Chemical interaction between epoxidized natural rubber and silica: Studies on cure characteristics and low-temperature dynamic mechanical properties

The unusual reinforcement mechanism exhibited by silica in epoxidized natural rubber (ENR) may be attributed to the specific chemical interaction or the chemical cross-linking taking place between silica and the epoxy groups while heating the mix. Evidence for the higher interaction is established through rheometric studies conducted at 180°C and changes in the dynamic mechanical characteristics studied over a wide temperature range using a dynamic viscoelastometer for the heated and unheated silica-filled mixes.     

Natural rubber-graft-poly(2-hydroxyethyl acrylate) on cure characteristics and mechanical properties of silica-filled natural rubber composites

The grafting of poly(2-hydroxyethyl acrylate) onto natural rubber (NR-g-PHEA) was used to compatibilize NR composites with silica filler. The NR/silica compounds were prepared with various grafting percentages of NR-g-PHEA (0, 6.5, 10.5, and 14.5%) and fixed amounts of 3 parts per hundred of rubber (phr) NR-g-PHEA and 20 phr silica. The cure characteristics were examined using a moving die rheometer. The physicomechanical properties of NR/silica composites were determined in terms of tensile strength, bound rubber content, and dynamic mechanical analysis. Thermal properties were assessed with thermogravimetric analysis. The results showed that scorch time and cure time tend to decrease with the level of grafting in NR-g-PHEA. The NR-g-PHEA decreased tan δ, whereas bound rubber content in NR/silica compounds increased, which indicates improved silica dispersion in the NR matrix. The mechanical properties improved with level of grafting in NR-g-PHEA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48738.     

Rheology,cure characteristics,physical and mechanical properties of tire tread reclaimed rubber/natural rubber compounds

This work aimed to examine the effect of addition of tire‐tread reclaimed rubber on the properties of two natural rubber (NR) compounds with respect to the reclaimed rubber concentration and mastication time, the properties of interest including rheological and cure characteristics, physical and mechanical properties. The results under the test conditions suggested that Mooney Plasticity and shear viscosity increased with reclaimed rubber content, but decreased with mastication time. The greater the molar mass of the natural rubber the higher the sensitivity to the change in compound viscosity due to mastication and reclaimed rubber content. The die swell was more dependent on the reclaimed rubber than the molar mass of the rubbers. The cure rate and scorch time were found to increase and decrease with reclaimed rubber content, respectively, whereas the cure time was independent of the reclaimed rubber content. For vulcanized rubbers, it was also observed that 100% modulus of the rubber increased with reclaimed rubber content, but this was not the case for tensile stress and elongation at break. The hardness and heat buildup properties of the vulcanizates increased with reclaimed rubber content whereas the tear strength became independent of the reclaimed rubber. The findings in this work suggested that the variations in the rheological and cure characteristics for the unvulcanized rubber were very much dependent on the molar mass of the rubber whereas the mechanical properties for the vulcanized rubber were influenced by crosslink density. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1723–1731, 2003     

Styrene–butadiene rubber/natural rubber blends: Morphology,transport behavior,and dynamic mechanical and mechanical properties

Blends of styrene–butadiene rubber (SBR) and natural rubber (NR) were prepared and their morphology, transport behavior, and dynamic mechanical and mechanical properties were studied. The transport behavior of SBR/NR blends was examined in an atmosphere of n‐alkanes in the temperature range of 25–60°C. Transport parameters such as diffusivity, sorptivity, and permeability were estimated. Network characterization was done using phantom and affine models. The effect of the blend ratio on the dynamic mechanical properties of SBR/NR blends was investigated at different temperatures. The storage modulus of the blend decreased with increase of the temperature. Attempts were made to correlate the properties with the morphology of the blend. To understand the stability of the membranes, mechanical testing was carried out for unswollen, swollen, and deswollen samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1280–1303, 2000     

Effect of particulate fillers on short jute fiber-reinforced natural rubber composites

The effect of carbon black on the processing characteristics and physical properties of jute fiber-reinforced composites and the role of silica and carbon black in promoting the adhesion between jute fiber and natural rubber have been studied. It was found that presence of silica is not essential to develop adhesion between fiber and rubber in the presence of carbon black. However, silica and carbon black can improve adhesion by minimizing the resin formation and controlling it to a low molecular weight species. Processing properties like green strength and mill shrinkage are improved by the addition of fiber. Carbon black does not affect mill shrinkage, but improves the green strength. Breakage of jute fiber during mixing is severe, but the extent of breakage is not affected by the presence of carbon black. The minimum loading of fiber to achieve reinforcement is reduced in the presence of carbon black. It was also found that the presence of clay in jute fiber rubber composites impairs the properties. Scanning electron microscopy (SEM) has been used to assess the failure criteria.     

天然胶乳/炭黑复合材料的动态力学性能研究

通过添加阴离子表面活性剂,制备了稳定性能优异的炭黑分散液;然后将其添加到天然胶乳(NRL)中,采用胶乳共沉法制备NRL/炭黑复合材料,并对其物理性能、动态力学性能和内生热等进行了探讨。研究结果表明:当炭黑类型相同时,由胶乳共沉法制备的硫化胶之力学性能普遍优于由机械法制备的硫化胶;当采用炭黑N375补强时,由胶乳共沉法制备的硫化胶之力学性能相对最佳,其拉伸强度、撕裂强度和硬度分别比由机械法制备的硫化胶提高了6.5%、4.6%和8.8%;由胶乳共沉法制备的硫化胶之损耗因子(tanδ)小于由机械法制备的硫化胶,故前者的滞后损失更小、内生热更少且温升更低。     

Effects of types of fillers on the molecular relaxation characteristics,dynamic mechanical,and physical properties of rubber vulcanizates

The dynamic mechanical, and physical properties of bromobutyl rubber were investigated to determine the effect of particle size and of the structure of carbon black and silica. Filler loading was so adjusted that all the experimental compositions had the same hardness level. The results indicate that the type and loading of filler have no significant effect on the molecular relaxation transition. However, elastomer having a desirable storage modulus with low sensitivity to temperature change can be developed using filler with smaller particle size. Higher elongation at break, and better tensile strength, energy density at break, and fatigue life could be obtained by using finer particle or high structure black than with the low structure and higher particle size black. Finer particle size filler loaded systems exhibit pronounced strain dependence, higher thixotropic change, and delayed recovery in dynamic mechanical properties compared to that exhibited by large particle size filler.     

Physical properties and cure characteristics of natural rubber/nanoclay composites with two different compatibilizers

The effects of epoxidized natural rubber (ENR) and maleic anhydride‐grafted polybutadiene (PB‐g‐MA) as compatibilizers to rubber formulations with and without organo‐modified layered silicates are investigated. The physical properties and curing characteristics of composites are studied by moving die rheometer, rubber process analyzer, tensile, tear, and hardness testing. The state of organoclay intercalation was determined by X‐ray diffraction method. The addition of compatibilizers, especially ENR 50, results in further intercalation or exfoliation of the organoclay that increased the clay dispersion in the rubber matrix. ENR 50 with organo‐modified clay improves the physical properties and changes the curing profile. The addition of PB‐g‐MA without organoclay increases the tensile strength (σ_max) by increasing the stock viscosity of the rubber compound. Interestingly, simultaneous increase in hardness and σ_max is achieved in the presence of both compatibilizers, a characteristic that is difficult to achieve and sometimes required in rubber processing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of epoxidized natural rubber on mechanical properties of siliceous earth/natural rubber composites

Siliceous earth (SE) is a kind of mineral consisting of lamellar kaolinite, muscovite (aluminum silicate) and corpuscular silica. Natural rubber (NR) composites containing NR as matrix, epoxidized natural rubber (ENR) as compatibilizer and SE as filler were produced by latex coagulating process and cured using a conventional sulfuric system. Monsanto measurements have shown that the ENR accelerates the vulcanization reaction and gives rise to a marked increase of the torque. The results of physico-mechanical properties of NR vulcanizates show that, when SE modified by silane coupling agent and in the meanwhile adding 4 phr of ENR as compatibilizer, maximum tensile strength, elongation at break, reinforcing index (M300/100) of NR/SE vulcanizates were obtained. The dynamic-mechanical properties exhibit the addition of ENR can enhance wet grip characteristics and reduce rolling resistance by lowering tan δ values at 60 °C and increasing tan δ values at 0 °C of NR compounds. The overall results show that properties of SE-reinforced NR substantially improved by adding ENR as compatibilizer. The addition of silane coupling agent and combining an appropriate amount of ENR would be better choice to improve the properties of NR/SE compounds.     

Cure characteristics and mechanical properties of hydrogenated natural rubber/natural rubber blends

The cure characteristics and mechanical properties of blends consisting of hydrogenated natural rubber (HNR) and natural rubber (NR) blends were investigated. The HNR/NR blends at 50/50 wt ratio were vulcanized using various cure systems: peroxide vulcanization, conventional vulcanization with peroxide, and efficient vulcanization with peroxide. The HNR/NR vulcanizates cured by the combination of peroxide and sulfur donor (tetramethylthiuram disulfide, TMTD) in the efficient vulcanization with peroxide exhibited the best mechanical properties. It was also found that the hydrogenation level of HNR did not affect the tensile strength of the vulcanizates. The tensile strength of the blends decreased with increasing HNR content because of the higher incompatibility to cause the noncoherency behavior between NR and HNR. However, the HNR/NR vulcanizate at 50/50 wt ratio showed the maximum ultimate elongation corresponding to a co‐continuous morphology as attested to by scanning electron micrographs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The influence of structural order of anthracite fillers on the curing behavior,morphology, and dynamic mechanical thermal properties of epoxy composites

This article concerns the study of polymer composites with anthracite fillers of various structural order. Raw Svierdlovski anthracite of turbostratic structure and the anthracite thermally treated at 2,000°C of graphite‐like structure were used as fillers of low‐molecular‐weight diglycidyl ether of bisphenol A cross‐linked with aliphatic amine. Two anthracites of extremely different structures were compared to natural graphite that is composed of well‐ordered graphene sheets. Systematic studies of the influence of the structure of anthracite filler on the curing behavior, morphology, dynamic mechanical thermal properties, and thermal stability of epoxy composite were performed. It was found that the structure of anthracite filler affects the cross‐linking reactions of the epoxy matrix as well as the morphology of the composites and their viscoelastic properties. Raw anthracite added to epoxy matrix had a visible effect on the activation energy and differential scanning calorimeter parameters of the curing process, in contrast to the epoxy matrix modified with anthracite heated at 2,000°C. On the contrary, the effect of anthracite on dynamic mechanical behavior of composites is more evident when the anthracite prepared at 2,000°C was used as a filler. POLYM. COMPOS., 36:336–347, 2015. © 2014 Society of Plastics Engineers     

Acrylic rubber‐fluorocarbon rubber miscible blends: Effect of curatives and fillers on cure,mechanical, aging,and swelling properties

The cure characteristics and mechanical properties of gum and filled acrylic rubber (ACM), fluorocarbon rubber (FKM), and their blends of varying compositions were studied both under unaged and aged conditions. The rheometric study showed that optimum cure properties were obtained using a mixed curing system of blocked diamine, hexamethylenediamine carbamate (Diak #1), and ammonium benzoate. From varying the curing agents, the optimum levels of Diak #1 and ammonium benzoate were found to be 1.5 and 2.5 phr, respectively. The addition of different fillers and their loading influenced the cure properties, with increased torque and reduced scorch safety. The gum and filled 50:50 (w/w) ACM‐FKM showed overall performance in strength properties. Postcuring improved the strength of all the systems, especially the systems with a higher proportion of FKM. None of the properties changed significantly during aging of the blends. FKM and the blends containing a higher proportion of FKM were affected least by aging. Swelling of the blends was reduced by the addition of fillers. Dynamic mechanical thermal analysis showed a single tan δ peak corresponding to a single phase transition for both cured and filled blends. The storage modulus of the blend increased from the gum blend to the filled blend, indicating the presence of polymer‐filler interaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1442–1452, 2003     

Influence of nanoclay‐carbon black hybrid fillers on cure and properties of natural rubber compounds

The influence of organically modified nanoclay‐carbon black (CB) hybrid filler on the curing behavior of natural rubber (NR) was explored in this investigation. Here an effort was paid to understand the curing kinetics of organomodified nanoclay filled rubber compounds. On the basis of two different types of modified clay, NR nanocomposites were prepared and cured by a conventional vulcanization system. A faster curing rate and lower torque values were found when the modification was done by quaternary ammonium compounds. The activation energy of the rubber curing process decreased with the incorporation of nanoclay. In addition, it was revealed that the quaternary ammonium compounds used as modifier in the clay show a plasticization effect. Additionally, X‐ray diffraction studies indicated, that the basal spacing of the clay minerals was increased in both cases after incorporation in the rubber matrix. The dynamic mechanical analysis using a strain sweep mode showed that the Payne effect decreases because of an improved dispersion of CB induced by the presence of nanoclay. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Influences of dielectric and conductive fillers on dielectric and mechanical properties of solid silicone rubber composites

Dielectric elastomers are materials being used for electromechanical transduction applications. Their electromechanical response depends on permittivity, Young’s modulus and electric breakdown strength. A factor that limits its application is high operating voltages that can be reduced through improvement in permittivity. One of the methods is by incorporating high permittivity fillers into polymer matrix to obtain dielectric–dielectric composites (DDC).These composites show high permittivity at the cost of reduced flexibility. An alternative solution is development of composites by incorporating organic or inorganic conductive fillers into polymer matrix. These composites show high permittivity with high dielectric loss and low breakdown strength. To overcome both the above limitations both dielectric and conductive fillers are incorporated into dielectric polymer matrix to obtain conductor–dielectric composites (CDC). In this study, high temperature vulcanized solid silicone rubber as matrix has been used to prepare DDC composites with barium titanate (BT) filler and CDC composites with both BT as dielectric and ketjenblack as conductive fillers, using Taguchi design of experiments. The effect of factors such as amount of fillers and curing agent, mixing time in roll mill and curing temperature on the dielectric and mechanical properties are reported. Lichtenecker model predicts the permittivity of the DDC composite more accurately. For the CDC composites permittivity increased by 390%, effective resistivity decreased by 80%, Young’s modulus increased by 368% and Shore A hardness increased by 90% as compared to those of reference matrix. Important interaction effects are observed among both the fillers that are uniformly dispersed without any aggregation.

     

Vinyl acetate ethylene copolymer and nanosilica reinforced epoxidized natural rubber: Effects of sulfur curing systems on cure characteristics,tensile properties,thermal stability,dynamic mechanical properties and oil resistance

This study aimed at preparing nanocomposite from epoxidized natural rubber with about 40 mol% epoxidation (ENR40), vinyl acetate ethylene copolymer (VAE) contained about 70 wt% acetate groups and nanosilica (nSiO₂). Two parts by weight per hundred parts of rubber/resin of nSiO₂ were assembled to 80/20 (w/w) ENR40/VAE blend via latex blending. The resulting nanocomposite latex was coagulated before compounding with curing agents in an internal mixer. Tetrabenzylthiuram disulphide was used as a non‐carcinogenic accelerator in three sulfur vulcanization/curing systems, namely conventional (CV), semi‐efficient (semi‐EV) and efficient (EV) systems. The rubber compounds were sheeted on a two‐roll mill and press‐cured using a compression molding machine. Influence of curing systems on cure characteristics, tensile properties, thermal stability, dynamic mechanical properties and oil resistance of the nanocomposites was investigated. The results revealed that the CV system exhibited the highest crosslink density, tensile properties and storage modulus, while the EV system exhibited the longest scorch and cure time and the highest thermal stability and oil resistance. Moreover, the percentage retention of the tensile properties after thermal aging for CV system was lower than that of semi‐EV and EV systems. However, the pristine ENR40 and 80/20 (w/w) ENR40/VAE blend were also prepared for comparison. J. VINYL ADDIT. TECHNOL., 25:E28–E38, 2019. © 2018 Society of Plastics Engineers     

Sepiolite hybridized commercial fillers,and their effects on curing process,mechanical properties,thermal stability,and flammability of ethylene propylene diene monomer rubber composites

Ethylene propylene diene monomer rubber (EPDM)-based composites containing sepiolite (sep) hybridized with calcium carbonate (CaCO₃), silica (Sil) or carbon black (CB) were prepared on a two-roll mill. The influence of fillers’ contents on the curing, mechanical, thermal and flammability of the composites was investigated. In comparison with EPDM/sep at 30 parts per hundred rubbers (phr) as a control composite, EPDM/sep/CB composites exhibited an outstanding improvement in tensile strength followed by EPDM/sep/Sil and EPDM/sep/CaCO₃ composites. EPDM/sep/CB displayed the highest thermal stability and also improved flammability resistance. In addition, a higher amount of carbon black gave higher tensile strength. The results were influenced by the ability of CB to disperse well and form protective layers acting as mass transport barriers in the matrix. The field emission scanning electron microscopy analyses proved better dispersion of CB in the matrix. The presence of protective layers on the surface of samples consequently improved the thermal properties of the EPDM composites. The mechanism of formation of char protective layer in hybrid EPDM composites was also investigated based on morphological observations of char residues. According to this work, Sil and CB were able to hybrid with sep, while sep could be a potential substitution of CaCO₃ in the EPDM composites.     

Effect of natural coagula maturation on the processability,cure, and mechanical properties of unfilled vulcanizates of Hevea natural rubber

Fresh latex from different Hevea brasiliensis clones was naturally coagulated, subjected to different durations of maturation, processed into solid rubber, and compounded into pure gum stocks and vulcanized. Coagula maturation had clone‐specific effects on the processability of the raw rubber: reduced for some clones, while others was less sensitive. The cure and mechanical behaviors of the compounded stocks and vulcanizates, respectively, were not sensitive to the clonal origin of coagula and their duration of maturation. Although coagula maturation could be associated with leaching, deactivation of inherent antioxidants in Hevea latex, as well as crosslinking and/or oxidation of polyisoprene chains, these results show that compounding with a standard pure gum recipe compensates for the Hevea latex constituents affected by maturation. Hence, extended maturation of Hevea coagula, for economic or other reasons, would influence much more the bulk behavior of raw rubber and have insignificant effects on the compounded stocks and vulcanizates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2359–2363, 2007     

Dielectric behavior of natural rubber composites in microwave fields

In this article, we report the preparation of conducting natural rubber (NR) with polyaniline (Pani). NR was made into a conductive material by the compounding of NR with Pani in powder form. NR latex was made into a conductive material by the in situ polymerization of aniline in the presence of NR latex. Different compositions of Pani–NR semi‐interpenetrating networks were prepared, and the dielectric properties of all of the samples were determined in microwave frequencies. The cavity perturbation technique was used for this study. A HP8510 vector network analyzer with a rectangular cavity resonator was used for this study. S bands 2–4 GHz in frequency were used. Thermal studies were also carried out with thermogravimetric analysis and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2682–2686, 2007     

Correction to: Influences of dielectric and conductive fillers on dielectric and mechanical properties of solid silicone rubber composites

Iranian Polymer Journal - The article listed above was initially published with incorrect Table 1 and Table 2 values.     

Effect of nano zinc oxide on the cure characteristics and mechanical properties of the silica‐filled natural rubber/butadiene rubber compounds

With the increasing interest in environmental and health issues, legal restrictions, such as European Union (EU) End of Life Vehicle Directives, were strengthened. This led us to incorporate nano zinc oxide (nano‐ZnO), with particle sizes of 30–40 nm and specific surface areas of 25.0–50.0 m²/g, instead of conventional ZnO into natural rubber (NR)/butadiene rubber (BR) compounds to decrease the content of zinc in the formulation. In the unfilled system, only a 20 wt % nano‐ZnO content, compared to conventional zinc oxide content, showed the cure characteristics and mechanical properties of the same level. This was because the increase in the specific surface area of the nano‐ZnO led to an increase in the degree of crosslinking. The effect of nano‐ZnO on the cure characteristics and mechanical properties was more pronounced in the silica‐filled system than in the unfilled system. This was mainly because of the dispersing agent used in the silica‐filled system, which also improved the dispersion of nano‐ZnO. The silica‐filled NR/BR compounds containing 0.3–3.0 phr of nano‐ZnO showed improved curing characteristics and mechanical properties, such as optimum cure time, 100 and 300% modulus, tensile strength, and tear strength compared to the compound with 5 phr of conventional ZnO. The optimum amounts of nano‐ZnO and stearic acid were only 1.0 and 0.1 phr, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010