EPDM rubber reclaim from devulcanized EPDM

Two types of ethylene–propylene–diene monomer (EPDM) rubbers, namely an efficient vulcanized (EV) and a semiefficient vulcanized (SEV), have been used to produce devulcanizates in a continuous setup. The devulcanizates are re‐cured using the same recipes as for the virgin rubber. The influence of mixing it with virgin rubber compound, the addition of extra sulfur, the operating devulcanization conditions, and the excess of devulcanizing agent on the mechanical properties (hardness, tensile strength, and compression set) of the reclaim rubbers are studied. Most of the reclaims produced show slightly inferior mechanical properties compared to the virgin rubber. Surface imperfection was observed on the devulcanizate with high devulcanizing agent content. Excellent mechanical properties (all above the standards) of the reclaim were found when the devulcanized profile material was used (EV‐EPDM) to replace the virgin one for application as a roofing sheet material (SEV‐EPDM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5948–5957, 2006     

Continuous ultrasonic devulcanization of NR/SBR blends

The ultrasonic devulcanization of sulfur‐cured natural rubber (NR)/styrene–butadiene rubber (SBR) blends was studied with the goal of understanding the devulcanization of rubber vulcanizates in which two networks of different natures were present. Also, similarities and differences in the devulcanization behaviors of NR, SBR, and their blends were found. During the devulcanization of cured NR/SBR blends, we observed that, as for NR, the ultrasonic power consumption for 75/25 and 50/50 (w/w) NR/SBR blends passed through a maximum at 7.5 μm. For SBR and 25/75 (w/w) NR/SBR blends, the power consumption increased with increasing ultrasonic amplitude. The higher power consumption led to a higher degree of devulcanization. The crosslink densities of the devulcanized 25/75, 50/50, and 75/25 (w/w) NR/SBR blends were lower than those of the devulcanized NR and SBR, possibly because of the reduced degree of unsaturation. The tensile properties of the revulcanized blends were lower than those of the virgin vulcanized blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 160–168, 2002     

Effects of cashew nut shell liquid as a plasticizer on cure characteristics,processability, and mechanical properties of 50 : 50 NR/EPDM blends: A comparison with paraffin oil

50 : 50 natural rubber (NR) and ethylene–propylene–diene monomer rubber (EPDM) blends were prepared with different contents of cashew nut shell liquid (CNSL), a natural product obtained from the shells of the cashew nut, as a plasticizer. For comparison, a commercial paraffin oil plasticizer was also used. The effect of plasticizer content on the cure characteristics, processability, and mechanical properties such as tensile strength, elongation at break, and Young's modulus before and after ageing was investigated. Scanning electron microscopy (SEM) was used to observe the blend morphology. The results indicated that the CNSL plasticizer resulted in lower Mooney viscosity and lower cure time of the 50 : 50 NR/EPDM blends. The incorporation of CNSL into 50 : 50 NR/EPDM blends improved tensile strength and elongation at break but decreased Young's modulus. On addition of CNSL the resistance of the blends to heat and weathering ageing improved. Scanning electron micrographs revealed that the morphology of the blend plasticized with CNSL is finer and more homogeneous compared with the blend plasticized with paraffin oil. Overall results indicate that CNSL can be used as a cheaper plasticizer to replace paraffin oil in NR/EPDM blends with improved processability and mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of ultrasonic oscillation on processing behaviors of PS,EPDM, and PS/EPDM blend

In this study, the extrusion processing behaviors of polystyrene (PS), ethylene–propylene–diene terpolymer (EPDM), and their blend (PS/EPDM, 80/20) were studied by using a special ultrasonic oscillation extrusion system developed in our laboratory. The die pressure and volume flow rate were measured at different ultrasonic intensities and screw rotation speeds. The dependences on ultrasonic intensity of die pressure, volume flow rate, and apparent viscosity of polymers, as well as die swell at the same screw rotation speed were investigated. The effects of screw rotation speed on the processing behaviors of polymers and their blend at the same ultrasonic intensity were also studied. The experimental results showed that in the presence of ultrasonic irradiation, the processibilities of polymers and their blend were improved. Their possible mechanism is discussed in this article. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1856–1863, 2006     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of monomer sequence distribution in EPDM by 13C‐NMR: Third monomer effects

The methods for sequencing ethylene–propylene copolymers (EPMs) by ¹³C‐NMR were extended to account for third monomer effects. The equations for calculating the ethylene content and monomer sequence distribution in EPMs were corrected for the presence of the third monomers 1,4 hexadiene, 2‐ethylidene‐5‐norbornene, and 5,8‐dicyclopentadiene that display resonances that overlap with the main chain EPM carbons. These corrections dramatically reduce the standard deviation among equivalent calculation methods. We also examined the effects of experimental conditions on the sequencing data including the choice of solvent, Cr³⁺ doping, and the presence of the nuclear Overhauser effect. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 523–530, 1999     

Continuous ultrasonic devulcanization of unfilled NR vulcanizates

Sulfur-cured unfilled natural rubber (NR) is successfully devulcanized in a continuous extrusion process under the application of high-power ultrasonic energy. The die characteristics and ultrasonic power consumption are measured. A unique correlation is found between the crosslink density and gel fraction of the devulcanized NR. This correlation is independent of the processing parameters, such as barrel temperature, die gap, flow rate, and amplitude of ultrasound. However, these parameters do influence the degree of devulcanization. In most cases, the degree of devulcanization is found to pass through a maximum at an intermediate level of ultrasonic energy. It is hypothesized that simultaneous breakup and reformation of crosslinks occur during the devulcanization of NR, with the relative contribution of each being determined by the process parameters. The cure curves and mechanical properties of the revulcanized NR are studied. The mechanical properties are found to depend on the revulcanization recipe. On optimizing it, tensile strength as high as 14.2 MPa is achieved, which is about 70% of that of the virgin NR vulcanizate. Ultimate elongation as high as 670% is obtained, which is the same as that of the virgin NR vulcanizate. Such stress–strain behavior is an indication that the devulcanized NR maintains the strain-induced crystallization characteristics inherent to the virgin NR vulcanizates. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2007–2019, 1998     

Surface behavior of blends of SBR with ultrasonically devulcanized silicone rubber

The application of silicone polymers as additives in commercial polymers for improving their surface properties is an attractive method. Use of reclaimed silicone rubber for blending with commercial organic polymers is an equally attractive possibility. Ultrasonically devulcanized silicone rubber was mixed with virgin and ultrasonically devulcanized styrene–butadiene rubber (SBR). The surface and bulk mechanical properties and curing behavior of the blends of SBR with ultrasonically devulcanized silicone rubber were investigated. Contact angles of these blends were measured, and the concentration of silicone rubber on the surface was calculated. It was shown that the soluble part of devulcanized silicone rubber migrates to the surface. The addition of 5 phr of devulcanized silicone rubber led to the formation of a continuous surface layer containing 100% silicone rubber. In general, the mechanical properties of the blends remain intact and, in some cases, are even better than those of SBR. Curing behavior shows that the blends have the similar cure kinetics as virgin or devulcanized SBR, but a lower final torque. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2691–2696, 1998     

Morphology,rheology, and mechanical properties of dynamically cured EPDM/PP blend: Effect of curing agent dose variation

The structure development, rheological behavior, viscoelastic, and mechanical properties of dynamically cured blend based on the ethylene–propylene–diene terpolymer (EPDM) and polypropylene (PP) with a ratio of 60/40 by weight were studied. The variation of two‐phase morphology was observed and compared as the level of curing agent was increased. Meanwhile, as the level of curing agent increased, viscosity as a function of shear stress always increased at a shear stress range of 2.2 × 10⁴ to 3.4 × 10⁵ Pa at the temperature of 200°C, yet viscosity of the blend approached each other at high shear stress. Dynamic mechanical spectra at different temperatures show that dynamic modulus (E′) of the blend exhibits two drastic transitions corresponding to glass transition temperature (T_g) of EPDM and T_g of PP, respectively. In the blends T_gs of EPDM increase and T_gs of PP almost remain unchangeable with an increase in curing agent level. Tensile strength increased, yet elongation at break decreased as the level of curing agent is increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 357–362, 2004     

Influence of calcium carbonate filler and mixing type process on structure and properties of styrene–acrylonitrile/ethylene–propylene–diene polymer blends

The properties of styrene–acrylonitrile (SAN) and ethylene–propylene–diene (EPDM) blends containing different types of calcium carbonate filler were studied. The influence of mixing type process on the blend properties was also studied. Two different mixing processes were used. The first one includes mixing of all components together. The other process is a two‐step mixing procedure: masterbatch (MB; EPDM/SAN/filler blend) was prepared and then it was mixed with previously prepared polymer blend. Surface energy of samples was determined to predict the strength of interactions between polymer blend components and used fillers. The phase morphology of blends and their thermal and mechanical properties were studied. From the results, it can be concluded that the type of mixing process has a strong influence on the morphological, thermal, and mechanical properties of blends. The two‐step mixing process causes better dispersion of fillers in blends as well as better dispersion of EPDM in SAN matrix, and therefore, the finest morphology and improved properties are observed in blends with MB. It can be concluded that the type of mixing process and carefully chosen compatibilizer are the important factors for obtaining the improved compatibility of SAN/EPDM blends. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mercapto‐modified copolymers in elastomer blends. IV. The compatibilization of natural rubber/EPDM blends

Ethylene—propylene—diene functionalized with mercapto groups (EPDMSH) was employed as compatibilizing agent for natural rubber (NR)/EPDM blends, resulting in a substantial increase of the ultimate tensile strength of these blends without affecting the elongation at break. There is also a decrease of the curing time with the addition of as low as 2.5 phr of EPDMSH, mainly in NR/EPDM (70:30 wt %) blend, indicating the accelerator effect of this functionalized copolymer. This copolymer also increased the crosslink degree and the gel content. From dynamic mechanical analysis (DMTA), it was demonstrated that EPDMSH improves the covulcanization process. The reactive compatibilization of EPDMSH was demonstrated by the presence of insoluble material in nonvulcanized/compatibilized blends and by its thermogravimetric (TGA) analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2892–2900, 2002; DOI 10.1002/app.10283     

Influence of γ-irradiation on proton spin–lattice relaxation of SBR used as antirads and its ESR investigation

Proton spin–lattice relaxation time t₁ was measured on SBR samples with carbon black or kaolin filler using modified linseed oil. The NMR pulse technique at 90MHz was used in the temperature range from 180 to 400 K. The temperature dependence of t₁ indicates that samples filled with carbon black have similar molecular dynamics to the standard unfilled SBR samples. The activation energy for the motion of the main chain for these samples amounts to 16.4kJ/mol. Samples containing linseed oil modified with para-toluidine showed an activation energy of about 14.6kJ/mol and were not affected by γ-irradiation. Values of the minimum relaxation time t^min₁ were increased by γ-irradiation in comparison with a standard SBR sample. ESR measurements carried out at room temperature by means of an X-band spectrometer indicated that unidentified radicals within the rubber were formed during its mastication with vulcanizing additives. The ESR spectra did not change during the vulcanization process. Samples filled with carbon black showed a broadening of the ESR line; this is consistent with the increase in the electrical conductivity.     

Effect of hot air aging on properties of EPDM/SmBO3/EVA and EPDM/ATO/EVA composites

Ethylene–propylene–diene rubber (EPDM)/samarium borate (SmBO₃)/ethylene‐vinyl acetate (EVA) copolymer and EPDM/antimony‐doped tin oxide (ATO)/EVA composites are aged at 150°C for different intervals. Surface modification is used to improve filler to matrix interphase. The main aim is to investigate the effect of filler type and vinyl acetate (VA) content in EVA on stability of EPDM composites. It is found that acidic ATO particles can lower pH level of EPDM composites and then promote the degradation of acetic acid during aging. Moreover, when VA content exceeds 14 wt %, the instable VA content causes more acetic acids escape during aging. With the increasing of aging time, EPDM/SmBO₃ control and EPDM/SmBO₃/EVA composites tend to become darker while EPDM/ATO and EPDM/ATO/EVA composites would become yellow. And the color change is correlated well with the variation of carbonyl index. The chemical crosslink points prevent crystals in EVA from melting at aging temperature (150°C), and the variation of crosslink density influences the crystallinity during aging. The tendency of tensile strength is well consistent with that of swelling ratios, and electric properties are correlated with increased polar groups and crystallinity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of filler loading on cure time and swelling behaviour of SMR L/ENR 25 and SMR L/SBR blends

The effect of filler loading on the cure time (t₉₀) and swelling behaviour of SMR L/ENR 25 and SMR L/SBR blends has been studied. Carbon black (N330), silica (Vulcasil C) and calcium carbonate were used as fillers and the loading range was from 0 to 40 phr. Results show that for SMR L/ENR 25 blends the cure time decreases with increasing carbon black loading, whereas silica shows an increasing trend, and calcium carbonate does not show significant changes. For SMR L/SBR blends, the cure time of carbon black, silica and calcium carbonate generally decreases with increasing filler loading. The percentage swelling in toluene and ASTM oil no 3 decreases for both blends with increasing filler loading, with calcium carbonate giving the highest value, followed by silica‐ and carbon black‐filled blends. At a fixed filler loading, SMR L/ENR 25 blend shows a lower percentage swelling than SMR L/SBR blends. © 2003 Society of Chemical Industry     

Ultrasound devulcanization of unfilled natural rubber networks,studied via component molecular mobility

¹³C NMR solids spectroscopy and transverse relaxation, and ¹H relaxation and pulsed‐gradient spin‐echo self‐diffusion measurements at 70 °C were used to study molecular and segmental mobilities in natural rubber before and after sulfur crosslinking, and after subsequent devulcanization using intense ultrasound. NMR relaxation does not clearly distinguish between entangled and crosslinked network mobility, but unentangled sol and oligomeric species are separable within the longer T₂ decay components. Ultrasound reactor settings affect the amount of extractable sol generated. Some two‐thirds of the sol is entangled, with number‐average molecular weights (M_n) above 10 000 g mol^?1. Samples also contain near 2 wt% of inert light species (M_n < 400 g mol^?1); ultrasound is relatively ineffective in producing additional oligomeric material. All proton mobilities increase as more sol is produced, but ¹³C relaxation, reflecting intramolecular effects, indicates a slight decrease in backbone mobility. In contrast with other rubbers, in natural rubber, neither the glass transition nor the sol diffusion rate is greatly affected by the extent of ultrasound exposure. Comparisons with previous similar work of this laboratory, particularly styrene‐butadiene rubber, are useful in confirming the molecular mechanisms involved. Copyright © 2007 Society of Chemical Industry     

The use of experimental design to study the responses of continuous devulcanization processes

This paper presents the use of statistical analysis for studying the responses of two continuous devulcanization processes (of the EPDM roofing sheet and the EPDM profile) in the extruder. The response is represented by the reaction conversion, which is denoted as the relative decrease in crosslink density. Experimental design is considered as a useful tool when the kinetic data for the physical modeling are not available. The models derived show similar tendency of both processes with respect to the temperature and the screw speed. A difference is observed in their responses to the feed rate, which might be the consequence of their different devulcanization rates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5028–5038, 2006     

NR/SBR内胎胶配方的改进

对天然橡胶(NR)/丁苯橡胶(SBR)内胎胶配方进行调整:降低NR用量比例,调整补强体系和硫化体系。结果表明:NR/SBR并用比由60/40减小到50/50,胶料的门尼粘度较大,焦烧时间较长,加工安全性较好,热老化后性能下降率低,其他性能差异不大;成品内胎的耐热老化后性能明显改善,生产成本降低。     

纳米氧化锌在NR/BR并用胶及SBR胶料中的应用

研究纳米氧化锌替代普通氧化锌在天然橡胶(NR)/顺丁橡胶(BR)并用胶以及丁苯橡胶(SBR)胶料中的应用。结果表明,纳米氧化锌减量10%代替普通氧化锌,NR/BR并用胶及SBR胶料的加工性能和物理性能基本不变,质量减小,成本降低。     

High-strain hysteresis of rubber vulcanizates over a range of compositions,rates, and temperatures

Hysteresis loss of natural rubber (NR) and styrene–butadiene rubber (SBR) vulcanizates having variations of loading of carbon black, silica, clay, resin, and curatives has been measured over a wide range of strain rates and temperatures as well as under swollen conditions. Hysteresis loss increases with an increase in strain rate, filler loading, resin loading (at high rates), crosslink density, and strain level. Hysteresis decreases with an increase in temperature, particle diameter of filler, and resin loading at high testing temperature. All the data of hysteresis loss of filled NR and SBR compounds have been found to be superimposable on single master curves with the help of the WLF shift factor. The master curves can be divided into three regions. The slope of the intermediate region, Δlog(hysteresis)/Δlog(Ra_T) has been found to be 0.1 for almost all the vulcanizates. Similar master plots have been obtained when the hysteresis loss has been measured at higher cycles and higher extensions and also by using the data of the hysteresis loss ratio. The hysteresis loss ratio of all the vulcanizates follows a similar trend, except for the highly crosslinked system, which shows a lower value. Carbon black contributes significantly to the hysteresis loss even when the energy dissipation is minimized by swelling. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1429–1439, 1997     

Synthesis of high rubber styrene–EPDM–acrylonitrile graft copolymer and its toughening effect on SAN

High rubber styrene–EPDM–acrylonitrile (AES) was prepared by the graft copolymerization of styrene (St) and acrylonitrile (AN) onto ethylene–propylene–diene terpolymer (EPDM) in n‐heptane/toluene cosolvent using benzoyl peroxide as an initiator. The effects of reaction conditions, such as reaction temperature, initiator concentration, EPDM content, the solvent component, and reaction time, on the graft copolymerization are discussed. In addition, according to the research on mechanical properties of the SAN/AES blend, a remarkable toughening effect of AES on SAN resin was found. By means of scanning electron microscopy, the toughening mechanism is proposed to be crazing initiation from rubber particles and shear deformation of SAN matrix. Uniform dispersion of rubber particles, as shown by transmission electron microscopy, is attributed to the good compatibility of SAN and AES. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 416–423, 2004