Enhanced mechanical properties of graphene/natural rubber nanocomposites at low content

Graphene/natural rubber (GE/NR) nanocomposites were prepared by a modified latex mixing method combined with in situ chemical reduction. It was found that the GE nanosheets are well dispersed and have strong interfacial interaction with NR. Thus, adding a low content of GE can remarkably increase the tensile strength and the initial tensile modulus of NR. With incorporation of as low as 0.5 phr of GE, a 48% increase in the tensile strength and an 80% increase in the initial tensile modulus are achieved without sacrificing the ultimate strain. But further increasing the GE loading degrades the tensile strength and the ultimate strain. Dynamic mechanical measurement indicates that the storage modulus of the nanocomposites is greatly enhanced with addition of GE, while the loss tangent peak is depressed due to the reduced mobility of the rubber molecules. The reinforcement effect of GE on NR is interpreted as a change in the strain induced crystallization and network structure of the nanocomposites, based on the analysis of Mooney ? Rivlin plots and the tube model.© 2013 Society of Chemical Industry     

Physical properties of natural rubber/organoclay nanocomposites compatibilized with epoxidized natural rubber

Onium ion‐modified montmorillonite (organoclay) was melt compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) was used in 10 parts per hundred rubber (phr) as a compatibilizer. The effect of organoclay with different filler loading up to 10 phr was studied. Cure characteristics were determined by a Monsanto MDR2000 rheometer, whereas the tensile, compression, and tear properties of the nanocomposites were measured according to the related ASTM standards. While the torque maximum and torque minimum increased slightly, both scorch time and cure time reduced with the incorporation of organoclay. The tensile strength, elongation at break, and tear properties went through a maximum (at about 2 phr) as a function of the organoclay content. As expected, the hardness, moduli at 100% (M100) and 300% elongations (M300) increased continuously with increasing organoclay loading. The compression set decreased with incorporation of organoclay. The dispersion of the organoclay in the NR stocks was investigated by X‐ray diffraction and transmission electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1083–1092, 2006     

Sulfonic acid-functionalized mesoporous silica catalyst with different morphology for biodiesel production

Sulfonic acid functionalized mesoporous silica based solid acid catalysts with different morphology were designed and fabricated. The synthesized materials were characterized by various physicochemical and spectroscopic techniques like scanning electron microscope-energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface area, thermogravimetric analysis and n-butylamine acidity. The shape of catalysts particles plays an important role in its activity. The sulfonic acid functionalized mesoporous silica catalysts of spherical shape and the cube shape were assessed for catalytic activity in biodiesel production. The catalytic biodiesel production reaction over the catalysts were studied by esterification of free fatty acid, oleic acid with methanol. The effect of various reaction parameters such as catalyst concentration, acid/alcohol molar ratio, catalyst amount, reaction temperature and reaction time on catalytic activity were investigated to optimize the conditions for maximum conversion. It was sulfonated cubic shape mesoporous silica which exhibited better activity as compared to the spherical shape silica catalysts. Additionally, the catalyst was regenerated and reused up to three cycles without any significant loss in activity. The present catalysts exhibit superior performance in biodiesel production and it can be used for the several biodiesel feedstock’s that are rich in free fatty acids.     

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.     

Synthesis of hexagonal and cubic mesoporous silica using power plant bottom ash

An alkali fusion method was adopted to extract silicate species from coal bottom ash in a power plant and the supernatant solution was used for the synthesis of MCM-41, SBA-15, and SBA-16 mesoporous silica materials. The minor impurities present in the bottom ash were not found to be detrimental to the successful formation of mesoporous silica phases. Additional silica from sodium metasilicate was introduced to improve the textural properties for SBA-15 and SBA-16. According to SEM analyses, particle morphology of the samples gradually approaches those prepared using pure chemical as the amount of external silica source increases. XRD analyses confirmed well-ordered mesostructures in all of these silica materials. N₂ adsorption–desorption isotherms of MCM-41 prepared using bottom ash showed a type IV isotherm with a region of steep increase due to capillary condensation, whilst SBA-15 and SBA-16 showed type IV isotherm with H1 and H2 hysteresis loops, respectively. ²⁷Al MAS NMR analysis of MCM-41 synthesized from the supernatant solution reveals that the extracted Al species from bottom ash were tetrahedrally incorporated in the framework. TEM clearly showed the uniform pore structure of the materials prepared using the industrial waste.     

Compatibility enhancement of silica and natural rubber compound using UVA-induced silane-grafted saponified skim natural rubber

Silane coupling agents are potential reagents widely used to improve the compatibility between silica and less polar rubber, especially natural rubber (NR). Nevertheless, high temperature is generally required to generate the interaction between the components during the mixing process. Accordingly, an alternative method by grafting the silane coupling agent onto the rubber molecules would be a desirable approach to develop a compatibilizer for the silica-filled NR compound. In this work, skim NR was used as a starting material due to its linear structure. The optimal conditions of the grafting reaction were found to be 1 phr of an alkoxy silane and 5 phr of benzoyl peroxide under 8 min of UVA irradiation time. These conditions were applied for producing the rubber material used in the mixing process of STR 5L and silica. The cure characteristics, silica dispersion and mechanical properties of the rubber compounds were improved, suggesting that the modified rubber was an efficient material for increasing the compatibility between silica and NR.     

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。     

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。     

Effect of nanosized mesoporous MCM-41 (with template) material on properties of natural rubber nanocomposites

Abstract

Mesoporous mobil composition of matter 41 (MCM-41) (with template) was used directly as a new filler for naural rubber (NR). Inside the pore chanels, and on the outer surface of the MCM-41 particle, were cationic surfactant CTAB and Pluronic F₁₂₇ (molecular weight = 11 500) mixture. Results showed that the tensile properties and the thermal stability of NR/mesoporous MCM-41 (with template) nanocomposite were improved at low filler loading as compared with those of NR compound. Scanning electron microscopy observations revealed that enhancement of the interface was obtained by adding MCM-41 (with template).     

壳聚糖改性二氧化硅/天然橡胶复合材料的性能

采用溶胶-凝胶法制备了壳聚糖改性二氧化硅,并采用共沉降法制备了壳聚糖改性二氧化硅/天然橡胶（NR）复合材料,考察了壳聚糖用量对复合材料硫化特性、拉伸性能、耐老化性能的影响,并用扫描电子显微镜观察了拉伸试样的断面形貌。结果表明,壳聚糖的加入使NR复合材料的性能得到明显改善,当其用量为0.5 g时,复合材料的硫化特性与拉伸性能最佳,正硫化时间为1.95 min,拉伸强度为24.01 MPa,扯断伸长率达到256%;当壳聚糖添加量为0.3 g时,硫化胶的拉伸强度与扯断伸长率的性能保持指数最高,耐老化性能最佳;经壳聚糖改性的二氧化硅在NR中的分散性得到改善。     

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。     

白炭黑用量对氯丁橡胶/天然橡胶共混物性能的影响

研究了不同用量的沉淀法白炭黑填充质量比75/25的氯丁橡胶/天然橡胶共混物的物理机械性能、耐热老化性能和耐油性能,并用扫描电镜研究了共混物的结构。结果显示,白炭黑的加入改善了共混硫化物的拉伸强度、100%定伸应力和邵尔A硬度。压缩永久变形减小,黏度增大,从而导致在形变的过程中天然橡胶分散相占有率相对减少。相关性能也证明随着白炭黑用量的增加,硫化胶的耐热和耐油性能显著提高。     

Thermal conductivity of natural rubber nanocomposites with hybrid fillers

Natural rubber nanocomposites filled with hybrid fillers of multi-walled carbon nanotubes(CNTs) and carbon black(CB) were prepared. CNTs were ultrasonically modified in mixture of hydrogen peroxide(H_2O_2) and distilled water(H_2O). The functional groups on the surface of CNTs, changes in nanotube structure and morphology were characterized by Fourier transform infrared spectroscopy(FT-IR), Raman Spectroscopy, and transmission electron microscopy(TEM). It shows that hydroxyl(OH·) is successfully introduced. The surface defects of modified CNTs were obviously higher than those of original CNTs, and the degree of agglomeration was greatly reduced. Thermal conductivity of the composites was tested by protection heat flow meter method. Compared with unmodified CNTs/CB filling system, the thermal conductivity of hybrid composites is improved by an average of 5.8% with 1.5 phr(phr is parts per hundred rubber) of hydroxyl CNTs and 40 phr of CB filled. A three-dimensional heat conduction network composed of hydroxyl CNTs and CB, as observed by TEM, contributes to the good properties. Thermal conductivity of the hybrid composites increases as temperature rises. The mechanical properties of hybrid composites are also good with hydroxyl CNTs filled nanocomposites; the tensile strength, 100% and 300% tensile stress are improved by 10.1%, 22.4% and 26.2% respectively.     

短纤维/白炭黑/天然橡胶复合材料撕裂性能的研究

采用新型裤形撕裂试样,研究白炭黑和短纤维补强的天然橡胶(NR)复合材料在不同撕裂速率下的撕裂性能。结果表明:白炭黑/NR复合材料在低撕裂速率下有较高的撕裂强度,反之撕裂强度降低,撕裂在中低撕裂速率下呈现典型的"粘附-滑移"特点,在高撕裂速率下呈现"锯齿状";在短纤维/白炭黑/NR复合材料中,撕裂路径在中低撕裂速率下明显向腿部偏移,在高撕裂速率下也出现波动较小的"锯齿状"撕裂,撕裂路径和撕裂强度更为稳定。     

Facile synthesis of mesoporous titanium dioxide nanocomposites with controllable phase compositions by microwave-assisted esterification

Mesoporous titanium dioxide nanocomposites with controllable phase compositions and high surface areas were synthesized through convenient, fast, and one-step microwave-assisted esterification method. The introduction of microwave in the synthetic reactions not only accelerates the esterification reaction but also promotes the fast crystallization. By changing reaction temperature, microwave irradiation time, the amount of staring materials and the composition of solvents, pure anatase, pure rutile or mixed phase titanium dioxide nanocomposites were obtained in minutes. Meanwhile, the size of crystallite can be controlled by the reaction temperature. The as-synthesized materials display significative photocatalytic activities without any further disposal, among which the material with 3.6% rutile shows the best effect in degradation of methylene blue under UV-light irradiation. Moreover, the nitrogen adsorption–desorption results illustrate the obtained samples are mesophases. It is also interesting that the pure rutile has specific surface area as high as 210 m² g^?1 calculated by BET equation. The method can control the hydrolysis of TiCl₄ well and dramatically shorten the preparation time of titanium dioxide.     

Preparation,microstructure, and property of silicon rubber/organically modified montmorillonite nanocomposites and silicon rubber/OMMT/fumed silica ternary nanocomposites

Five different types of organically modified montmorillonites (OMMT), including Nanomor® I.30P, I.44P, I.24TL, I.34TCN, and I.31PS, were incorporated into silicone rubber (SiR), respectively, by using a melt‐blending method. The intercalation structure and spatial dispersion of OMMT in the obtained composites were characterized with wide‐angle X‐ray diffraction and transmission electron microscopy. The results revealed that the high‐polar organic intercalants or silane‐coupling agent might play the negative roles in the melt intercalation of SiR into OMMT, and the higher the initial interlayer spacing of the OMMT, the easier the intercalation. The intercalated structure in the SiR/I.44P OMMT nanocomposite has the largest interlayer spacing, and the spatial dispersion of OMMT is also the best. When OMMT loading is low (i.e., less than 10 phr), the dispersion of OMMT is poor. The dispersion of OMMT improves with increasing OMMT dosage, when the loading does not exceed 30 phr. The gas barrier property and the mechanical properties of the SiR are obviously improved by the incorporation of OMMT. The nitrogen gas permeability coefficient of the SiR nanocomposite containing 30 phr OMMT (I.44P) is lower than that of net SiR by 31%. To further improve the dispersion of OMMT in SiR, 20 phr fumed silica (FS) was added to the compound before mixing OMMT for increasing viscosity of the compound and mechanical shearing force during compounding OMMT. The resultant SiR/OMMT/FS ternary nanocomposites exhibit improved dispersion of OMMT and better gas barrier property than the binary counterparts. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Fracture properties of silica/carbon black-filled natural rubber vulcanizates

Crack growth property of natural rubber (NR) vulcanizate with varying silica/carbon black content was examined. Tensile specimen with edge cut was used for estimating fracture properties. All filled NR specimens showed critical cut-size (C _cr ), which is related to abrupt decrease in tensile strength. Carbon black-filled NR, S0 (Si/N330=0/50) has higher tensile strength than equivalently loaded silica-filled NR vulcanizates, S5 (Si/N330=50/0). When the precut size of specimen was less than critical cut-size, tensile strength of S1 (Si/N330=10/40) composition was the highest and that of S5 was the lowest. The critical cut-size passes through a maximum for S2 (Si/N330=20/30) and then decreases gradually with silica loading. An interesting result was that silica and carbon black-blended compounds gave higher critical cut size than the all-carbon black compounds, S0. The inherent flaw size decreased from 246 μm for S0 to 80 μm for S5 as the silica content increased.     

乳液法天然橡胶/丁腈橡胶/蒙脱土纳米复合材料的结构与性能

采用乳液法制备了天然橡胶/丁腈橡胶/蒙脱土纳米复合材料,考察了其微观形态,探讨了复合材料的硫化特性及静态和动态力学性能.结果表明,蒙脱土以纳米尺寸均匀分布于丁腈橡胶基质中,橡胶分子链并未插层进入蒙脱土片层;蒙脱土使复合材料的焦烧时间和正硫化时间增加,可明显提高复合材料的静态力学性能;复合材料具有与天然橡胶/丁腈橡胶共混...     

N,N-二甲基甲酰胺-硫酸二甲酯对羧酸酯化反应的研究

N,N-二甲基甲酰胺二甲基缩醛(简称 DMFDMA)是一种在有机合成中应用很广的多 功能试剂,该试剂以其反应条件温和,产率高,快 速及简便的后处理等优点,已广泛用于多种化合 物的合成[1～4].     

Preparation and properties of nylon 6/carboxylic silica nanocomposites via in situ polymerization

Nylon 6/carboxylic acid‐functionalized silica nanoparticles (SiO₂‐COOH) nanocomposites were prepared by in situ polymerization of caprolactam in the presence of SiO₂‐COOH. The aim of this work was to study the effect of carboxylic silica on the properties of the nylon 6 through the interfacial interactions between the SiO₂‐COOH nanoparticles and the nylon 6 matrix. For comparison, pure nylon 6, nylon 6/SiO₂ (unmodified) and nylon 6/amino‐functionalized SiO₂ (SiO₂‐NH₂) were also prepared via the same method. Fourier transform infrared spectrometer (FTIR) spectroscopy was used to evaluate the structure of SiO₂‐COOH and nylon 6/SiO₂‐COOH. The results from thermal gravimetric analysis (TGA) indicated that decomposition temperatures of nylon 6/SiO₂‐COOH nanocomposites at the 5 wt % of the total weight loss were higher than the pure nylon 6. Differential scanning calorimeter (DSC) studies showed that the melting point (T_m) and degree of crystallinity (X_c) of nylon 6/SiO₂‐COOH were lower than the pure nylon 6. Mechanical properties results of the nanocomposites showed that nylon 6 with incorporation of SiO₂‐COOH had better mechanical properties than that of pure nylon 6, nylon 6/SiO₂, and nylon 6/SiO₂‐NH₂. The morphology of SiO₂, SiO₂‐NH₂, and SiO₂‐COOH nanoparticles in nylon 6 matrix was observed using SEM measurements. The results revealed that the dispersion of SiO₂‐COOH nanoparticles in nylon 6 matrix was better than SiO₂ and SiO₂‐NH₂ nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011