On the potential of organoclay with respect to conventional fillers (carbon black,silica) for epoxidized natural rubber compatibilized natural rubber vulcanizates

Onium modified montmorillonite (organoclay) was 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) in 10 parts per hundred rubber (phr) was used as a compatibilizer in this study. For comparison purposes, two commercial fillers: carbon black (grade N330) and silica (grade vulcasil‐S) were used. Cure characteristics were carried out on a Monsanto MDR2000 Rheometer. Organoclay filled vulcanizate showed the lowest values of torque maximum, torque minimum, scorch, and cure times. The kinetics of cure reaction showed organoclay could behave as a cocuring agent. The mechanical testing of the vulcanizates involved the determination of tensile and tear properties. The improvement of tensile strength, elongation at break, and tear properties in organoclay filled vulcanizate were significantly higher compared to silica and carbon black filled vulcanizates. In terms of reinforcing efficiency (RE), organoclay exhibited the highest stiffness followed by silica and carbon black filled vulcanizates. Scanning electron microscopy revealed that incorporation of various types of fillers has transformed the failure mechanism of the resulting NR vulcanizates compared to the gum vulcanizates. Dynamic mechanical thermal analysis (DMTA) revealed that the stiffness and molecular relaxation of NR vulcanizates are strongly affected by the filler–rubber interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2438–2445, 2004     

Preparation and characterization of organoclay‐rubber nanocomposites via a new route with skim natural rubber latex

Skim natural rubber latex (SNRL) is a protein rich by‐product obtained during the centrifugal concentration of natural rubber (NR) latex. A new method to recover rubber hydrocarbon and to obtain nanocomposites with organoclay (OC) was investigated. The approach involved treatment of SNRL with alkali and surfactant, leading to creaming of skim latex and removal of clear aqueous phase before addition of OC dispersion. Clay mixed latex was then coagulated to a consolidated mass by formic acid, followed by drying and vulcanization like a conventional rubber vulcanizate. X‐ray diffraction (XRD) studies revealed that NR nanocomposites exhibited a highly intercalated structure up to a loading of 15 phr (parts per hundred rubber) of OC. Transmission electron microscopy studies showed a highly exfoliated and intercalated structure for the NR nanocomposites at loadings of 3–5 phr organically modified montmorillonite (OMMT). The presence of clay resulted in a faster onset of cure and higher rheometric torque. The rubber recovered from skim latex had a high gum strength, and a low amount of OC (5 phr) improved the modulus and tensile strength of NR. The high tensile strength was supported by the tensile fractography from scanning electron microscopy. Thermal ageing at 70°C for 6 days resulted in an improvement in the modulus of the samples; the effect was greater for unfilled NR vulcanizate. The maximum degradation temperature was found to be independent of the presence and concentration of OC. The increased restriction to swelling with the loading of OC suggested a higher level of crosslinking and reinforcement in its presence. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3277–3285, 2006     

反式聚辛烯橡胶改性天然橡胶/顺丁橡胶共混胶的性能

研究了反式聚辛烯橡胶(TOR)改性天然橡胶(NR)/顺丁橡胶(BR)(二者质量比80/20)共混胶的性能.结果表明,采用5～15份(质量,下同)TOR改性NR/BR混炼胶的门尼黏度逐渐降低、Payne效应基本不变,共混胶的焦烧时间和工艺正硫化时间延长、硫化速率减慢.相比NR/BR硫化胶,NR/BR/TOR硫化胶的拉伸强...     

硅藻土/天然橡胶复合材料的性能研究

利用环氧化天然胶乳作为硅藻土的界面改性剂,制备了硅藻土/天然橡胶复合材料,通过无转子流变仪、电子万能材料试验机和橡胶动态压缩生热仪,研究了复合材料的硫化特性,物理机械性能和温升特性。结果表明,硅藻土/天然橡胶复合材料的焦烧与正硫化时间随着硅藻土含量的增加,先增后减;最大与最小扭矩随硅藻土含量的增加而增加;硅藻土/天然橡胶复合材料的拉伸与撕裂强度均有提高,当硅藻土含量为4phr时,拉伸强度最高,为28.5MPa;当硅藻土的含量为2phr时,撕裂强度最高,为37.9N/mm;由于硅藻土的加入,材料的内生热显著降低。     

Properties of polypropylene/(natural rubber)/organomontmorillonite nanocomposites prepared by melt blending

The aim of this work was to study the effects of an organomontmorillonite or organoclay (OMMT) on the properties of a thermoplastic elastomer blend prepared by melt blending and based on polypropylene (PP) and natural rubber (NR). The results obtained showed a slight improvement of the blend mechanical (strength, modulus, and elongation), thermal, and solvent resistance properties when the amount of the organoclay was 3 phr. Results obtained by XRD analysis showed that at 3 phr of organoclay loading there was a shift toward low angles of the organoclay (001) plane diffraction peak and a disappearance of the PP β–phase peak. This shift signifies an intercalation of the polypropylene/(natural rubber) chains between organoclay platelets. An SEM study revealed that at the 3 phr organoclay concentration the blend became tougher, and the organoclay was located both at the PP/NR interface and inside the NR dispersed phase. A DSC study showed a decrease of the melting temperature of the PP phase at the 3 phr organoclay loading. A rheological study revealed that the addition of organoclay had not increased the melt viscosity of the PP/NR blend, and the stiffness was related to the maximum torque increase as a function of the organoclay loading. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

天然橡胶/顺丁橡胶/丁苯橡胶自润滑喷蜡橡胶材料的性能

在天然橡胶(NR)/顺丁橡胶(BR)/丁苯橡胶(SBR)为基体的自润滑喷蜡橡胶材料中加入芥酸酰胺,考察芥酸酰胺作为润滑剂时对NR/BR/SBR自润滑喷蜡橡胶材料的硫化特性、力学性能、门尼黏度、摩擦系数及耐老化性能的影响。结果表明,与未加芥酸酰胺的胶料相比,当芥酸酰胺用量为10份时,胶料转矩减小,焦烧时间和正硫化时间缩短,扯断伸长率从388%增加至523%,拉伸强度降低了21.36%,邵尔A硬度、压缩永久变形分别下降5.56%和8.74%,动、静摩擦系数分别减小23.46%和24.82%,门尼黏度降低20.89%,耐热氧老化性能下降。硫化胶拉伸100%停放5 min后,表面出现明显的白色润滑膜,胶料流动性变好,各组分分散得更均匀,断面更光滑。     

Organoclay Filled Natural Rubber Nanocomposites: The Effects of Filler Loading

Organoclay filled natural rubber (NR) nanocomposites were prepared using a laboratory two-roll mill. The effect of organoclay loading up to 10 phr was studied. The vulcanized nanocomposites were subjected to mechanical, thermal, and swelling tests. The results indicated that the tensile strength and elongation at break reached optimum at 4 phr of organoclay loading, and the incorporation of organoclay increased the tensile modulus and hardness of NR nanocomposites. The thermal degradation was shifted to a higher temperature and the weight loss decreased with incorporation of organoclay. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were employed to characterize the microstructure of NR nanocomposites. Results from TEM and XRD show the formation of intercalated and exfoliated individual silicate layers of organoclay filled NR nanocomposites particularly at low filler loading (< 4 phr).     

Organo-montmorillonite as substitute of carbon black in natural rubber compounds

The use of octadecylamine modified montmorillonite as substitute of carbon black in natural rubber (NR) compounds is studied. Rubber with 10 parts per hundred resin (phr) of pristine (clay) and octadecylamine modified montmorillonite (organoclay) were compared with 10 and 40 phr carbon black as filler. The modified silicate is analysed by X-ray, FTIR and thermogravimetric analysis. Vulcametric curves show that the organoclay and carbon black accelerate the vulcanization reaction and, furthermore, give rise to a marked increase in the torque, indicating a higher degree of crosslinking as was also confirmed by swelling measurements and DSC. The vulcanisation rate and torque value of the organoclay compound are sensibly higher than the carbon black compound even at high contents (40 phr). Mechanical characterization shows the strong reinforcing effect of both fillers up to 350% in the strength in relation to NR. The mechanical properties of NR with 10 phr organoclay are comparable to the compound with 40 phr carbon black. Moreover, the organoclay improves the strength of the NR without hardly any reduction in the elasticity of the material.     

Mechanical properties and blend compatibility of natural rubber –chlorosulfonated polyethylene blends

Natural rubber (NR) was blended with chlorosulfonated polyethylene (CSM) with various formulation and blend ratios (NR/CSM: 80/20 –20/80, wt/wt). Rubber blends were prepared by using a two‐roll mill and vulcanized in a compression mold to obtain the 2 mm‐thick sheets. Tensile properties, tear resistance, thermal aging resistance, ozone resistance, and oil resistance were determined according to ASTM. Compatible NR/CSM blends are derived from certain blends containing 20–30% CSM without adding any compatibilizing agent. Tensile and tear strength of NR‐rich blends for certain formulations show positive deviation from the rule of mixture. Thermal aging resistance depends on formulation and blend ratio, while ozone and oil resistance of the blends increase with CSM content. Homogenizing agents used were Stuktol®60NS and Epoxyprene®25. Stuktol®60NS tends to decrease the mechanical properties of the blends and shows no significant effect on blend morphology. Addition of 5–10 phr of epoxidized natural rubber (ENR, Epoxyprene® 25) increases tensile strength, thermal aging resistance, and ozone resistance of the blends. It is found that ENR acts as a compatibilizer of the NR/CSM blends by decreasing both CSM particle size diameter and α transition temperature of CSM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 127–140, 2006     

Curing characteristics and mechanical properties of rattan‐powder‐filled natural rubber composites as a function of filler loading and silane coupling agent

Curing characteristics, tensile properties, morphological studies of tensile fractured surfaces using scanning electron microscopy (SEM), and the extent of rubber filler interactions of rattan‐powder‐filled natural rubber (NR) composites were investigated as a function of filler loading and silane coupling agent (CA). NR composites were prepared by the incorporation of rattan powder at filler loading range of 0–30 phr into a NR matrix with a laboratory size two roll mill. The results indicate that in the presence of silane CA, scorch time (t_s2), and cure time (t₉₀) of rattan‐powder‐filled NR composites were shorten, while, maximum torque (M_H) increased compared with NR composites without silane CA. Tensile strength and tensile modulus of composites were enhanced whereas elongation at break reduced in the presence of silane CA mainly due to increase in rubber‐filler interaction. It is proven by SEM studies that the bonding between the filler and rubber matrix has improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of carbon black loading on curing characteristics and mechanical properties of waste tyre dust/carbon black hybrid filler filled natural rubber compounds

Curing characteristics, tensile properties, fatigue life, swelling behavior, and morphology of waste tire dust (WTD)/carbon black (CB) hybrid filler filled natural rubber (NR) compounds were studied. The WTD/CB hybrid filler filled NR compounds were compounded at 30 phr hybrid filler loading with increasing partial replacement of CB at 0, 10, 15, 20, and 30 phr. The curing characteristics such as scorch time, t₂ and cure time, t₉₀ decreased and increased with increment of CB loading in hybrid filler (30 phr content), respectively. Whereas maximum torque (M_HR) and minimum torque (M_L) increased with increasing CB loading. The tensile properties such as tensile strength, elongation at break, and tensile modulus of WTD/CB hybrid filler filled NR compounds showed steady increment as CB loading increased. The fatigue test showed that fatigue life increased with increment of CB loading. Rubber–filler interaction, Q_f/Q_g indicated that the NR compounds with the highest CB loading exhibited the highest rubber–filler interactions. Scanning electron microscopy (SEM) micrographs of tensile and fatigue fractured surfaces and rubber–filler interaction study supported the observed result on tensile properties and fatigue life. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Fly ash particles and precipitated silica as fillers in rubbers. I. Untreated fillers in natural rubber and styrene–butadiene rubber compounds

In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004     

Preparation,characterization, and application of NR/SBR/Organoclay nanocomposites in the tire industry

The natural rubber/styrene butadiene rubber/organoclay (NR/SBR/organoclay) nanocomposites were successfully prepared with different types of organoclay by direct compounding. The optimal type of organoclay was selected by the mechanical properties characterization of the NR/SBR/organoclay composites. The series of NR/SBR/organoclay (the optimal organoclay) nanocomposites were prepared with various organoclay contents loading from 1.0 to 7.0 parts per hundreds of rubber (phr). The nearly completely exfoliated organoclay nanocomposites with uniform dispersion were confirmed by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The results of mechanical properties measurement showed that the tensile strength, tensile modulus, and tear strength were improved significantly when the organoclay content was less than 5.0 phr. The tensile strength and the tear strength of the nanocomposite with only 3.0 phr organoclay were improved by 92.8% and 63.4%, respectively. It showed organoclay has excellent reinforcement effect with low content. The reduction of the score and cure times of the composites indicated that the organoclay acted as accelerator in the process of vulcanization. The incorporation of a small amount of organoclay greatly improved the swelling behavior and thermal stability, which was attributed to the good barrier properties of the dispersed organoclay layers. The outstanding performance of co‐reinforcement system with organoclay in the tire formulation showed that the organoclay had a good application prospect in the tire industry, especially for the improvement of abrasion resistance and the reduction of production cost. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

无机填料的表面处理及其在导热天然橡胶复合材料中的应用

用季戊四醇、丙三醇和钛酸酯偶联剂分别对氧化铝、氧化镁和高岭土进行表面改性,并将改性填料填充天然橡胶(NR)制备了导热复合材料,考察了表面处理剂种类及其用量对无机填料的影响,并研究了季戊四醇改性氧化铝填充NR复合材料的硫化特性、物理机械性能和导热性能.结果表明,3种填料中季戊四醇的改性效果最好,且其用量为1.0～1.5份时对氧化铝的改性效果最佳;随着改性氧化铝填充量的增加,复合材料的最大转矩、300%定伸应力、拉伸强度和热导率均增大,当其用量为60份时,改性氧化铝填充NR复合材料的热导率比未填充NR复合材料提高了23.9%.     

Natural rubber/poly(ethylene‐co‐vinyl acetate)‐blend‐based nanocomposites

Natural rubber (NR)/poly(ethylene‐co‐vinyl acetate) (EVA) blend–clay nanocomposites were prepared and characterized. The blend nanocomposites were prepared through the melt mixing of NR/EVA in a ratio of 40/60 with various amounts of organoclay with an internal mixer followed by compression molding. X‐ray diffraction patterns revealed that the nanocomposites formed were intercalated. The formation of the intercalated nanocomposites was also indicated by transmission electron microscopy. Scanning electron microscopy, used to study the fractured surface morphology, showed that the distribution of the organoclay in the polymer matrix was homogeneous. The tensile modulus of the nanocomposites increased with an increase in the organoclay content. However, an increase in the organoclay content up to 5 phr did not affect the tensile strength, but the organoclay reduced this property when it was increased further. This study also indicated that a low silicate content dispersed in the blend matrix was capable of increasing the storage modulus of the material. The addition of the organoclay also increased the decomposition temperature of the NR/EVA blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 353–362, 2006     

Studies on blends of natural rubber and ethylene propylene diene rubber modified with phosphorylated cardanol prepolymer: Processability,physico‐mechanical properties,and morphology

The melt processability and physico‐mechanical properties of blends of natural rubber (NR) and ethylene propylene diene rubber (EPDM) containing different dosages (0–10 phr) of phosphorylated cardanol prepolymer (PCP) were studied in unfilled and china‐clay‐filled mixes. The plasticizing effect of PCP in the blends was evidenced by progressive reduction in power consumption of the mixing and activation energy for melt flow with an increase in the dosage of PCP. The PCP‐modified blend vulcanizates showed higher tensile properties and tear strength despite a decrease in the chemical crosslink density (CLD) index. This is presumably due to the formation of a crosslinked network structure of PCP with the rubbers and improved dispersion of the filler particles in the rubber matrix, as evidenced by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Thermogravimetric analysis showed an increase in thermal stability of the blend vulcanizate in presence of 5 phr of PCP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5123–5130, 2006     

Curing Characteristics,Mechanical, Thermal,and Morphological Properties of Halloysite Nanotubes (HNTs)-Filled Natural Rubber Nanocomposites

Halloysite nanotubes (HNTs)-filled natural rubber (NR) nanocomposites with various filler loading were prepared by using a two-roll mill. The addition of HNTs increased the scorch time, cure time and maximum torque but reduced curing rate index. The tensile strength increased up to 20 phr of HNTs and then decreased. When HNTs loading increased, the elongations of break, swelling percentage and fatigue life were decreased while modulus at 100% and 300% elongation and thermal properties showed inversely. The dispersion of HNTs inside the NR matrix is shown from SEM images.     

Study on polypropylene/natural rubber blend with polystyrene‐modified natural rubber as compatibilizer

Polystyrene‐modified natural rubber (SNR) was prepared in the laboratory and subsequently used as compatibilizer in polypropylene/natural rubber (PP/NR) blends. The effect of SNR (at 5%, 10%, 15% and 20% by volume) in PP/NR (70/30) blend was studied by maintaining the rubber volume while PP volume was replaced by SNR accordingly. The sequence of mixing was found to affect the blend morphology and tensile properties. The effect of curatives on the tensile properties of the blends was also investigated. The addition of curatives into the rubbers in PP/NR/SNR improved the tensile properties significantly compared with the PP/NR reference blend. For a semi‐efficient curative system, SNR loading at 10% gave the best overall tensile properties, while for an efficient curative system, 5% SNR loading resulted in improvements in tensile strength and stiffness of over 20% and 40%, respectively, compared with the reference. © 2002 Society of Chemical Industry     

Cure Characteristics and Mechanical Properties of Natural Rubber–Layered Clay Nanocomposites

The effect of interlayer distance of nanoclay on mechanical properties, cure characteristics, and swelling resistance of natural rubber (NR) in varying clay proportion were studied. X-ray diffraction results of nanocomposite with 10 phr of nanoclay showed the formation of an intercalated structure. The rate of vulcanization and maximum torque value of the nanocomposite are higher than the gum compound. Nanocomposites with clay having higher interlayer distance shows superior mechanical properties. Mechanical properties gradually increase with increase in clay loading up to 10 phr. A 50% increase in tensile strength and about 150% increase in modulus at 300% elongation were observed for the nanocomposite with 10 phr clay loading. Better barrier properties offered by the nanocomposites due to the presence of tortous path was confirmed by the Nielson's model.