A model study on effect of glucose on the basic characteristics and physical properties of natural rubber

Glucose at various concentrations was incorporated into sugar free purified natural rubber (PNR) latex to model the effect of carbohydrate on the basic characteristics and physical properties of natural rubber (NR). PNR samples treated with various concentrations of glucose were characterized for the basic properties of unvulcanized NR, i.e., gel content, molecular weight distribution and Mooney viscosity to evaluate the effect of sugar on these parameters. In addition, the effect of glucose on the physical properties of vulcanizates derived using sulfur and peroxide vulcanization was investigated. Glucose was shown to affect the viscosity of unvulcanized NR and the discoloration of vulcanized NR. Moreover, glucose was found to have a strong effect on crosslink density, as well as tensile and dynamic properties of sulfur vulcanizates, while those properties of peroxide vulcanizates was not much affected by glucose.     

Magnetic composites based on natural rubber prepared by using peroxide and sulfur curing system

In this work, rubber magnetic composites were prepared by incorporation of strontium ferrite into elastomeric matrix based on natural rubber. Cross‐linking of the rubber matrix was performed by using sulfur and peroxide curing system. The study was aimed at the investigation of the type of curing system and magnetic filler content on curing process and cross‐link density of prepared materials. Then, the influence of both factors on physical–mechanical and magnetic properties was observed. The obtained results demonstrate that sulfur‐cured composites show better physical–mechanical properties, especially at lower content of strontium ferrite. With increasing amount of ferrite, the differences between the characteristics of both types of composites became less visible, while peroxide‐cured sample with maximum ferrite content showed superior tensile strength in comparison with tensile strength of maximally filled sample cured with sulfur system. The obtained results demonstrate better compatibility between the rubber and the filler when peroxide system was introduced for cross‐linking of the rubber matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

Microbial desulfurization of waste latex rubber with Alicyclobacillus sp.

A microbe with desulfurizing capability, Alicyclobacillus sp., was selected to recycle waste latex rubber (WLR). The growth characteristics of the microorganism and the technical conditions in the co-culture desulfurization process were studied. The desulfurization effect of Alicyclobacillus sp. on the WLR was characterized, and the mechanism for the microbial desulfurization of WLR was tentatively explored. The results showed that adding 5% (w/v) WLR into medium had little effect on the growth of Alicyclobacillus sp. The surfactant polysorbate 80 (Tween 80) had a toxic effect on Alicyclobacillus sp., but the growth of the microbe was vigorous if the proper technique was used: the mixing of WLR with Tween 80, followed by the addition of the mixture into the culture media. With the increase of desulfurization time, the swelling value of desulfurizated waste latex rubber (DWLR) increased, but the crosslink density decreased. After co-culture desulfurization for 8–10 days, a DWLR with good desulfurization effect was obtained. The mechanical properties of natural rubber (NR)/DWLR composite improved significantly over those of NR/WLR composite. XPS and FTIR results revealed that Alicyclobacillus sp. could break the crosslinked sulfur bonds and oxidize them to sulfones groups. The increase of O element content on the surface of DWLR was confirmed by water contact angle measurements. The relationship between the crosslink density and sol fraction of DWLR with different desulfurization times agreed with the Horikx equation, an indication that the microorganisms could break the crosslinked sulfur bonds on the surface of WLR, but leaving the main chains intact.     

New double negative and positive temperature coefficients of conductive EPDM rubber TiC ceramic composites

In this paper, we have successfully prepared ethylene-propylene-diene monomer (EPDM)/TiC composites as thermistors, with new double negative and positive temperature coefficients of conductivity (NTCC/PTCC). EPDM composites loaded with 50 phr HAF carbon black and different concentrations of TiC were prepared. This study focuses on the effect of TiC content on the vulcanization process, the network structure and the electrical and thermal properties of EPDM/TiC composites. The effect of TiC on the network structure was evaluated e.g. the curing process, the characteristic time constant during vulcanization, the volume fraction of rubber, gel fraction, interparticle distance between conductive particles, the extent of TiC reinforcement in the rubber matrix and molecular weight between cross-linking through experimental and affine-phantom models. The effects of TiC content on the percolation theory, electrical conductivity, conducting mechanism of conductivity, conducting hysteresis and I-V characteristics were also studied, as well as its TiC on the (NTCC/PTCC), thermoelectric power, dielectric constant and thermal conductivity. Stability and reproducibility of the thermal cycles for heating element applications was tested. Specific heat and the amount of heat transfer by radiation and convection as a function of TiC content was calculated using both the calorimetric technique and a theoretical model. It was proved that TiC improves the network structure, electrical and thermal properties of EPDM composites for practical applications.     

NMR imaging of elastomeric polymers

We have used NMR imaging to determine the dispersion in crosslinking density in complex elastomers both along the chains as well as spatially. Our work has established that the ordinary industrial accelerator systems generate a broad distribution of crosslink densities in rubber articles due to the poor mixing of the solid accelerator/sulfur recipe in the raw rubber. This high inhomogeneity in elastomeric network has an adverse effect on the properties of the elastomer system. In particular, the variation in crosslink density leads to substantial differences in the coefficients of thermal expansion and high internal stresses in the rubber article.     

轮胎橡胶多组分分析方法的研究

轮胎橡胶物证是涉车案件中常见物证,对于相关案件的侦破具有重要的物证价值。本文根据轮胎橡胶组分体系的特点,设计了以大型仪器为主线的多组分分析方案。所选用的仪器设备及方法有:裂解气相色谱仪(Py-GC)、裂解气相色谱与质谱联用仪(Py-GCMS)、差示扫描量热仪(DSC)、热重分析仪(TGA)、原子吸收分光光度计(AAS)、化学法;实验中,测试了轮胎橡胶的胶型、配合剂定性(防老剂定性、促进剂定性、其他助剂定性)、玻璃化温度,焓值,高聚物含量、配合剂含量、炭黑含量、无机填料(盐酸不溶物、氧化锌含量、二氧化硅含量)、硫含量等十三个测试项目;并将已知配方的硫化胶理论值与测试样品结果比对分析。分析结果表明:建立的系列方法的测试结果准确、可靠,可以为轮胎橡胶的分析鉴别提供技术支持。     

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.     

Reclaiming of ground rubber tire (GRT) by a novel reclaiming agent

The present paper describes the mechanical reclaiming of ground rubber tire (GRT) by tetra methyl thiuram disulfide (TMTD), a multi-functional reclaiming agent. The versatility of the proposed agent is that it acts as a reclaiming agent during reclaiming and as a curing agent during revulcanization of the reclaimed sample. Reclaiming of GRT was carried out on an open two roll mixing mill at various time intervals and different concentrations of the reclaiming agent (TMTD). The degree of reclaiming was evaluated by measurement of the gel content, inherent viscosity of sol rubber, Mooney viscosity of the reclaimed rubber, crosslink density, swelling ratio and molecular weight between two crosslink bonds as a function of milling time. Also, the influence of the gel content on crosslink density at various time intervals on the open two roll mixing mill was determined. A unique correlation between gel fraction and crosslink density obtained at various time intervals and concentrations of reclaiming agent indicated that an optimization of the concentration of TMTD and milling time has a positive influence on improving the efficiency of reclaiming. The reclaiming conditions have been optimized in view of the mechanical properties of the revulcanized GRT and the aging resistance properties of the revulcanized reclaim. The influence of the concentration of sulfur on the mechanical properties in the revulcanized reclaim was also studied. Scanning electron microscopy (SEM) studies further indicate the coherency and homogeneity in the revulcanized reclaim rubber when reclamation is carried out by optimum concentration of TMTD after maximum time of reclaiming.     

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.     

Studies of conventional sulfur vulcanization of SBR rubber: Analysing the reaction products from thermal degradation of the accelerator by means of MCC-IMS technique

A combination of knowledge on curing process of rubber mixes with novel methods of chemical analysis, a new unconventional approach to analysis of rubber vulcanization is presented in this study. Six SBR samples containing various N-tert-butyl-2-benzothiazole sulfenamide (TBBS) accelerator: sulfur ratios (within) the range of conventional (CV) sulfur vulcanization system were studied using multi-capillary column ion mobility spectrometry (MCC-IMS) technique. For these analysis, calibration/dilution curves were established. Moreover, data from MCC-IMS were correlated with other parameters of the rubber vulcanizates – their crosslink density and structure as well as their tensile strength and modulus at elongation. For such comparison, one of the reaction products from thermal decomposition of TBBS, benzothiazole was selected. Furthermore, the concentration of benzothiazole released during the vulcanization process corresponded well with the crosslink density of the rubber vulcanizates studied. It was even possible to calculate the crosslink density from the concentration of benzothiazole determined by MCC-IMS, using Boltzmann fitting curve. The presented results could be an important contribution in understanding the mechanisms occurring during rubber vulcanization, demonstrating a new approach to testing and evaluation of the process.     

Rubber magnets based on NBR and lithium ferrite with the ability to absorb electromagnetic radiation

Rubber magnetic composites were prepared through the incorporation of magnetic soft lithium ferrite into acrylonitrile butadiene rubber. Standard sulfur‐based curing and peroxide curing systems were used for cross‐linking of rubber matrices. The experimental part was focused on the investigation of ferrite content and curing system composition on cross‐link density, physical‐mechanical, magnetic and shielding characteristics of composites. The results demonstrated that cross‐link density and physical‐mechanical properties of composites can be modified by both the amount of ferrite and composition of the curing system. The influence of curing systems on magnetic properties was negligible. It can be stated that the application of lithium ferrite to rubber matrix leads to the preparation of rubber composites with the ability to efficiently absorb harmful electromagnetic radiation in the tested frequency range. The shielding efficiency of composites increased with increasing content of magnetic filler.     

An investigation of dynamic mechanical, thermal, and electrical properties of housing materials for outdoor polymeric insulators

The present paper reports the results about a study of mechanical, thermal, dynamic mechanical and electrical properties of housing (weather shed) materials for outdoor polymeric insulators. Silicone rubber, ethylene-propylene-diene monomer (EPDM) and alloys of silicon-EPDM are known polymers for use as housing in high voltage insulators. The result of dynamical mechanical measurement shows that the storage modulus of blends enhances with increase EPDM in formulation. It can be seen from the result of TGA measurement that initial thermal degradation of silicone rubber improves by the effect of EPDM in blends. The blends of silicone-EPDM show good breakdown voltage strength compared to silicone rubber. Surface and volume resistance of silicone rubber improve by EPDM content. The mechanical properties of EPDM such as strength, modulus and elongation at break improve by silicone.     

Thermoanalytical methods in vulcanizete analysis. Differential scanning calorimetry. Observations on the vulcanization process

Differential scanning calorimetry was used to follow the unaccelerated and accelerated sulfur vulcanization process in natural rubber and polybutadiene compounds. It was established that in both hard and soft rubber vulcanization, the heat of vulcanization (ΔH_v) depends only on the sulfur concentration provided other ingredients (carbon black, zinc oxide, stearic acid) and the elastomer blend ratio remain constant. Organic accelerators alter the temperature dependence of the exotherm but have no effect on ΔH_v over a considerable concentration range.The DSC exotherm was used to determine variations in sulfur/accelerator concentrations in production compounds. Analysis time is short—approx. 5 min—and a routine quality control method is suggested.     

Mercapto-modified copolymers in polymer blends, 1. Functionalization of EPDM with mercapto groups and its use in NBR/EPDM blends

Ethylene-propylene-diene rubber (EPDM) was reacted with thioacetic acid in the presence of 2,2′-azoisobutyronitrile (AIBN), giving rise to thioacetate-modified EPDM (EPDMTA). The extent of the incorporation was studied as a function of both thioacetic acid and AIBN concentration and reaction time. The products were analyzed by FTIR spectroscopy, sulfur content, and ¹H NMR spectroscopy. The hydrolysis of EPDMTA in a NaOH methanolic solution resulted in mercapto-modified EPDM (EPDMSH). The addition of 5 wt.-% of this functionalized copolymer to a sulfur-vulcanized nitrile rubber (NBR)/EPDM (70 : 30 wt.-%) blend accelerated the vulcanization process as indicated by oscillating disk rheometer analysis. In addition, an improvement of mechanical and ageing properties was also observed.     

Solution-based Preparation of High Sulfur Content Sulfur/Graphene Cathode Material for Li-S Battery

Practical Li-sulfur batteries require the high sulfur loading cathode to meet the large-capacity power demand of electrical equipment.However,the sulfur content in cathode materials is usually unsatisfactory due to the excessive use of carbon for improving the conductivity.Traditional cathode fabrication strategies can hardly realize both high sulfur content and homogeneous sulfur distribution without aggregation.Herein,we designed a cathode material with ultrahigh sulfur content of 88%(mass fraction)by uniformly distributing the water dispersible sulfur nanoparticles on three-dimensionally conductive graphene framework.The water processable fabrication can maximize the homogeneous contact between sulfur nanoparticles and graphene,improving the utilization of the interconnected conductive surface.The obtained cathode material showed a capacity of 500 mA·h/g after 500 cycles at 2.0 A/g with an areal loading of 2 mg/cm2.This strategy provides possibility for the mass production of high-performance electrode materials for high-capacity Li-S battery.     

Effect of fly ash silica and precipitated silica fillers on the viscosity,cure, and viscoelastic properties of natural rubber

The viscosity, cure properties, storage, and loss moduli and tan δ of natural rubber (NR) filled with the same amounts of precipitated silica (PSi) and fly ash silica (FASi) fillers were measured. The fillers were treated with bis[3‐triethoxysilylpropyl‐]tetrasulfide (TESPT), or, used in the rubber untreated. TESPT is a sulfur‐containing bi‐functional organosilane that chemically adheres silica to rubber and also prevents silica from interfering with the reaction mechanism of sulfur cure. The dispersion of PSi and FASi in the rubber was investigated using scanning electron microscope (SEM). The effects of silica type and loading and surface treatment on the aforementioned properties were of interest. The SEM results showed that the FASi particles were larger in size and had a wider particle size distribution when compared with the PSi particles. The viscosity of the compounds decreased progressively with mixing time, and the compounds with FASi had a lower viscosity than those filled with PSi. The treatment with Si69 had no beneficial effect on the dispersion of the fillers in the rubber matrix. At low temperatures, the type and loading of the filler had no effect on the storage and loss moduli of the compounds, but the effect was more pronounced at high temperatures. There was also evidence from the tan δ and glass transition temperature (T_g) measurements that some limited interaction between the filler particles and rubber had occurred because of TESPT. Copyright © 2008 John Wiley & Sons, Ltd.     

Study of electrical,mechanical, and nanoscale free‐volume properties of NBR and EPDM rubber reinforced by bentonite or kaolin

The effect of Na bentonite, Ca bentonite, and kaolin fillers on the macrostructure and microstructure of acrylonitrile butadiene rubber, ethylene propylene diene rubber, and their blend (50/50) was studied through electrical and mechanical measurements, as well as with positron annihilation lifetime spectroscopy. The real part of permittivity (ε′), dielectric loss (ε″), and the crosslinking density were found to increase with increasing filler content. The increase of crosslinking density of the blend with increasing amount of fillers reflects a decrease in the equilibrium swelling up to 21.50 wt % compared with that of the unfilled blends. The mechanical investigation showed pronounced increase in the tensile strength, and in elongation at break with the addition of up to 21.50 wt % of filler. In addition, comparing between different fillers showed that the reinforcing effect of Na bentonite is more effective than Ca bentonite and kaolin but the physico‐mechanical of Ca bentonite is less than that for kaolin. The positron annihilation lifetime measurements revealed that the free‐volume properties were strongly affected by the amount and type of filler, in particular, the free‐volume fraction was dramatically decreased with increasing filler content. Furthermore, correlations were made between the free‐volume parameters and both electrical and mechanical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1825–1838, 2009     

Raman investigation of thermoplastic vulcanizates based on hydrogenated natural rubber/polypropylene blends

Raman spectroscopy including mapping technique appears as a powerful technique for the characterization of polymer blends like thermoplastic elastomers (TPEs) and thermoplastic vulcanizates (TPVs). The Raman spectra of polymers blends such as natural rubber/polypropylene (NR/PP) and 65% hydrogenated natural rubber/polypropylene (65%HNR/PP) were identified and the phase distribution was determined. The study was driven for the same type of blends in TPEs state and TPVs state obtained after to 2 different processes, either peroxide cure or sulfur cure. The morphology of TPEs and TPVs obtained by Raman spectroscopy were compared and confirmed using scanning electronic microscopy.Raman mapping shows that the phase morphology of NR/PP, 65%HNR/PP, were characterized as continuous rubber phase morphology of the thermoplastic elastomers (TPEs) and a fine dispersion of cross-linked rubber phase in a continuous matrix of the thermoplastic vulcanizates (TPVs). Raman spectroscopy is demonstrated to be a reference to determine the content ratio of each component in the TPVs. Moreover, Raman mapping could be used to calculate the phase size of cross-linked rubber phase dispersed in the thermoplastic vulcanizates (TPVs).     

The influence of physical ageing on the electrical and swelling behaviour of ternary rubber vulcanizates

The effects of pre-annealing ageing time at 70 °C on the electrical properties and swelling behaviour in kerosene of a new tri-block rubber based on blends of natural rubber (NR) and different concentration ratios of both styrene-butadiene rubber (SBR) and butyl rubber (IIR), all incorporating 40 phr (parts per hundred parts of rubber by weight) of high abrasion furnace (HAF) carbon black, were investigated.

It was found that the interspacing distance, d, between carbon particles or aggregates is greatly affected by physical ageing and also by the rubber ratios in the test specimens.

Moreover, the degree of swelling, Q (%), in kerosene was found to decrease with both physical ageing and IIR content of the specimen.     

Cross‐linking and properties of rubber magnetic composites cured with different curing systems

Rubber magnetic composites were prepared by incorporation of strontium ferrite into rubber compounds based on acrylonitrile butadiene rubber and ethylene propylene diene monomer rubber. The sulfur, peroxide, and mixed sulfur/peroxide curing systems were introduced as cross‐linking agents for rubber matrices. The aim was to investigate the influence of curing system composition on curing process and cross‐link density of composite materials. Then, static and dynamic mechanical properties and thermal and magnetic characteristics were investigated in relation to the cross‐link density of rubber magnetic composites and structure of the formed cross‐links. The changes of dynamical and physicomechanical properties were in close correlation with the change of cross‐link density, whereas the tensile strength of magnetic composites showed increasing trend with increasing amount of peroxide in mixed curing systems. On the other hand, thermal conductivity and magnetic characteristics were found not to be dependent on the curing system composition.