Optimisation of physical and mechanical properties of rubber compounds by response surface methodology--Two component modelling using vegetable oil and carbon black

Response surface methodology was used for predicting the optimal composition of vegetable oil and carbon black in rubber compounding. Central composite rotatable design for two variables at five levels was chosen as the experimental design. The data obtained from measurement of properties was fitted as a two variable second order equation and were plotted as contour plots using programme developed in MATLAB v.5. It is observed from the contour plots that the increase in cross-link density caused by the formation of rubber mono-layer from its multi-layer on increasing the carbon black loading upto the central point (50 phr) of experimental region increases 300% modulus and elongation at break and reduces the ultimate properties like tear strength and tensile strength. On the other-hand hardness increases with increase in solid inclusion of carbon black. From the contours it is observed that the addition of vegetable oil upto 2-3 phr, cross-link density increases due to its coupling action leading to increase in hardness and modulus and lowering of ultimate properties like tensile strength and elongation at break. Addition of further amount of vegetable oil shows less coupling and more plasticising effect leading to increase in tear strength, tensile strength and elongation at break and decrease in hardness and 300% modulus.     

Compounding,mechanical and morphological properties of carbon-black-filled natural rubber/recycled ethylene-propylene-diene-monomer (NR/R-EPDM) blends

Blends of natural rubber/virgin ethylene-propylene-diene-monomer (NR/EPDM) and natural rubber/recycled ethylene-propylene-diene-monomer (NR/R-EPDM) were prepared. A fixed amount of carbon black (30 phr) was also incorporated. The effect of the blend ratio (90/10, 80/20, 70/30, 60/40 and 50/50 (phr/phr)) on the compounding, mechanical and morphological properties of carbon-black-filled NR/EPDM and NR/R-EPDM blends was studied. The results indicated that both the carbon-black-filled NR/EPDM and NR/R-EPDM blends exhibited a decrease in tensile strength and elongation at break for increasing weight ratio of EPDM or R-EPDM. The maximum torque (S′M_H), minimum torque (S′M_L), torque difference (S′M_H?M_L), scorch time (ts₂) and cure time (tc₉₀) of carbon-black-filled NR/EPDM or NR/R-EPDM blends increased with increasing weight ratio of virgin EPDM or R-EPDM in the blend. SEM micrographs proved that, for low weight ratios of virgin EPDM or R-EPDM, the blends exhibited high surface roughness and matrix tearing lines. The blends also showed a reduction in crack path with increasing virgin EPDM or R-EPDM content over 30 phr. This reduction in crack path could lead to less resistance to crack propagation and, therefore, low tensile strength.     

Dynamically vulcanized ethylene propylene diene terpolymer/nylon thermoplastic elastomers

A thermoplastic elastomer (TPE) of ethylene propylene diene terpolymer (EPDM) and nylon with excellent mechanical properties was prepared by dynamic vulcanization. The effects of the curing systems, compatibilizer, nylon content and reprocessing on the mechanical properties of EPDM/nylon TPEs were investigated in detail. Experimental results indicate that maleic anhydride (MAH) grafted EPR has a better performance in compatibilizing the EPDM/nylon blends compared with other compatibilizers containing acid group. Tensile strength and elongation at break go through a maximum value at a compatibilizer resin content (on total rubber dosage) of 20%. EPDM/nylon TPE using sulfur as curative has higher tensile strength and elongation than that of TPE using phenolic resin or peroxide as curatives. Tensile strength and elongation at break increase with increasing nylon content. Scanning electron microscopy results show that rubber particles distributed at an average size of 1 μm in dynamic vulcanized EPDM/MAH-g-EPR/nylon TPE.     

High performance hybrid reinforcement of nitrile rubber using short pineapple leaf fiber and carbon black

Rubber composites with very high moduli at low elongation, high elongation at break and high ultimate breaking strength have been developed. The matrix was acrylonitrile butadiene rubber (NBR) and the hybrid (fibrous and particulate) reinforcements were short, fine pineapple leaf fiber (PALF) and carbon black. The amount of PALF was fixed at 10 parts (by weight) per hundred of rubber (phr) while that of carbon black was varied from 0 to 30 phr. Uniaxial NBR composites were prepared. Tensile strength, elongation at break, modulus and tear strength of the hybrid composites were characterized in both longitudinal (parallel to the fiber axis) and transverse (perpendicular to the fiber axis) directions. The addition of carbon black causes the slope of the early part of the stress–strain curve to increase and also extends breaking to greater strains. At carbon black contents of 20 phr and above, the stress–strain relation displays an upturn at high elongations, providing greater ultimate strength. Comparison with the usual carbon black filled rubber shows that the composite behavior at low strains is determined by the PALF, and at high strains by the carbon black. This high performance PALF-carbon black reinforced NBR shows great promise for engineering applications.     

Radiation vulcanization of NR/SBR composite enhanced with different polyfunctional monomers

The effect of different polyfunctional monomers (PFMs) as enhancing agents on the properties of natural rubber/styrene-butadiene rubber blend reinforced with 40 (phr) part per hundred part of rubber, by weight of HAF carbon black and vulcanized with gamma irradiation was investigated. The coagents N,N’ methylene diacrylamide (MDA), trimethylol propane-trimethacrylate (TMPTMA) and trimethylol-methane tetraacrylate (TMMTA) were used at a constant content of 5 phr. The physico-chemical properties such as tensile strength, tensile modulus at 100 % elongation, elongation at break, gel fraction and swelling number were studied. The results indicated that the properties are greatly improved by PFMs at lower doses. TMMTA as coagent is more effective than TMPTMA and MDA.     

Effect of dendrimer modified montmorillonite on structure and properties of EPDM nanocomposites

The purpose of this work was to study the effect of dendrimer modified clay minerals on the structure and properties of ethylene-propylene-diene monomer (EPDM) nanocomposites.Flame-retardant and dendrimer modified organic montmorillonite (FR-DOMt) was successfully prepared by Na⁺-montmorillonite, tetrahydroxymethyl phosphonium chloride (THPC), N, N-dihydroxyl-3-aminomethyl propionate, and boric acid. This dendritic type of organoclay (OC) was used in preparation of EPDM/FR-DOMt nanocomposites. The properties of these nanocomposites were studied. The dispersion status of the layered silicates in EPDM was revealed by X-ray diffractometer (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRD and TEM results showed that FR-DOMt was exfoliated in the EPDM matrix when 10 phr of FR-DOMt was incorporated. The mechanical behavior, thermal stability, and flame retardance of the samples were examined. The experimental data demonstrated that the EPDM hybrids owned an improved tensile strength and elongation at break. In addition, the nanocomposites exhibited higher thermal stability and flame retardance than that of unfilled EPDM matrix.     

基于乘用车轮胎胎面胶粉的再生橡胶的制备及性能

通过力化学再生法制备了以废轮胎胶粉为原料的再生橡胶，研究了不同活化剂420用量对再生橡胶性能的影响，测试表明：再生橡胶含硫键断裂生成了硫自由基，随着活化剂含量的增加，再生橡胶的邵氏硬度和交联密度持续降低；拉伸强度、断裂延伸率和凝胶含量均先升高后降低，在活化剂用量为0.9 phr时，拉伸强度和断裂延伸率最大，再生橡胶的凝胶含量最大为19.7%。 微观形貌发现，废轮胎胎面胶粉的颗粒较为分散，再生橡胶的结构颗粒相互粘连，孔洞和缺陷较多，再生橡胶的门尼黏度随着活化剂含量的增加而降低。 综合来看，活化剂420的最佳含量为0.9 phr，再生橡胶各项性能最优。     

Preparation and cryogenic mechanical properties of epoxy resins modified by poly(ethersulfone)

A thermoplastic, poly(ethersulfone) (PES) was used to modify a bisphenol‐F based epoxy resin cured with an aromatic diamine. The initial mixtures before curing, prepared by melt mixing, were homogeneous. Scanning electron microscopy (SEM) micrographs of solvent‐etched fracture surfaces of the cured blends indicated that phase separation occurred after curing. The cryogenic mechanical behaviors of the epoxy resins were studied in terms of tensile properties and Charpy impact strength at cryogenic temperature (77 K) and compared to their corresponding behaviors at room temperature (RT). The addition of PES generally improved the tensile strength, elongation at break, and impact strength at both RT and 77 K except the RT tensile strength at 25 phr PES content. It was interesting to observe that and the maximum values of the tensile strength, elongation at break, and impact strength occurred at 20 phr PES content where a co‐continuous phase formed. Young's modulus decreased slightly with the increase of the PES content. Moreover, the tensile strength and Young's modulus at 77 K were higher than those at RT at the same composition, whereas the elongation at break and impact strength showed the opposite results. Finally, the differential scanning calorimetry analysis showed that the glass transition temperature (T_g) was enhanced by the addition of PES. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 612–624, 2008     

Radiation effect on properties of carbon black filled NBR/EPDM rubber blends

Rubber blend of acrylonitrile butadiene rubber (NBR) and ethylene-propylene diene monomer (EPDM) rubber (50/50) has been loaded with increasing contents, up to 100 phr, of reinforcing filler, namely, high abrasion furnace (HAF) carbon black. Prepared composites have been subjected to gamma radiation doses up to 250 kGy to induce radiation vulcanization under atmospheric conditions. Mechanical properties, namely, tensile strength (TS), tensile modulus at 100% elongation (M₁₀₀), and hardness have been followed up as a function of irradiation dose and degree of loading with filler. On the other hand, variation of the swelling number as a physical property, as a function of same parameters, however, in car oil as well as brake oil has been undertaken. In addition, the electrical properties of prepared composites, namely, their electrical conductivity, were also evaluated. The thermal behavior of the prepared composites was also investigated. The results obtained indicate that improvement has been attained in different properties of loaded NBR/EPDM composites with respect to unloaded ones.     

羟基不饱和脂肪酸改性纳米碳酸钙对聚丙烯微观形态和流变性能的影响

采用羟基不饱和脂肪酸,通过固相法对硬脂酸改性的工业纳米碳酸钙CCR进行表面改性制备了R-CCR,红外光谱(FTIR)显示改性剂已结合在碳酸钙表面.通过熔融共混法制备了聚丙烯(PP)/乙丙橡胶(EPDM)/纳米碳酸钙二元和三元复合材料.并利用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察复合材料的微观形态,发现R-CCR的加入,使PP复合材料的拉伸断面出现明显的拉丝状结构和大面积的屈服变形,与PP/EPDM/CCR相比,PP/EPDM/R-CCR冲击断面的空穴明显增加并细化,R-CCR在PP基体中分散均匀,且界面模糊,与基体的相容性明显优于CCR.复合材料流变行为的研究表明R-CCR的加入,体系储存模量G′和损耗模量G″随频率的增加而增加,对损耗因子和复数粘度的影响不大;但PP/EPDM/R-CCR复合材料的表观粘度,明显低于PP/EPDM/CCR和纯PP,同时,剪切速率的增加可有效降低体系的表观粘度.力学性能表明,R-CCR对PP同时起到增韧和增强的效果.且R-CCR和EPDM对PP具有协同增韧的效果.在保持聚丙烯的模量和强度基本不变的前提下,大幅度的改善聚丙烯的韧性,同时加工性能保持不变.     

Properties of ethylene propylene diene rubber/white and black filler composites cured by gamma radiation in presence of sorbic acid

The effect of incorporating sorbic acid (SA), an echo-friendly curing agent, and silica or carbon black (CB) filler, as well as gamma irradiation on the physico-chemical, mechanical and thermal properties of ethylene propylene diene monomer rubber (EPDM) was investigated. The results indicated that the developed composites revealed improvement in the studied parameters over the untreated samples. Filler incorporation into rubber matrix has been proven a key factor in enhancing the swelling resistance, tensile strength and thermal properties of the fabricated composites. The improvement in tensile strength and modulus was attributed to better interfacial bonding via SA. Alternatively, a comparison was established between the performance of the white and black fillers. The utmost mechanical performance was reported for the incorporated ratios 10 phr SA and 40 phr white filler into a 50 kGy irradiated composite. Meanwhile, the incorporation of CB yielded better thermally stable composites than those filled with silica at similar conditions.     

Effect of silane coupling agent on the polymer‐filler interaction and mechanical properties of silica‐filled NR

The effects of filler loading and a new silane coupling agent 3‐octanoylthio‐1‐ propyltriethoxysilane (NXT silane) on the polymer‐filler interaction and mechanical properties of silica‐filled and carbon black‐filled natural rubber (NR) compounds were studied. Silica (high dispersion silica7000GR, VN2, and VN3) and carbon black (N330) were used as the fillers, and the loading range was from 0 to 50 phr. The loading of NXT silane was from 0 to 6 phr. Experimental results show that the maximum and minimum torques of silica and carbon black‐filled NR increase with increasing filler loading. With increasing filler loading, the scorch time and optimum cure time decrease for carbon black‐filled NR, but increase for silica‐filled NR. The minimum torque, scorch time, and optimum cure time decrease because of the presence of NXT silane. For the carbon black and silica‐filled NR, the tensile strength and elongation at break have maximum values, but the hardness, M300, M100, and tear strength keep increasing with filler loading. The mechanical properties of silica‐filled NR were improved in the presence of NXT silane. With increasing filler loading, the storage modulus of filled NR increases, but the loss factor decreases. Carbon black shows the strongest polymer‐filler interaction, followed by VN3, 7000GR, and VN2. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 573–584, 2005     

Curing and Physical Properties of Natural Rubber/Wood Flour Composites

Natural rubber based composites were prepared by incorporating Wood flour of two different particle size ranges (250–300 µm) and (300–425 µm) and concentrations (15 and 30 phr) into the matrix, using a Banbury® internal mixer according to a base formulation. Curing characteristics of the samples were studied. Influence of particle size and loading of filler on the properties of the composites was analyzed. Results obtained show that the addition of wood flour to natural rubber increased scorch time and curing time and caused improvement in modulus at 300% strain and in tear properties. However, it decreased tensile strength and elongation at break. The particle size range of 300–425 µm was found to offer the best overall balance of mechanical and dynamic properties (tan δ and viscous torque). Swelling behavior of the composites in toluene was also analyzed in order to determine the rubber volume fraction and crosslinking density. Composites with the bigger particle size wood flour were found to have greater crosslinking density than the ones with smaller particle size, fact that could possibly indicate a better rubber-filler interaction in the former. Major percentage of filler increased slightly this interaction. Water absorption behavior of the composites with wood flour reached a maximum of 12% w/w when 30 phr of filler were incorporated; nonetheless, particle size did not affect this property. The ageing study in presence of air at 70 °C revealed that natural rubber composites with wood flour maintained the same classification cell with temperature as the pure rubber. A compound with 30 phr of carbon black was prepared for comparative purposes. Results obtained were as expected. Scorch time decreased and higher values of modulus at 300% strain and tensile strength were achieved, due to strongest interaction between filler and elastomer.     

改性纳米炭黑/聚氨酯复合物的制备及表征

利用有机硅偶联剂改性的纳米炭黑和聚氨酯制备了纳米炭黑/聚氨酯复合物. 采用红外光谱、透射电镜、流变学及力学性能等测试方法对纳米粒子及其聚氨酯复合物进行了表征. 红外光谱表明, 纳米粒子的存在使聚氨酯的氢键结构发生了改变. 适量改性纳米炭黑粒子明显提高了聚氨酯的拉伸强度和断裂伸长率等力学性能. 流变学测试结果表明, 溶液中改性纳米炭黑粒子与聚氨酯分子间存在明显的相互作用.     

The influence of nano silica particles on gamma-irradiation ageing of elastomers based on chlorosulphonated polyethylene and acrylonitrile butadiene rubber

The goal of this work was to study gamma irradiation ageing of rubber blends based on acrylonitrile butadiene rubber (NBR) and chlorosulphonated polyethylene rubber (CSM) reinforced by silica nano particles. The NBR/CSM compounds (50: 50, w/w) filled with different content of filler (0–100 phr) were crosslinked by sulfur. The vulcanization characteristics were assessed using the rheometer with an oscillating disk. The vulcanizates were prepared in a hydraulic press. The obtained materials were exposed to the different irradiation doses (100, 200, 300 and 400 kGy). The mechanical properties (hardness, modulus at 100% elongation, tensile strength and elongation at break) and swelling numbers were assessed before and after gamma irradiation ageing.     

The Effect of 3-aminopropyltrimethyoxysilane (AMEO) as a Coupling Agent on Curing and Mechanical Properties of Natural Rubber/Palm Kernel Shell Powder Composites

This research is conducted using palm kernel shell powder (PKS) as filler in natural rubber The effect of 3-aminopropyltrimethoxysilane as coupling agent on composites were studied at different palm kernel shell loading i.e, 0 5, 10, 15 and 20 phr The palm kernel shell was crushed and sieved to an average particle size of 5.53 μm The palm kernel shell filled natural rubber composites were prepared using laboratory size two roll mill The curing characteristics such as scorch time, cure time and maximum torque were obtained from rheometer The palm kernel shell powder filled natural rubber composites were cured at 150^oC using hot press according to their cure time Curing characteristics, tensile properties, rubber-filler interaction and morphological properties of palm kernel shell powder filled natural rubber were studied Scorch time and cure time show reduction but tensile strength, elongation at break, modulus at 100% (M100) and modulus at 300% (M300) increased with the presence of 3-aminopropyltrimethyloxysilane Rubber-filler interaction studies showed that rubber filler interaction in natural rubber filled with palm kernel shell powder improved with incorporation of 3-aminopropyltrimethyoxysilane.     

Physical characterization of coupled poly(lactic acid)/starch/maleic anhydride blends plasticized by acetyl triethyl citrate

Acetyl triethyl citrate (ATC) was used as a plasticizer for poly(lactic acid) (PLA)/starch blends coupled with maleic anhydride and an initiator of 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (L101). Elongation of the blend at break was markedly increased when the ATC content was above the 8% loading level, which is referred to as the percolation threshold. The extended elongation was achieved at the expense of tensile strength and elastic modulus. Thermal transitions of the blend, including the glass transition temperature (T(g)), cold crystallization temperature (T(c)) and melting temperature (T(m)), decreased with ATC content. Thermally induced ATC migration affected the thermal behavior of the plasticized blends and reduced elongation and tensile strength, whereas the elasticity modulus increased. ATC migration increased with ambient temperature, which was controlled by the activation energy of the blend system. Leaching of ATC was slow at room temperature in distilled water, but significant in boiling water. Additionally, the leaching rate was also directly proportional to the ATC content of the blend. Glass transition temperatures of PLA/starch/MA/L101 blends with various acetryl triethyl citrate contents.     

Morphological and mechanical properties of nascent polyethylene fibers produced via ethylene extrusion polymerization with a metallocene catalyst supported on MCM‐41 particles

Polyethylene (PE) fibers were prepared by ethylene extrusion polymerization with an MCM‐41‐supported titanocene catalyst. The morphological and mechanical properties of these nascent PE fibers were investigated. Three levels of fibrous morphologies were identified in the fiber samples through an extensive scanning electron microscopy study. Extended‐chain PE nanofibrils with diameters of about 60 nm were the major morphological units present in the fiber structure. The nanofibrils were parallel‐packed into individual microfibers with diameters of about 1–30 μm. The microfibers were further aggregated irregularly into fiber aggregates and bundles. In comparison with commercial PE fibers and data reported in the literature, the individual microfibers produced in situ via ethylene extrusion polymerization without posttreatment exhibited a high tensile strength (0.3–1.0 GPa), a low tensile modulus (3.0–7.0 GPa), and a high elongation at break (8.5–20%) at 35 °C. The defects in the alignment of the nanofibrils were believed to be the major reason for the low modulus values. It was also found that a slight tensile drawing could increase the microfiber strength and modulus. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2433–2443, 2003     

Study of viscoelastic properties of white carbon black reinforced synthetic polyisoprene

The viscoelastic properties of synthetic polyisoprenes(PI) reinforced by white carbon black(WCB) have been investigated and compared with WCB reinforced natural rubber(NR), including cure characteristics, physio-mechanical and dynamic mechanical properties. Compared with NR, PI loaded with the same amount of WCB(PI/WCB) exhibited shorter scorch time and optimal cure time, indicating that WCB fillers are comparatively easier to conjugate with PI. The tensile strength and elongation at break decreased with WCB filling in both PI and NR vulcanizates. The hardness of the rubber vulcanizates increased with the WCB filling in the rubber matrix. PI/WCB blends exhibited smaller hardness data, lower tensile strength, as well as lower elongation at break and tensile stress. Increasing the amount of WCB in rubber matrix induced the Payne effect. However, the Payne effect is much more obvious for the PI/WCB system, and PI/WCB also displayed higher storage modulus whereas lower loss modulus and loss tangent than NR/WCB, which could all be attributed to the poor dispersibilities of WCB in the PI matrix.     

Effect of Ionizing Radiation on the Characteristics of EPDM/UHMW-PE Composites

Ultra high molecular weight polyethylene (UHMW-PE) fibers were used in a chopped form and at different concentrations as a reinforcing material in ethylene–propylene–diene terpolymers (EPDM). The effect of radiation dose and fiber concentration on the mechanical properties of the vulcanized rubber composites obtained was measured. It was found that γ-irradiation improves the interfacial adhesion between UHMW-PE fiber (Spectra 1000) and EPDM matrix which was detected by scanning electron microscopy (SEM). In addition, the Young modulus of the composites increases as the irradiation dose increases. Increasing the concentration of the fibers up to 40 phr leads to an enhancement in mechanical properties and swelling resistance of obtained composites, especially in the absence of carbon black. The absolute value of the modulus increased by a factor of at least two with the addition of carbon black. Moreover the tear strength of reinforced and filled EPDM was improved with respect to reinforced rubber. © 1997 John Wiley & Sons, Ltd.