5 phr) is used. The results from mechanical tests showed that the nanocomposites presented better mechanical properties than SBR gum vulcanizate. Furthermore, 5 phr of clay is enough to achieve the best tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料,研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明,黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比,邵尔A型硬度、定伸应力和撕裂强度较高,拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响,填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。     

Structure and properties of strain‐induced crystallization rubber–clay nanocomposites by co‐coagulating the rubber latex and clay aqueous suspension

Natural rubber (NR)–clay (clay is montmorillonite) and chloroprene rubber (CR)–clay nanocomposites were prepared by co‐coagulating the rubber latex and clay aqueous suspension. Transmission electron microscopy showed that the layers of clay were dispersed in the NR matrix at a nano level, and the aspect ratio (width/thickness) of the platelet inclusions was reduced and clay layers aligned more orderly during the compounding operation on an open mill. However, X‐ray diffraction indicated that there were some nonexfoliated clay layers in the NR matrix. Stress–strain curves showed that the moduli of NR were significantly improved with the increase of the amount of clay. At the same time, the clay layers inhibited the crystallization of NR on stretch, especially clay content of more than 10 phr. Compared with the carbon‐black‐filled NR composites, NR–clay nanocomposites exhibited high hardness, high modulus, high tear strength, and excellent antiaging and gas barrier properties. Similar to NR–clay nanocomposites, CR–clay nanocomposites also exhibited high hardness, high modulus, and high tear strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 318–323, 2005     

胶乳-悬浮液共沉法天然橡胶/埃洛石纳米管复合材料的结构与性能

利用天然橡胶(NR)胶乳和埃洛石纳米管(HNTs)悬浮液的负电稳定性,采用胶乳-悬浮液共沉法制备了NR/HNTs复合材料,并对其硫化特性、微观结构、力学性能以及动态力学性能进行了研究.结果表明,HNTs的引入可促进NR的硫化反应,随HNTs用量的增加,焦烧期和正硫化时间缩短;HNTs在复合材料中的分散性极佳;随着HNTs用量的增加,纳米复合材料的定伸应力和邵尔A硬度明显增大,扯断伸长率有所下降,综合力学性能在20份时最好;随着HNTs用量的增加,纳米复合材料的玻璃化转变温度略有升高,转变区的损耗因子明显下降.     

淀粉对蒙脱土/丁腈橡胶纳米复合材料结构和性能的影响

采用蒙脱土水悬浮液/橡胶乳液共混-共凝复合技术制备蒙脱土/丁腈橡胶纳米复合材料时,在蒙脱土水悬浮液和丁腈胶乳的混合体系中加入淀粉,考察了淀粉用量对蒙脱土/丁腈橡胶纳米复合材料结构和性能的影响。结果表明,淀粉的加入有利于蒙脱土片层形成剥离型结构。当蒙脱土用量为5份、淀粉用量为10份时,蒙脱土几乎呈完全剥离状态;随着淀粉用量的增加,该复合材料的邵尔A硬度、100%定伸应力、拉伸强度、扯断伸长率和撕裂强度均有所提高。     

A Novel Interface Agent for Preparation of High Gas Barrier Organic Montmorillonite/Brominated Butyl Rubber Nanocomposites

Organic montmorillonite/brominated butyl rubber nanocomposites are prepared by improved solution blending, i.e., preparation of organic clay suspension and suspension blending with brominated butyl rubber solution by adding polytetramethylene ether glycol as interface agent. Scanning electron microscopy and atomic force microscopy show that polytetramethylene ether glycol has good dispersing effect on organic clay. Transmission electron microscopy and X-ray diffraction analysis demonstrates that both intercalated and exfoliated structures are obtained in organic montmorillonite/brominated butyl rubber nanocomposites. The mechanical performances and the gas barrier properties of the organic montmorillonite/brominated butyl rubber nanocomposites are improved greatly, which proves that the high-performance clay/rubber nanocomposites are prepared in nonpolar solvent.     

Preparation and properties of natural rubber nanocomposites with solid‐state organomodified montmorillonite

A novel organomodified montmorillonite prepared by solid‐state method and its nanocomposites with natural rubber were studied. The nanocomposites were prepared by traditional rubber mixing and vulcanizing process. The properties of solid‐state organomodified montmorillonite were investigated by Fourier‐transform infrared spectroscopy (FITR) and thermogravimetric analysis (TGA). The dispersion of the layered silicate in rubber matrix was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the nanocomposites consisting of solid‐state organomodified montmorillonite and natural rubber are obtained. The solid‐state organomodified montmorillonite can not only accelerate the curing process, but also improve the mechanical and aging resistance properties of NR. The properties improvement caused by the fillers are attributed to partial intercalation of the organophilic clay by NR macromolecules. In addition, the dynamic mechanical analysis (DMA) results showed a decrease of tanδmax and increase of T_g when the organoclay is added to the rubber matrix, which is due to the confinement of the macromolecular segments into the organoclay nanolayers and the strong interaction between the filler and rubber matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of organoclay loading level on mechanical properties,thermomechanical behavior,and heat build‐up of natural rubber/organoclay nanocomposites

Sodium‐montmorillonite nanoclay was modified with octadecylamine and compounded with natural rubber (NR) by dry mixing method. The effects of organoclay loading level on mechanical properties, thermal–mechanical behavior, and heat build‐up of NR/organoclay nanocomposites were investigated. Temperature scanning stress relaxation technique was used to characterize the thermal–mechanical behavior of the composites. The morphological properties were assessed by X‐ray diffraction and transmission electron microscopy. Loading levels of organoclay below 5 phr gave improved mechanical properties and heat build‐up, along with exfoliated clay structure in the nanocomposites. On the other hand, with loading levels above 7 phr the organoclay tended to agglomerate, and X‐ray diffraction revealed an intercalated structure. In these cases, the excess residual organoclay caused significantly increased stress relaxation and heat build‐up. Unmodified sodium‐montmorillonite as filler did not significantly affect the mechanical and heat build‐up properties of NR vulcanizates. POLYM. COMPOS., 37:1735–1743, 2016. © 2014 Society of Plastics Engineers     

Montmorillonite clay nanocomposites based on vinyl pyridine‐styrene‐butadiene terpolymer (VPR)/acrylonitrile‐butadiene rubber (NBR) blend

This study describes a novel route to synthesize vinyl pyridine‐styrene‐butadiene terpolymer rubber (VP rubber) montmorillonite clay nanocomposites by latex blending technique. The pyridine moiety of the VP rubber was modified with methyl iodide to form the pyridinium ion during latex blending. Cation exchange reaction of the pyridinium ion of the VP rubber latex with sodium montmorillonite occurred during latex stage mixing which helped to form VP rubber‐montmorillonite clay nanocomposites. Coagulation of the latex‐clay slurry produced nanocomposites master batch. The master batch was compounded with acrylonitrile butadiene rubber (NBR). Fourier Transform Infrared Spectroscopy (FTIR) confirmed the modification of the pyridine moiety of VP rubber. Wide angle X‐ray diffraction (WAXD), scanning electron microscopy‐energy dispersive X‐ray spectrophotometry (SEM‐EDS) and transmission electron microscopy (TEM) provided the evidences of formation of nanocomposite. Remarkable improvements in the mechanical properties were found by addition of small amount of modified clay. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Curing Characteristics and Aging Properties of Natural Rubber/Epoxidized Natural Rubber and Cellulose II

In this work, natural rubber (NR) and regenerated cellulose (cel II) latexes were co-coagulated and to the mixture epoxidized natural rubber (ENR) was added on a two-roll mill. The cellulose content was fixed at 20 phr while ENR content varied from 0 to 75 phr. The influence of ENR was studied through the cure characteristics, aging and dynamic-mechanical properties. The aging provides nanocomposites with better solvent resistance and increased tensile strength at ENR content of 25 phr. The results suggest that a new type of light-colored nanocomposites were obtained, which presented high mechanical performance and resistance to solvents.     

聚苯胺改性蒙脱土/天然橡胶纳米复合材料的制备与性能

采用原位聚合法制备了聚苯胺质量分数为20% 的聚苯胺改性蒙脱土,并以此作为增强剂利用机械混炼法制备了聚苯胺改性蒙脱土( PANI － MMT) /天然橡胶( NR) 纳米复合材料。使用X 射线衍射仪、傅里叶变换红外光谱仪及扫描电镜等对PANI － MMT 和PANI － MMT/NR 复合材料的结构进行了表征,并考察了PANI － MMT/NR 复合材料的力学性能。结果表明,PANI － MMT/NR 复合材料形成了插层型纳米结构; 与普通的有机蒙脱土/NR 复合材料相比,PANI － MMT/NR 复合材料的力学性能明显提高,PANI － MMT 添加质量为20 份时其力学性能达到最好,并超过了添加40 份炭黑N 660 的NR 的力学性能。     

Thermal stability,aging properties,and flame resistance of NR‐based nanocomposite

Polymer/clay nanocomposites have some unique properties due to combination of flame resistance and improved mechanical and thermal stability properties which are important to enhance the material quality and performance. The objective of this work was to investigate the effect of organically modified montmorillonite (org‐MMT) on the thermal and flame retardant as well as hardness and mechanical properties of the nanocomposites based on the natural rubber (NR). It was shown that by the addition of 3 wt % of org‐MMT to NR, its aging hardness rise was decreased more than 55% and the ignition time was delayed about 150%. The reduction in heat release rate peak value was equal to 54% compared to the pristine NR. Addition of org‐MMT improved the thermal stability of the NR. Furthermore, nanocomposites which were calendared before curing showed much more thermal stability and fire resistance than those which contained similar amount of organoclay. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Mechanical properties of NR/BR/cellulose II composites

Summary Blends of natural rubber (NR) and butadiene rubber (BR) with cellulose filler have been investigated. The coprecipitation of the rubber latex-cellulose xanthate mixtures by acidulation lead to elastomer-cellulose II composites in granular form. In these blends, the NR/BR ratio has been varied from 75/25 to 25/75, and the cellulose content has been increased from 0 to 25 phr. Mechanical tests have been applied to the composite samples, and the results showed that cellulose II may be considered as a reinforcing agent. Those results gave also an insight into the role of NR and BR on the properties of the composite samples.     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005     

Synthesis of exfoliated acrylonitrile-butadiene-styrene copolymer (ABS) clay nanocomposites: role of clay as a colloidal stabilizer

Acrylonitrile-butadiene-styrene copolymer (ABS) clay nanocomposites were synthesized using two clays (sodium montmorillonite, laponite). Both colloidal stability and mechanical properties of the nanocomposites were dependant on aspect ratios of clays. Laponite, a low aspect ratio clay, reduced particle sizes of ABS clay nanocomposite latexes, enhanced colloidal stabilities, and increased viscosity of the latexes. The colloidal stability of ABS clay latexes may result from four factors. Firstly, the electrostatic repulsion forces originated from surface charges of clays and anionic surfactant contribute to colloidal stability. Secondly, laponite layers separate sodium montmorillonite layers and polybudadiene latex particles preventing the coagulation. Thirdly, the laponite layers adsorbed on latexes act like steric barriers against coagulation. Fourthly, increased viscosity reduces latex mobility, lowering collision possibility among latex particles. Resultant ABS clay nanocomposites showed exfoliated structures, and their mechanical properties related to the relative weight ratio of sodium montmorillonite to laponite: as portions of sodium montmorillonite increased, dynamic moduli of the nanocomposites increased, because sodium montmorillonite has higher aspect (length/thickness) ratio than laponite.     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

乳液插层法天然橡胶/蒙脱土纳米复合材料的制备及其性能

采用乳液插层法制备了天然橡胶/蒙脱土（NR/MMT）纳米复合材料,采用透射电子显微镜（TEM）研究了复合材料的亚微观形态,并对复合材料的力学性能和耐磨耗性能进行了研究。TEM结果显示,MMT片层以纳米尺寸均匀分散在NR基体中;力学性能测试结果表明,当MMT用量小于12份时,纳米复合材料的力学性能随MMT用量的增加而逐渐增大,NR/MMT纳米复合材料具有优良的力学性能;蒙脱土的加入稍微降低纳米复合材料的耐磨性。     

黏土及界面剂对乳液插层法天然橡胶纳米复合材料结构与性能的影响

采用乳液插层法制备了黏土/天然橡胶(NR)纳米复合材料,考察了蒙脱土(MMT)、累托石(REC)2种黏土和用界面剂等量替代NR的方式对复合材料微观结构及性能的影响.结果表明,在2种纳米复合材料中,大部分MMT和REC均以纳米片层结构分散在橡胶基体中,与REC片层相比,MMT片层边界模糊且稍微有些弯曲,且层间距变化较大,...     

有机改性与乳液插层法相结合制备的丁苯橡胶/黏土纳米复合材料的结构与性能

针对现有的乳液插层法所制备的橡胶／黏土纳米复合材料中填料与橡胶之间界面结合较弱的缺点,在乳液插层法中对无机黏土进行有机改性,制备出力学性能优异的纳米复合材料。X射线衍射和透射电子显微镜技术分析表明,有机改性后的复合材料中黏土被部分地有机改性,且在基体中以纳米尺寸分散。