Synthesis and properties of composites of starch and chemically modified natural rubber

A means is developed for forming polysaccharide-based composites with useful material properties through use of unmodified and chemically modified natural rubber latex (NRL). Starch was used as a model for polysaccharides. The NRL was modified by grafting with dimethylaminoethyl methacrylate (DMAEMA) to form a latex with cationic water-soluble polymeric ‘hairs’ of polyDMAEMA, which should form hydrogen bonds with starch. Starch solutions, containing 20% glycerol as a film-forming aid, and the modified NRL were mixed and films allowed to form. The unmodified latex acted only as filler in the starch films, but with modified NRL, the mechanical properties of the films were significantly altered. The elastic modulus was greatly decreased and strain at break greatly increased. The glass transition temperature increased from −48 °C to −32 °C, suggesting significant compatibilization. Freeze-fracture TEM micrographs indicate strong interactions between the surface of the modified NRL and starch. The polyDMAEMA chains are more hydrophilic than the starch, and the addition of grafted latex results in a 20° drop of the water contact angle of the formed film, and a 25% increase of the water absorption compared to the native starch; with unmodified NRL, the opposite effect was observed.     

Evaluation of microstructure of natural rubber/nano-calcium carbonate nanocomposites by solvent transport properties

Abstract

The research on rubber reinforcement is a traditional but vitally essential topic. However, many issues in this aspect are presently still not well understood and explained. Moreover, when rubber reinforcement is obtained by using nanoparticles, it is even more difficult to clearly understand the relationship between the microstructure and properties. The special character of rubber, being a multicomponent system (rubber, vulcanising agent, accelerants, reinforcements, etc.), complicates even more the analysis of the parameters affecting the rubber/nanoparticle composite formation. Therefore, we believe the results obtained by means of transport experiments represent a good approach for understanding the reinforcing capability of nanofillers. The reinforcing capability of nano-CaCO₃ in natural rubber (NR) was characterised by means of transport properties such as diffusion, sorption and permeability coefficients, swelling ratio, enthalpy, entropy and activation energy. Concentration of nano-CaCo₃ in NR was varied from 0 to 20 parts per one hundred parts of rubber by weight (phr). Transport process of toluene by use of equilibrium weight swelling of the NR and nanofilled composites have been studied in details. The effects of nanofiller concentration and temperature on transport of toluene through nano-CaCO₃ filled NR vulcanisates were studied. The microstructure of the nanocomposites was investigated by scanning electron microscopy. The diffusivity data of the systems have shown the dependence on the temperature and microstructure of nanocomposite. Generally, the concentration of nano-CaCO₃ plays an important role in transport process.     

白炭黑/天然橡胶复合材料疲劳过程中微观结构与性能演变

本研究采用单轴疲劳机对白炭黑/天然橡胶复合材料样品进行了不同程度的疲劳,并对样品在不同阶段的微观结构和力学性能进行了表征。透射电镜扫描显示在疲劳过程中白炭黑的分散程度以及填料网络出现了先变好后变差的现象。溶胀法测试交联密度显示交联密度也经历了一个先降低后升高再降低的过程,说明复合材料的填料网络和交联网络在疲劳的过程中经历了一个破坏重建再破坏的过程。动态热机械分析仪(DMA)显示在疲劳过程中样品的玻璃化转变温度是先降低后升高。模量-应变曲线显示10万次疲劳后的试样内部填料的分散非常均匀,Payne效应减弱。力学性能测试表明经历了5-10万次的疲劳后,样品的力学性能超过了未疲劳样品。     

Preparation and performance of oleylamine modified silica-reinforced natural rubber composites

Oleylamine (OA) modified silica (SiO₂-g-OA) was prepared using γ-(2,3-epoxypropoxy) propytrimethoxysilane (KH560) and OA, silica/natural rubber (NR) and SiO₂-g-OA/NR composites were prepared by mechanical blending in an internal mixer, and SiO₂-g-OA was characterized by Fourier transform infrared spectroscopy, thermal gravimetric analyzer, and contact angle analyzer. The mechanical properties, abrasion resistance, curing characteristics, Payne effect, and morphology of silica/NR and SiO₂-g-OA /NR composites were investigated using universal testing machine, Akron abrasion tester, rubber processing analyzer, and scanning electron microscope, respectively. The results showed that SiO₂-g-OA became more hydrophobic and had better compatibility with NR. Moreover, SiO₂-g-OA/NR had weaker Payne effect, better vulcanization performance, and more excellent mechanical properties. As the content of filler was more than 30 phr, SiO₂-g-OA/NR had lower rolling resistance and higher wet skid resistance. Compared with silica modified by other coupling agents, SiO₂-g-OA had the best reinforcement effect on NR.     

氧化石墨烯/天然橡胶复合材料的制备与性能

采用己内酰胺（CPL）改性氧化石墨烯（GO）（CPL-GO）,与天然橡胶（NR）复合后通过熔融共混法制备了CPL-GO/NR复合材料。考察了CPL-GO用量对CPL-GO/NR复合材料物理机械性能、界面相互作用和气体阻隔性能的影响。结果表明,CPL改性GO后,X射线衍射层间距增加,片层堆砌更为松散,CPL-GO与水接触角增至91.2°。当CPL-GO的质量分数为2.0%时,CPL-GO/NR复合材料的拉伸强度为26.1 MPa,较纯NR提高了50.9%。随着CPL-GO用量的增加,复合材料的储能模量增加,损耗因子的峰值减小,表明GO经CPL表面改性后与NR复合,增强了两相界面间的相互作用,从而提高了复合材料抵抗变形的能力。在40 ℃下,当CPL-GO的质量分数为3.0%时,CPL-GO/NR复合材料的气体渗透系数较纯NR下降了57.1%。     

Evaluation of fatigue performance of filled and unfilled natural rubber/styrene-butadiene rubber composites

This paper deals with the fatigue life analysis of a blend of natural rubber (NR) and styrene-butadiene rubber (SBR) with and without nanoclay particles. Various damage parameters based on strain are investigated. A nonlinear finite element analysis is carried out by using ABAQUS. To formulate the life prediction models, the measured fatigue life is used together with various damage parameters. It is shown that all the damage parameters can estimate the fatigue lives effectively with correlation coefficients greater than 0.9. There is a good agreement between the obtained fatigue live predictions and the measured fatigue results. The effect of various parameters such as true strain and nanoparticles' loading is also investigated. The results of sensitivity analysis show that the strain has a greater effect on the variation of the rubber compounds' fatigue life. The test samples' fracture surface is assessed via scanning electron microscopy (SEM). SEM results show that as the strain increases, the test samples softly fail while the fracture surface of the nanocomposite is roughened by the addition of nanoclay.     

Effect of natural and organically modified montmorillonite clays on the properties of polydimethylsiloxane rubber

The effects of natural (MT) and organically modified (O‐MT) montmorillonite clays on the properties of polydimethylsiloxane (PDMS) rubber were evaluated. Rubber composites with different clay contents were prepared by a compounding procedure in an open two‐roll mill, which was followed by a compression‐molding step in which the PDMS matrix was peroxide crosslinked. The clay rubber composites were characterized by swelling measurements in toluene, thermogravimetric analyses, X‐ray diffraction, scanning electron microscopy, and tensile tests. The introduction of MT restricted the solvent swelling and increased the crosslinking density of the rubber, which indicated the formation of a covalent filler–matrix interface. The enhanced interaction between MT and PDMS reduced the aggregation size of MT particles in the MT composites and promoted an increase in the separation of the clay layers. When the rubber was filled with O‐MT, a higher solvent amount was incorporated in the material, and this trend increased with the clay content. Moreover, the low interaction between O‐MT and the PDMS chains resulted in larger clay aggregates in the O‐MT composites compared to those with MT. Despite the different interface natures, both clays enhanced thermal stability and acted as reinforcing fillers in relation to Young's modulus and tensile strength. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of graphene oxide/natural rubber composites by latex cocoagulation: Relationship between microstructure and reinforcement

Graphene oxide(GO) has recently attracted substantial interest as a possible reinforcing agent for next generation rubber composite materials. In this research, GO was incorporated in natural rubber(NR) composites through latex co-coagulation technique. The microstructures of GO/NR composites were characterized through a combination of transmission electron microscope, scanning electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and Differential scanning calorimeter. The results showed that highly exfoliated GO sheets were finely dispersed into NR rubber matrix with strong interface interaction between GO and NR. The mechanical properties of the GO/NR composites were further evaluated. The results showed that the tensile strength, tear strength and modulus can be significantly improved at a content of less than 2 phr. Especially,GO exhibited specific reinforce mechanism in NR due to the stress-induced crystallization effects of NR. The stress transfer from the NR to the GO sheets and the hindrance of GO sheets to the stress-induced crystallization of NR were further displayed in stress–strain behavior of GO/NR composites. These enhanced properties were attributed to the high surface area of GO sheets and highly exfoliated microstructures of GO sheets in NR.     

Mechanical and sorption properties of poly(ethylene-co-vinyl acetate)(EVA) compatibilized acrylonitrile butadiene rubber/natural rubber blend systems

Poly (ethylene-co-vinyl acetate) (EVA) has been used as a compatibilizer for heterogeneous natural rubber/acrylonitrile butadiene rubber (NR/NBR) blends. NR/NBR (50/50) blends were compatibilized with varying amounts, from 0 to 10 parts per hundred rubber (phr), of EVA. The compatibility of the blend components in presence of EVA has been evaluated in terms of mechanical and sorption characteristics. The mechanical properties were found to be improved by the addition of EVA upto 6 phr. The solvent resistance of the compatibilized samples has been observed to be higher compared to the uncompatibilized blends; attributed to the increased interfacial adhesion between the blend components. DSC studies showed a shift of glass transition temperatures of the blend components towards higher temperatures indicating increased rigidity of the matrix in presence of EVA.     

天然虾青素改性白炭黑/天然橡胶复合材料的制备与性能

采用天然虾青素对白炭黑表面进行物理改性，并与天然橡胶（NR）制备成复合材料。利用RPA、DMA、SEM等测试手段对天然虾青素改性白炭黑/天然橡胶复合材料的结构与性能进行表征。结果表明，在硫化特性方面，与未采用天然虾青素改性白炭黑相比，采用天然虾青素改性白炭黑所得胶料的焦烧时间和工艺正硫化时间均缩短，促进了橡胶的硫化过程；在物理力学性能方面，所得硫化胶的拉伸强度基本不变，回弹性和耐磨性明显增加，压缩生热降低；在动态黏弹性方面，所得硫化胶的Payne效应明显降低，填料的分散性在一定程度上得到改善；在动态力学性能方面，所得硫化胶的滚动阻力降低，玻璃化转变温度提高。特别地，在耐老化方面，天然虾青素改性白炭黑/天然橡胶复合材料的耐热空气老化性能明显提高。     

Characterization and transport properties of ceramic filler incorporated natural rubber composites

Crystalline glass–ceramic fillers were prepared from calcium carbonate, silica, alumina, and calcium fluoride by heating and subsequent quenching in cold water. The fillers were incorporated into natural rubber (1,4-cis-polyisoprene) and the filled rubber composites were crosslinked with sulfur in the presence of different rubber additives. The unfilled and filled rubber composites were characterized. The transport properties of benzene, toluene, and p-xylene (BTX) through the rubber composites were studied in terms of sorption, diffusion, permeation, and mass transfer coefficients. The effect of the ceramic fillers on the mechanical, thermal and transport properties were studied. The sorption data at different temperatures were used for calculating activation energy of diffusion, permeation, free energy, and enthalpy of sorption. The BTX remained in the liquid state within the composite matrix as evident from negative ΔS. The diffusion coefficient (D) and mass transfer coefficient (k_mtc) of BTX decreased with the increase in filler loading. Accordingly, for the transport of BTX the unfilled rubber showed a D (D × 10⁷ cm²/s) and mass transfer coefficient (k_mtc × 10⁴ cm/s) of 5.67/3.97/2.96 and 7.71/7.08/7.04, respectively which decreased to 5.06/2.95/2.57 and 7.53/6.95/6.90, respectively for the composite containing 50 wt.% ceramic filler.     

Dielectric and microwave properties of carbon nanotubes/carbon black filled natural rubber composites

Abstract

Natural rubber (NR) based nanocomposites containing a constant amount (50 phr) of standard furnace carbon black and carbon nanotube (CNT) at a concentration from 1 to 5 phr have been prepared. Their dielectric (dielectric permittivity and dielectric loss) and microwave properties (coefficients of absorption and reflection of the electromagnetic waves and electromagnetic interference shielding effectiveness) have been investigated in the 1–12 GHz frequency range. The results achieved allow recommending CNTs as second filler for NR based composites to afford specific absorbing properties.     

Magnetic and dielectric properties of natural rubber and polyurethane composites filled with cobalt ferrite

Abstract

Cobalt ferrite (CoFe₂O₄) powders synthesised by sol–gel techniques were incorporated into natural rubber (NR) and polyurethane (PU) by two-roll milling at different loadings from 0 to 45 phr. In either NR or PU composites, the magnetisations were proportional to the CoFe₂O₄ loading, but the coercive field remained rather insensitive to the loading. The frequency response from 1 MHz to 1 GHz revealed that the real part of the magnetic permeability increased significantly only in the case of 45 phr CoFe₂O₄, while the imaginary part was modest in both NR and PU composites. In contrast, the electrical permittivity of CoFe₂O₄–PU was larger than that of CoFe₂O₄–NR composites, and both parts at 100 MHz had linear variations with the loading, in agreement with Wagner’s equation.     

Cellulose nanofibres and cellulose nanowhiskers based natural rubber composites: Diffusion,sorption, and permeation of aromatic organic solvents

This article investigates the transport behavior of three aromatic organic solvents, viz. benzene, toluene, and p‐xylene in natural rubber nanocomposite membranes containing cellulose nanofibres (CNFs) and cellulose nanowhiskers (CNWs) isolated from bamboo pulp. The solvent molecules act as molecular probes to study the diffusion, sorption, and permeation through the nanocomposites, and provide information on the nanocomposite structure and matrix–filler interactions. Both the nanocelluloses were found to decrease the uptake of aromatic solvents in nanocomposite membranes, but the effect was more significant in the case on nanofibers compared to nanowhiskers. Furthermore, the uptake decreased with increased penetrant size; being the highest for benzene and the lowest for p‐xylene. Transport parameters such as diffusion coefficient, sorption coefficient, and permeation coefficient have been calculated. Comparison of the experimental values of equilibrium solvent uptake with the predicted values indicated that both the nanocelluloses have restricted the molecular mobility at the interphase and thereby decreased the transport of solvents through the materials; being more significant for nanofibers. The results showed that both the used cellulosic nanomaterials act as functional additives capable of manipulating and tailoring the transport of organic solvents through elastomeric membranes, even at concentrations as low as 2.5 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

纳米氧化锌对天然胶乳膜干燥及硫化性能影响研究

采用失重法和溶胀法研究了普通氧化锌和纳米氧化锌活化的天然胶乳膜的干燥动力学,以及干燥过程中胶乳膜交联密度变化.结果表明:天然胶乳厚胶膜在成膜后仍含有大量水分并且去除困难.纳米氧化锌活化胶膜的干燥速率明显高于普通氧化锌胶膜.干燥温度对干燥过程影响显著,干燥时间随干燥温度升高明显降低.随着干燥的进行,2种氧化锌活化的胶乳膜的交联密度均迅速上升,在相同条件下,纳米氧化锌活化胶乳膜交联密度均比普通氧化锌的大.纳米氧化锌对天然胶乳膜的干燥及硫化过程均有促进作用.     

Preparation and properties of octadecylamine modified graphene oxide/styrene‐butadiene rubber composites through an improved melt compounding method

Octadecylamine modified graphene oxide/styrene‐butadiene rubber (GO‐ODA/SBR) composites are prepared by a novel and environmental‐friendly method called “Improved melt compounding”. A GO‐ODA/ethanol paste mixture is prepared firstly, and then blended with SBR by melt compounding. GO‐ODA sheets are uniformly dispersed in SBR as confirmed by scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. The interfacial interaction between GO‐ODA and SBR is weaker than that between GO and SBR, which is proved by equilibrium swelling test and dynamic mechanical analysis. GO‐ODA/SBR show more pronounced “Payne effect” than GO/SBR composites, indicating enhanced filler networks resulted from the modification of GO with ODA. GO‐ODA/SBR composite has higher tensile strength and elongation at break than SBR and GO/SBR composite. The tensile strength and elongation at break for the composite with 5 parts GO‐ODA per hundred parts of rubber increase by 208% and 172% versus neat SBR, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42907.     

Development and molecular dynamics simulation of green natural rubber composites with modified sisal microcrystalline cellulose

In this study, green composites were prepared using natural rubber (NR) as the matrix and the sisal microcrystalline cellulose (MCC) as the filler. Three modifying agents oleic acid (OA), γ-aminopropyltriethoxylsilane (KH550), and bis-γ-(triethoxysilylpropyl)-tetrasulfide (Si69) were individually tested to modify the MCC to improve the interfacial compatibility of the NR and MCC. Combined with modern instrumental analysis technology and molecular dynamics simulation, the reinforcing effect and microscopic mechanism of modified MCC on NR were analyzed. The structure–activity relationship of NR and MCC composites was further revealed, and the interaction between the two components was clarified. At the same time, the reinforcing and compatibilizing effect of three kinds of modified MCC in NR matrix were also revealed. The results showed that the properties of NR/Mod-MCC composites were better than those of NR/MCC composites, where NR/OA-MCC presented the highest tensile strength, followed by NR/Si69-MCC. In addition, NR/Si69-MCC exhibited higher elongation at break and NR/KH550-MCC exhibited higher vulcanization characteristics. Molecular model systems were constructed through molecular dynamics simulation to investigate the interactions between the three modified cellulose molecules and the NR molecules. OA-cellulose has a better interaction with NR than KH550-cellulose and Si69-cellulose, The simulation results were consistent with the experimental results.     

Study of the thermomechanical and electrical properties of conducting composites containing natural rubber and carbon black

This work describes the preparation and characterization of composite materials obtained by the combination of natural rubber (NR) and carbon black (CB) in different percentages, aiming to improve their mechanical properties, processability, and electrical conductivity, aiming future applications as transducer in pressure sensors. The composites NR/CB were characterized through optical microscopy (OM), DC conductivity, thermal analysis using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermogravimetry (TGA), and stress–strain test. The electrical conductivity varied between 10^?9 and 10 S m^?1, depending on the percentage of CB in the composite. Furthermore, a linear (and reversible) dependence of the conductivity on the applied pressure between 0 and 1.6 MPa was observed for the sample with containing 80 wt % of NR and 20% of CB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characteristics of natural rubber/poly(ethylene oxide) salt hybrid mixtures as novel polymer electrolytes

Poly(ethylene oxide) (PEO) of molecular weight 1000 (PEO₁₀₀₀) containing lithium benzenesulfonate (LiBs) (PEO₁₀₀₀/LiBs), PEO derivatives having benzenesulfonate groups on both chain ends (PEO₁₀₀₀–(BSLi)₂), or 1-ethyl-2,3-dimethylimidazolium bromide (ImB), were each blended with natural rubber (NR). The ionic conductivity was measured from AC impedance values. The ionic conductivity of the mixture of NR and PEO₁₀₀₀/LiBs (40 wt%) was about 10⁻⁶ S cm⁻¹ at 50°C; this mixture retained rubbery physical characteristics. At NR content of 10 wt%, the ionic conductivity of the mixture (NR/PEO₁₀₀₀/LiBs) was 2.7×10⁻⁵ Scm⁻¹ at 50°C, approximately 10 times higher than that of the bulk PEO/LiBs mixture. For mixtures of NR and PEO₁₀₀₀–(BSLi)₂, no improvement in ionic conductivity by mixing was found. The ionic conductivity of the mixture of NR and ImB was about 10 times higher than for the bulk of PEO₁₀₀₀–(BSLi)₂ at a NR content of 10 wt%. We propose that the ionic conductivity of the mixture increases when an ion conducting matrix containing simple salt is added. On the other hand, the DSC curve for NR/PEO derivatives showed two T_gs based on the separate components, suggesting phase separation of the PEO derivative in the NR phase.     

天然橡胶/固相法改性纳米碳酸钙复合材料的微观形态与力学性能

研究了天然橡胶（NR）／硬脂酸包覆型纳米碳酸钙（CCR）复合材料和NR／固相法改性纳米碳酸钙（M-CCR）复合材料的微观形态、力学性能、耐老化性能和热稳定性能等。结果表明,与CCR相比,M—CCR在NR中的分散性更好,界面结合形态得到了改善;NR／M—CCR复合材料的力学性能、耐老化性能和热稳定性能显著提高,且当M—CCR用量少于10份时,NR／M—CCR复合材料的综合性能最佳。