Vulcanization kinetics of low‐protein natural rubber with use of a vulcameter

Kinetics of vulcanization of low‐protein natural rubber (LPNR) was studied with the use of a vulcameter. In the induction period of vulcanization, the time t₀ of LPNR is longer than that of natural rubber (NR), and the temperature dependences of the time t_dis and the rate constant of LPNR are greater than that of NR. Both the curing periods of LPNR and NR (except 170°C for LPNR) consist of two stages. The first stage follows first‐order reaction. The rate constant k₂ of LPNR in the first stage is substantially the same as that of NR at the same temperature, and so is the activation energy E₂. The second stage (end stage of the curing period) does not follow first‐order reaction, and the calculated reaction order n is in the range of 0.67–0.73. Both rate constants of LPNR (except 170°C) and NR at the same temperature are approximately the same, and so is the activation energy E_3. The whole process of curing period for LPNR at 170°C follows n = 0.7 order reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Transport studies of peanut shell powder reinforced natural rubber composites in aromatic solvents

This article investigates the transport behavior of three aromatic organic solvents, viz. benzene, toluene, and xylene in natural rubber (NR) composite membranes containing peanut shell powder (PSP) as filler at different temperatures by conventional weight‐gain experiments. PSP used in compounding the NR was processed in two particle sizes. The solvent swelling characteristics of NR composites containing both untreated and alkali‐treated fillers were investigated. The computed sorption characteristics were discussed in terms of PSP content, particle size, nature of solvent, and temperature. All the NR‐PSP composites were found to decrease with the uptake of aromatic solvents than NR, but the effect was more significant in the case of alkali‐treated PSP composites. Furthermore, the uptake of solvent decreased with decrease in penetrant size. The estimated Arrhenius activation energies (E_D) for the processes of sorption, diffusion, and permeation showed that E_D was generally highest in xylene at the filler contents investigated. The thermodynamic parameters of the sorption process were also evaluated. The relationship between the transport behavior and the morphology of the system was examined. The mechanism of diffusion is found to be close to Fickian trend in toluene and xylene and Fickian trend in benzene. Comparison between theoretical and experimental diffusion results was made to understand the mechanism of diffusion. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Rice‐husk‐ash‐filled natural rubber. II. Partial replacement of commercial fillers and the effect on the vulcanization process

In a previous investigation, we observed that in the presence of a conventional vulcanization system, the addition of white rice husk ash (WRHA) to natural rubber (NR) compounds increased the rate of crosslinking and lowered the apparent activation energy (E_a) of the vulcanization reaction more strongly than the other fillers used. In this work, commercial fillers, such as precipitated silica (Zeosil‐175) and carbon black (N762), were partially replaced by black rice husk ash and WRHA. Cure studies were carried out on a TI‐100 curometer at 150, 160, 170, and 180°C, and the overall rates and the E_a's for the vulcanization process were calculated for each compound, with the assumption that vulcanization followed first‐order kinetics. Again, WRHA showed some catalytic effect on the NR vulcanization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1405–1413, 2003     

Kinetics of natural rubber vulcanization in the end stage of curing period

It was found that the change of vulcameter torque in the end stage of curing period of natural rubber does not follow first‐order kinetics and can be expressed in a kinetic equation of . The reaction order n calculated by the above equation is in the range of 0.68–0.74. The rate constant of the end stage increases with a rise in temperature and is well satisfied with Arrherius equation, giving activation energy E = 79.321 kJ/mol. If whole curing period is treated by first‐order kinetics without a change of reaction order from n = 1 to n = 0.68–0.74, the values of torque in the end stage of curing period predicted with first‐order kinetics equation will be lower than that obtained from vulcameter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 580–583, 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     

Studies on thermal–oxidative degradation behaviours of raw natural rubber: PRI and thermogravimetry analysis

Abstract

Thermal–oxidative degradation behaviours of raw natural rubber (NR) have been investigated by using thermogravimetry analysis in inert and oxidative atmospheres and the plasticity retention index (PRI). The activation energy E_a, was calculated using Horowitz–Metzger and Coats–Redfern methods and compared with PRI. The E_a values obtained by each method were in good agreement with each other. The June samples are the least stable rubbers among the studied ones, whereas February samples exhibited the highest values of activation energy, therefore in agreement with the PRI behaviour, which indicates that the thermo-oxidative stability of the June samples are the poorest during the thermo-oxidative degradation reaction. Natural rubber is a product of biological origin, and thus these variations in the values of thermal behaviour and PRI might be related to the genetic differences and alterations of climatic conditions that act directly on the synthesis of non-rubber constituents, which are generally reflected in latex and rubber properties.     

酸凝固天然橡胶和微生物凝固天然橡胶硫化特性研究

采用硫化仪分析2种天然橡胶的硫化过程,探讨了炭黑和硫化温度对硫化诱导期、正硫化时间和最大转矩的影响。研究结果发现：微生物凝固胶和酸凝固胶的硫化诱导期和正硫化时间随硫化温度的上升显著下降,且都能很好符合阿仑尼乌斯方程;胶样的最大转矩与硫化温度呈很好的线性关系,且随着硫化温度的升高,逐渐降低;当采用纯胶配方时,微生物凝固胶的MH0显著高于酸凝固胶,而加入炭黑后．2种胶样的MH0均显著提高。但微生物凝固胶的MH0稍低于酸凝固胶。     

Relation between activation energy and induction in rubber sulfur vulcanization: An experimental study

The article presents the possibility to use the so-called frequency factors in order to select the optimal temperature to mix rubber blend recipes before vulcanization without inducing premature crosslinking. As secondary result of the research, it provides a very simple approach to evaluate induction assuming a first order kinetic approach. It has been frequently observed that the activation energy in a first order rubber vulcanization scheme appears to be function of the particular activators used and that activation energy links to the so-called waiting time (and induction) by means of the frequency factor through an exponential relationship. A total of 212 rheometer curves are experimentally obtained and suitably postprocessed, consisting of pure natural rubber (NR), polybutadiene (PB), and 50–50 or 70%–30% NR-PR blends in presence of different concentrations of sulfur and accelerants (diphenyl guanidine [DPG] and N-t-butylbenzothiazole-sulfenamide [TBBS]). Data reduction is carried out to have an insight into the most suitable temperature to utilize in the different cases in order to: (a) Obtain the best mixed blends without risking premature vulcanization and (b) design the induction phase without over vulcanize the blend and/or delaying curing because the time required is too long. Waiting time and induction are evaluated by means of a well-established exponential law requiring the knowledge of the activation energy (assuming for the sake of simplicity that crosslinking occurs following a first order reaction kinetic law) and a constant called “frequency factor”. Frequency factor, considering all reactions monomolecular for the sake of simplicity, is assumed of the order of magnitude of 10⁻¹³–10⁻¹⁴ s. All experimental data carried out are critically compared and a wide explanation of the expected induction times and most suitable temperatures to use in the mixing phase is provided in the different cases considered. The article provides a meaningful insight into the importance of the link existing among activation energy, vulcanization recipe (with particular regard to concentration of accelerants, blend between two rubbers with very different activation energies and interaction between two accelerants) and mixing temperature to adopt before curing.     

Structural evolution of recycled tire rubber in asphalt

The performance of recycled‐tire‐rubber‐modified asphalt mainly depends on the structure of rubber in the asphalt. The effects of the curing temperature, mixing time, and shearing on the evolution of the chemical structure and morphological structure of crumb rubber in asphalt were investigated. The crosslink density, compositions, and morphological evolution of the residual crumb rubber were characterized. The results show that the structure evolution of tire rubber in asphalt was greatly affected by the curing temperature. At a low curing temperature (180°C), the crosslinking network of the tire rubber was broken down, and this led to the partial dissolution of natural rubber (NR). However, at high curing temperature (240°C), the dissolution of NR, synthetic rubber, carbon black, and inorganic filler was observed. The released carbon black covered with a thin layer of bound rubber dispersed at a microstructured or nanostructured size in the asphalt. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42954.     

Thermal degradation and ageing behavior of microcomposites of natural rubber,carboxylated styrene butadiene rubber latices,and their blends

The effect of microfillers on the thermal stability of natural rubber (NR), carboxylated styrene butadiene rubber (XSBR) latices, and their 70/30 NR/XSBR blend were studied using thermogravimetric method. Microcomposites of XSBR and their blend were found to be thermally more stable than unfilled samples. The activation energy needed for the degradation of polymer chain was calculated from Coats‐Redfern plot. Activation energy needed for the thermal degradation of filled samples was higher than unfilled system. It indicated the improved thermal stability of the filled samples. The ageing resistance of the micro‐filled samples was evaluated from the mechanical properties of aged samples. The thermal ageing was carried out by keeping the samples in hot air oven for 7 days at 70°C. The mechanical properties such as tensile strength, modulus at 300% elongation, and strain at break were computed. As compared to unfilled samples, micron‐sized fillers reinforced systems exhibited higher ageing resistance. Finally, an investigation was made on the influence of ion‐beam irradiation on microcomposites of NR, XSBR latices, and their 70/30 blend systems using ²⁸Si⁸⁺ performed at 100 MeV. The surface changes of the samples after irradiation were analyzed using X‐ray photoelectron spectroscopy. The results of XPS measurements revealed that the host elements were redistributed without any change in binding energies of C_1s, O_1s, and Si_2p. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Research on Payne effect of natural rubber reinforced by graft‐modified silica

Silica (SiO₂) modified by in situ solid‐phase grafting was used for natural rubber (NR) reinforcement. The physical mechanical properties and Payne effect of natural rubber reinforced by SiO₂ and graft‐modified silica (G‐SiO₂) were analyzed systematically. The results showed the comprehensive performance of NR/G‐SiO₂ was better than that of NR/SiO₂. There was a proportional relationship between the filler loading and Payne effect. NR/G‐SiO₂ presented weaker Payne effect in comparison with NR/SiO₂. A qualitative analysis on the correlation of filler 3D network structure and filler loading was carried out according to the relationship between the bound rubber content and the shear modulus. The Payne effect mechanisms of rubber compounds differed according to the different filler loading. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43891.     

Morphology and dynamic mechanical properties of natural rubber/nitrile rubber blends containing trans‐polyoctylene rubber as a compatibilizer

The use of trans‐polyoctylene rubber (TOR) as a compatibilizer for blends of natural rubber (NR) and acrylonitrile‐butadiene rubber (NBR) was investigated using atomic force microscopy (AFM) and dynamic mechanical analysis (DMA). The NR/NBR blends containing varying proportions of TOR were prepared in an internal mixer. AFM micrographs of NR/NBR blend at 50/50 (w/w) composition showed heterogeneous phase morphology with NR as a matrix and NBR as a dispersed phase. Inclusion of TOR in the NR/NBR blend altered the phase morphology by reducing the size of the NBR phase. DMA of NR/NBR/TOR showed reduction in tan δ peak height of NBR and an increase in storage modulus E′ in the rubbery region for the NR/NBR blends. A comparison of the E′ obtained from experimental data with that from theoretical models was made to deduce the location of TOR in the blend. Based on the fittings of calculated and experimental values of E′, it was inferred that TOR was incorporated into the NR phase at lower proportion as well as at the interfacial region at higher proportion. The Cole–Cole plot illustrated the compatibilizing effect of TOR. Copyright © 2004 Society of Chemical Industry     

Effects of silane coupling agents on the vulcanization characteristics of natural rubber

The vulcanization characteristics of silica‐filled natural rubber (NR) were studied in the presence of silane coupling agents, 3‐octanoylthio‐1‐propyltriethoxysilane (NXT) and bis [(3‐triethoxysilylpropyl) tetra sulfide] (TESPT, or Si‐69). The scorch time, cure rate index, and the rate constant of NR were measured using an Oscillating Disk Rheometer in the temperature range of 140–170°C. The scorch time of NR decreases with increasing TESPT and NXT concentrations, and the scorch time of NR compound with NXT is longer than that with TESPT. The apparent activation energies of vulcanization for the compounds with NXT and TESPT both decrease with increasing silane concentration. The apparent activation energy of vulcanization of NR compound with NXT is lower than that with TESPT at various concentrations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1511–1518, 2004     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

Preparation and characterization of organoclay nanocomposites based on natural rubber

Rubber compounds based on natural rubber (NR) reinforced with octadecylamine‐modified bentonite have been prepared via a vulcanization process and characterized by several techniques. The silicate nanolayers are exfoliated and uniformly dispersed in the polymer chains. Monsanto measurements have shown that the organoclay accelerates the vulcanization reaction and, furthermore, gives rise to a marked increase of the torque, indicating that the elastomer becomes more crosslinked in the presence of the organoclay. These results were corrobated by swelling measurements since a noticeable increase in the curing degree was observed when the organoclay was added to the rubber recipe. Moreover, thermodynamic parameters have shown an increase in the structural order of the nanocomposite. In addition, thermal analysis supports the assumption that the degree of curing of the elastomer increases when the organoclay is added to the elastomer. An appreciable increase of the involved heat during the curing reaction has been observed. Moreover, the T_g of the NR increases in the presence of the organoclay due to the confinement of the elastomer segment into the organoclay nanolayers, which restricts the mobility of the chains. Copyright © 2003 Society of Chemical Industry     

Preparation and properties of natural rubber nanocomposites with solid‐state organomodified montmorillonite

A novel organomodified montmorillonite prepared by solid‐state method and its nanocomposites with natural rubber were studied. The nanocomposites were prepared by traditional rubber mixing and vulcanizing process. The properties of solid‐state organomodified montmorillonite were investigated by Fourier‐transform infrared spectroscopy (FITR) and thermogravimetric analysis (TGA). The dispersion of the layered silicate in rubber matrix was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the nanocomposites consisting of solid‐state organomodified montmorillonite and natural rubber are obtained. The solid‐state organomodified montmorillonite can not only accelerate the curing process, but also improve the mechanical and aging resistance properties of NR. The properties improvement caused by the fillers are attributed to partial intercalation of the organophilic clay by NR macromolecules. In addition, the dynamic mechanical analysis (DMA) results showed a decrease of tanδmax and increase of T_g when the organoclay is added to the rubber matrix, which is due to the confinement of the macromolecular segments into the organoclay nanolayers and the strong interaction between the filler and rubber matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Waste natural gum as a multifunctional additive in rubber

Bahera gum, extracted from the bark of Terminalia bellerica, is a waste material. The present study involves the use of this natural gum as a multifunctional additive in natural rubber (NR) and brominated isobutylene‐co‐paramethyl styrene (BIMS). Fourier transform infrared (FTIR) analysis was employed to study the functional groups present in the gum. It was found that fatty acids/esters in the gum act as accelerator activator and can replace stearic acid in rubber formulations. Polyphenols in the gum act as antioxidant and the action is comparable with the commercial antioxidant 2,2,4‐trimethyl‐1,2‐dihydroquinoline (TQ) in natural rubber. The gum improves the tack strength of the rubbers (21% at 2.5 phr loading for NR and 54% at 10 phr loading for BIMS). The gum imparts plasticization effect which is reflected in the reduction in k and enhancement in n values, the exponents in the power law equation, with increasing gum concentration. The activation energy of flow is also reduced with the addition of the gum. Moreover, it decreases the elastic memory of the system which causes reduction in die swell. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4897–4907, 2006     

A study on the curing kinetics of epoxycyclohexyl polyhedral oligomeric silsesquioxanes and hydrogenated carboxylated nitrile rubber by dynamic differential scanning calorimetry

A new organic–inorganic hybrid material was prepared through reactive blending of hydrogenated carboxylated nitrile rubber (HXNBR) with epoxycyclohexyl polyhedral oligomeric silsesquioxanes (epoxycyclohexyl POSS). The structure of the composite was characterized by Fourier transform infrared spectroscopy (FTIR) and solid‐state ¹³C Nuclear Magnetic Resonance spectra (solid‐state ¹³C‐NMR). The differential scanning calorimetry (DSC) at different heating rates was conducted to investigate the curing kinetics. A single overall curing process by an nth‐order function (1 ? α)ⁿ was considered, and multiple‐heating‐rate models (Kissinger, Flynn–Wall–Ozawa, and Crane methods) and the single‐heating‐rate model were employed. The apparent activation energy (E_a) obtained showed dependence on the POSS content and the heating rate (β). The overall reaction order n was practically constant and close to 1. The isoconversion Flynn–Wall–Ozawa method was also performed and fit well in the study. With the single‐heating‐rate model, the average E_a for the compound with a certain POSS content, 66.90–104.13 kJ/mol was greater than that obtained with Kissinger and Flynn–Wall–Ozawa methods. Furthermore, the calculated reaction rate (dα/dt) versus temperature curves fit with the experimental data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of phenol functionalization of carbon nanotubes on properties of natural rubber nanocomposites

This paper reports the results of studies on the effect of phenol functionalization of carbon nanotubes (CNTs) on the mechanical and dynamic mechanical properties of natural rubber (NR) composites. Fourier transform infrared spectrometry (FTIR) indicates characteristic peaks for ether and aromatic rings in the case of phenol functionalized CNT. Although differential scanning calorimetric (DSC) studies show no changes in the glass‐rubber transition temperature (T_g) of NR in the nanocomposites due to surface modification of CNT, dynamic mechanical studies show marginal shifting of T_g to higher temperature, the effect being pronounced in the case of functionalized CNT. Stress‐strain plots suggest an optimum loading of 5 phr CNT in NR formulations and the phenolic functionalization of CNT does not affect significantly the stress‐strain properties of the NR nanocomposites. The storage moduli register an increase in the presence of CNT and this increase is greater in the case of functionalized CNT. Loss tangent showed a decrease in the presence of CNT, and the effect is more pronounced in the case of phenol functionalized CNT. Transmission electron microscopy (TEM) reveals that phenol functionalization causes improvement in dispersion of CNT in NR matrix. This is corroborated by the increase in electrical resistivity in the case of phenol functionalized CNT/NR composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheological characterization and modeling of vulcanization kinetics of natural rubber/starch blends

Vulcanization kinetics of natural rubber/starch (NR/ST) blends was investigated by oscillating disc rheometer. The scorch and cure times are significantly reduced with the loading of starch in all blends from 1.15 and 2.22 to 0.91 and 1.88 min, respectively, to improve curing rate. Meanwhile, the maximum torque values and the maximum vulcanization rate of NR/ST blend increase with the starch loading from 1.51 N m and 0.387 min^?1 to 2.224 N m and 0.492 min^?1 respectively. The results of vulcanization kinetics of NR and its blends revealed that it is controlled by two‐stages, chemical and diffusion. The experimental data of the vulcanization rate of NR/ST blends did not fit with autocatalytic kinetic model except the pure natural rubber. Therefore, the Criado method was used and it was observed that the reaction kinetic model of pure NR and its blends with starch is best described by the D diffusion model (D2). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46347.