Characterization of EPDM Vulcanizates Modified with Gamma Irradiation and Trichloroisocyanuric Acid and Their Adhesion Behavior with Natural Rubber

The adhesion strength between surface-modified vulcanized ethylene propylene diene methylene (EPDM) rubber and unmodified natural rubber (NR) was investigated by a 180° peel test. Surface modification of EPDM vulcanizate was carried out by two different techniques: (a) irradiation of the surface by gamma radiation in the presence and absence of trimethylol propane triacrylate (TMPTA) as a sensitizer and (b) chemical treatment of the surface with trichloroisocyanuric acid (TCICA). The modified EPDM surface was thoroughly characterized by attenuated total reflection infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray sulfur mapping (EDX), surface energy measurements, and free sulfur and gel content analysis. The joint between the modified vulcanized EPDM and the unmodified unvulcanized NR was prepared by a co-curing method. The adhesion strength between these two surfaces was found to depend on the nature of oxidation, roughness of the joining surfaces, and extent of blooming of sulfur on the modified surface. Surface modification of EPDM sample with 1 kGy of gamma irradiation in the presence of 10 wt% TMPTA resulted in a good increase in the adhesion strength between EPDM and NR (～76% improvement over the untreated sample). On the other hand, for the trichloroisocyanuric acid modified sample, maximum improvement of adhesion strength was observed at 0.5 wt% of TCICA (～29% improvement in comparison with the untreated sample).     

Electron beam-initiated surface modification of elastomers

Ethylene-propylene diene monomer (EPDM) containing dicyclopentadiene (DCPD) and ethylidene norbornene (ENB) as the termonomers, styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR) have been surface-modified by 10% methyl ethyl ketone (MEK) solutions of trimethylol propane triacrylate (TMPTA) at an irradiation dose of 100 kGy. The irradiation dose and TMPTA concentration were optimized using samples treated with 2, 5, 10, 20, and 50% TMPTA and 50, 100, 200, and 500 kGy doses. Two per cent solutions of acrylate rubber having diene, chloro, and epoxy groups at the reactive sites and tripropyleneglycol diacrylate (TPGDA) and tetramethylol methane tetracrylate (TMMT) were also employed as the surface modifiers. The level and nature of the vulcanization system were varied. The modified rubbers were characterized by attenuated total reflection infrared (ATR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and contact angle measurements. IR and XPS studies confirmed the generation of polar groups such as C=O and -C-O-C on the surfaces. The contact angles and the surface energy change with the nature of the modifiers, rubbers, diene monomers, the crosslinking system and the level of the curing agent. The total surface energy and the thermodynamic work of adhesion of the different systems have been correlated with the amount and the nature of the polar groups generated.     

Electron beam irradiation of sulphur vulcanised ethylene propylene diene monomer (EPDM) nanocomposites reinforced by halloysite nanotubes

Abstract

Modification of the tensile, thermomechanical, morphological and Fourier transform infrared properties of sulphur vulcanised ethylene propylene diene monomer (EPDM) nanocomposites filled with 0, 10, 30 and 100 parts per hundred rubber (phr) of halloysite nanotubes (HNTs) by electron beam (EB) irradiation in the presence of cross-link promoter trimethylolpropane triacrylate has been studied. The EB irradiation dosages of 0, 50, 100 and 150 kGy were applied on the EPDM/HNT nanocomposites after sulphur cross-linking. The tensile strength of the EPDM/HNT nanocomposites at low (<30 phr) and high (100 phr) HNT loadings increased and decreased respectively while the elongation at break decreased after applying EB irradiation.     

Barrier properties of electron‐beam‐modified EPDM rubber

EPDM rubber was surface‐ and bulk‐modified with varying concentrations of trimethylol propane triacrylate (TMPTA) in the presence of a constant electron‐beam irradiation dose of 100 kGy and over a wide range of irradiation doses from 0 to 200 kGy at a fixed TMPTA concentration (10%). The permeation rate and absorption of three homologous nonpolar solvents, namely, n‐hexane, n‐heptane, and n‐octane, along with an aromatic solvent, toluene, and a polar solvent, trichloroethylene, through unirradiated, unmodified control, and modified rubber membranes (≈150 μm) were studied. It was found that both the permeation rate and absorption decrease progressively with increase in the TMPTA concentration up to 10% for both the surface‐ and bulk‐modified rubbers. With increase in the radiation dose, there also is an initial drop in the values up to 50 kGy for the control and surface‐modified rubbers and up to about 100 kGy for the bulk‐modified one. The control rubber shows the highest absorption and permeation for all the solvents except trichloroethylene, followed by the bulk‐modified rubber membrane. Trichloroethylene is, however, absorbed and permeated most by the surface‐modified sample. The observations are explained in terms of the structural modifications of the rubber, crosslinking, changes in the relevant thermodynamic properties such as surface energy, the penetrant size, and the transport mechanism of the penetrants. The influence of temperature on the permeability characteristics of the control and modified rubbers was also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 784–795, 2000     

Tensile,flexural and morphological properties of electron beam-crosslinked LDPE–EPDM blends

The effect of electron beam (EB) irradiation on the tensile, flexural and morphological properties of low-density polyethylene (LDPE)/ethylene-propylene diene elastomer (EPDM) blends had been studied in the absence and presence of crosslink promoters, such as trimethylolpropane triacrylate (TMPTA) and triallyl cyanurate (TAC). Blends were prepared by melt mixing of LDPE and EPDM followed by EB irradiation at various doses. The gel fraction (%) of irradiated blends was increased with an increase in EPDM content as well as EB irradiation dose and consequently the tensile and flexural properties of the blends increased. The incorporation of crosslinking promoters accelerated the gel formation and improved the properties upon irradiation more efficiently. The phase morphology of fractured surface displayed immiscibility with a rough appearance before irradiation. But after irradiation, the surface became fine, smooth and uniform, which went on increasing upon irradiation, supporting the steady increase in mechanical properties. Surface appeared even smoother in the presence of TMPTA and TAC.     

Structure–property relationship of electron‐beam‐modified EPDM rubber

Electron‐beam‐initiated grafting of trimethylolpropane triacrylate (TMPTA) onto the bulk ethylene propylene diene monomer (EPDM) was carried out with varying concentrations of TMPTA at a constant irradiation dose of 100 kGy and over a wide range of irradiation doses (0–500 kGy) at a fixed concentration (10%) of TMPTA. The rubber was also modified in the bulk by tripropylene glycol diacrylate (TPGDA, 10%) and tetramethylol methane tetraacrylate (TMMT, 10%) at an irradiation dose of 100 kGy. The modified rubbers were characterized by IR spectroscopy, crosslinking density measurements, and mechanical, dynamic mechanical, and electrical properties. The IR studies indicated increased peak absorbances at 1730, 1260, and 1019 cm⁻¹ due to increased 〉CO and C O C concentrations up to certain levels of TMPTA and irradiation dose. These are accompanied by an increase in the crosslinking density. The tensile strength of the samples increases gradually with increasing both the concentration of the monomer and radiation dose up to a certain level. The values of the modulus also increase at the expense of the elongation at break. An increase in the number of double bonds from two in the case of the diacrylate to four in the case of the tetraacrylate also brings about an increase in the tensile strength and moduli values. The elongation at break, however, decreases. The DMTA measurements indicate changes in the glass transition temperature, T_g, and tan δ_max on modification. The T_g shifts to a higher temperature with a simultaneous lowering of the tan δ_max values as the TMPTA level is increased. A similar trend is observed when the irradiation dose is increased and the nature of the monomer changes from di‐ to tetraacrylate. The dielectric loss tangent registers an increase on modification by irradiation of TMPTA while the permittivity is decreased. All the results could be explained on the basis of the structural modification and crosslinking density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 323–337, 2000     

Vinyl acetate content and electron beam irradiation directed alteration of structure,morphology, and associated properties of EVA/EPDM blends

A series of ethylene vinyl acetate/ethylene–propylene diene elastomer (EVA/EPDM) blends with four types of EVAs with various vinyl acetate (VA) content, are prepared without and with crosslinker, trimethylol propane triacrylate (TMPTA). These are irradiated by electron beam (EB). As the VA content increases, the gel content, i.e., degree of crosslinking of EVA/EPDM blends, is increased. With increase in VA content, the modulus and tensile strength are decreased but elongation at break is increased due to increase in amorphousness. On EB irradiation, modulus and tensile strengths are increased but at the cost of elongation at break. Crystallinities of all blends are decreased with increase in VA and EB crosslinking. The thermal stability of EVA/EPDM blend is decreased with increase in VA content but increased after EB irradiation. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) show that with increase in VA content the miscibility of two polymers keeps on increasing, which even become more after EB irradiation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43468.     

用TMPTA改善过氧化物硫化EPDM性能的研究

在ＥＰＤＭ／白炭黑胶料的过氧化物硫化体系中,加入三羟甲基丙烷三丙烯酸酯（ＴＭＰＴＡ）能够迅速提高硫化胶的交联效率,增大网络密度,缩短硫化时间;当ＴＭＰＴＡ用量为０．５份时,ＥＰＤＭ硫化胶的拉伸强度保持率和扯断伸长率保持率达到最大值;在２．０份过氧化二异丙苯（ＤＣＰ）中加入０．５份ＴＭＰＴＡ,胶料的硫化时间比单独使用３．０份ＤＣＰ缩短４０％,且硫化胶的定伸应力、拉伸强度和撕裂强度均明显提高。     

Fatigue resistance of silica‐filled natural rubber vulcanizates: comparative study of the effect of phosphorylated cardanol prepolymer and a silane coupling agent

The fatigue resistance of silica‐filled natural rubber (NR) mixes modified with phosphorylated cardanol prepolymer (PCP) was studied in comparison with similar compositions without PCP and with those containing the same dosage of a silane coupling agent (Si‐69). Considerable improvement in the fatigue resistance was observed for the PCP‐modified NR vulcanizate containing 20 phr of silica compared with the unmodified and Si‐69 modified vulcanizates. In addition, the tear strength of the PCP‐modified NR vulcanizate was higher than that of the others. Atomic force microscopy and the scanning electron microscopy of the vulcanizates showed better dispersion of silica particles in the NR matrix in the presence of PCP than in the unmodified and Si‐69‐modified NR vulcanizates. It is assumed that, at a dosage of 5 phr, PCP functions as a coupling agent between NR and the silica particles thereby improving the filler dispersion and consequently the mechanical properties of the vulcanizate. Copyright © 2005 Society of Chemical Industry     

活性预处理三元乙丙橡胶/天然橡胶并用胶的性能

采用硫载体硫化剂4,4′-二硫化二吗啉(DTDM)对三元乙丙橡胶(EPDM)进行活性预处理,研究了活性预处理EPDM/天然橡胶(NR)并用胶的性能,并探讨了活性预处理EPDM对并用胶力学性能影响的机理。结果表明,预处理EPDM/NR并用胶的共硫化程度得到改善,并用硫化胶的力学性能提高;并用硫化胶的耐老化性能优于NR硫化胶,但比未处理EPDM/NR并用硫化胶差;并用胶只存在1个玻璃化温度的转变区,两相的相容性得到改善;在高温动态条件下,EPDM与DTDM发生活性反应,但未生成大量凝胶。     

Electron‐beam modification of nitrile rubber in the presence of polyfunctional monomers

The structural changes of nitrile rubber in both the presence and the absence of polyfunctional monomers, such as trimethylolpropane triacrylate (TMPTA), tripropyleneglycol diacrylate (TPGDA), and trimethylolmethane tetraacrylate (TMMT), at different doses of electron beam irradiations, were investigated with the help of FTIR spectroscopy (in the ATR mode), solid‐state NMR, dynamic mechanical thermal analysis, and sol–gel analysis. There was a significant decrease in the concentration of olefinic groups for modified system with 3% TMPTA compared to that of the unmodified nitrile rubber on irradiation. This was also confirmed by the increase in the carbon resonances attributed to C? C linkages from solid‐state NMR for the modified system, indicating more crosslinkages. The increase in crosslinking was also revealed by the increase in % gel content and dynamic storage moduli with radiation dose. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs, were determined for both grafted and ungrafted nitrile rubber using a mathematical model. The ratio of scissioning to crosslinking for nitrile rubber was determined using the Charlesby–Pinner equation. Mechanical properties were studied for the modified and the unmodified systems and the tensile strength was found to increase with grafting of polyfunctional monomers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 435–447, 2005     

The effect of irradiation on morphology and properties of the PET/HDPE blends with trimethylol propane trimethacrylate (TMPTA)

The mechanical properties of poly(ethylene terephthalate)/high-density poly(ethylene) (PET/HDPE) blends were improved by γ-ray irradiation combined with using a cross-linking agent—trimethylol propane trimethacrylate (TMPTA). The effect of the weight ratio of PET/HDPE, the content of TMPTA and the absorbed dose on the phase morphology and the mechanical properties of the PET/HDPE blends were investigated through scanning electron microscopy (SEM), gel fraction, Fourier transform infrared spectroscopy (FTIR), tensile and impact tests. SEM images showed that the phase structure changed significantly as TMPTA coexistence. The results of tensile and impact tests indicated that their mechanical properties depended on their structures. FTIR spectra suggested that a new structure of HDPE-g-PET was generated. When the weight ratio of PET/HDPE blend was 80/20, the content of TMPTA was 1 wt% and the absorbed dose was 30 kGy, the tensile strength, elongation at break and impact strength of irradiated blends were improved greatly compared with non-irradiated blends.     

Studies on Adhesion Between Natural Rubber and Polyethylene and the Role of Adhesion Promoters

Studies on adhesion between natural rubber (NR) and polyethylene (PE) with different levels of interaction (physical and chemical) have been carried out. Ethylene propylene diene rubber (EPDM) and chlorinated polyethylene (CPE) were used as physical promoters and epoxidised natural rubber/modified polyethylene (ENR/PEm) and sulfonated ethylene propylene diene rubber/modified polyethylene (S-EPDM/PEm) were used as chemical adhesion promoters. The failure surfaces were examined with the help of scanning electron microscopy (SEM), optical photography and electron spectroscopy for chemical analysis (ESCA) techniques.

The peel strength between natural rubber and polyethylene as measured in this study is 140 J/m². With the incorporation of physical promoters such as EPDM, the peel strength increases twenty fold because of structural similarity of EPDM with PE and the rubbery nature of EPDM. Similarly, the other promoters show significant improvement in peel strength. At high temperature and low rate of peeling, the nature of failure is mainly “stick-slip” for joints with interaction promoters. The average peel strength increases with increase in test rate and decrease in test temperature for most of the joints. All the data could be shifted onto a master curve indicating that the increase in strength is a result of viscoelastic dissipation. NR/EPDM/PE and NR/CPE/PE systems, however, behave in a different way probably because they alter the nature of crack propagation at or near the interface. ESCA results of the peeled PE surface show a chemical shift of C_1S peak. SEM photographs also indicate interaction at the interface when modifiers are used. An increase in crystallinity of PE from 30% to 64% and modulus increase the peel strength of NR/PE joints by a factor of four. The results of peel strength measurement at 90° are lower than those at 180°. Lap shear results are in line with peel strength.     

Electron‐beam irradiation of poly(vinyl chloride)/epoxidized natural rubber blends in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of poly(vinyl chloride)/epoxidized natural rubber blends, which contained trimethylolpropane triacrylate (TMPTA), was carried out over a range of irradiation doses (20–200 kGy) and concentrations of TMPTA (1–5 phr). The gel content increased with the irradiation dose and the TMPTA level, although the increase was marginal at higher doses and higher TMPTA levels. Blends containing 3–4 phr TMPTA achieved optimum crosslinking, which in effect caused the maximum tensile strength (TS) at a dose of 70 kGy. A further addition of TMPTA caused a decline in the TS above 40 kGy that was due to embrittlement, which is a consequence of excessive crosslinking and the breakdown of the network structure. The possible formation of a more open network as a result of the breakdown of the network structure was further confirmed by the modulus results. Dynamic mechanical analysis (tan δ curve) and scanning electron microscopy studies on samples irradiated at 0 and 200 kGy were undertaken in order to gain further evidence on the irradiation‐induced crosslinking. The plasticizing effect of TMPTA prior to irradiation and the formation of microgels upon irradiation were also discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1926–1935, 2001     

辐照交联PVC／EVA共混物的形态结构与性能

以电子束为辐照源，以三羟甲基丙烷三丙烯酸酯（TMPTA）单体为交联敏化剂，对聚氯乙烯与乙烯－醋酸乙烯共聚物（EVA）的共混物进行辐照交联。采用红外吸收光谱、扫描电镜方法分析了添加改性EVA的共混物形态结构。通过凝胶含量、力学性能的测定，得到结论：EVA共聚物与PVC共混可以促进PVC辐照交联，改性EVA促进效果更明显；辐照剂量增大、体系凝胶含量增加，力学性能及热延伸性能提高，但辐射剂量高于5Mrad之后，体系降解程度明显增加。     

Surface analysis and printability studies on electron beam-irradiated thermoplastic elastomeric films from LDPE and EVA blends

The electron beam-initiated surface modification of films prepared from various blends of low-density polyethylene (LDPE), ethylene vinyl acetate (EVA), and ditrimethylol propane tetraacrylate (DTMPTA) was carried out over a range of radiation doses (20-500 kGy) and concentrations of DTMPTA. The films were characterized by Fourier transform infrared-attenuated total reflectance (FT-ATR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), contact angle measurements, and peel adhesion. The printability of the films was also measured. FT-ATR and XPS revealed that the surface polarity of the films made from a 50 : 50 blend of LDPE and EVA increased up to a radiation dose of 100 kGy, compared with the unirradiated sample. The polarity decreased after 100 kGy radiation. Surface pitting and roughness were observed in the SEM photomicrographs of the same films, irradiated at higher radiation doses. Higher values of the surface energy were obtained at 100 kGy for the samples without DTMPTA and for the samples containing 3 wt% DTMPTA. Excellent printability was observed for all the films irradiated above an irradiation dose of 20 kGy. The data on the printability and peel adhesion of the irradiated films could be explained by surface energy, XPS, and SEM results.     

超微细SiO2的制备及其对天然橡胶硫化胶结构与性能的影响

研究了溶胶-凝胶法和反胶团法制备的超微细SiO2填充天然橡胶(NR)硫化胶的硫化特性和力学性能，并与未改性纳米SiO2、KH-570改性纳米SiO2进行了比较结果表明：SiO2的制备方法和SiO2的填充质量分数对NR硫化胶的硫化特性有很大的影响，溶胶-凝胶法和反胶团法制备的超微细SiO2填充NR硫化胶的门尼焦烧时间缩短，综合力学性能优于纳米SiO2／NR硫化胶；试片的拉伸断面电子扫描显微镜(SEM)观察表明，制备的超微细SiO2在NR硫化胶中的分散性较好，拉伸断面的NR基质产生了剪切变形的痕迹。体现了超微细SiO2对NR硫化胶较强的补强效果。     

Study on Blends of Ethylene Propylene Diene Rubber and Thermoplastic Polyurethanes

Blends of ethylene propylene diene rubber (EPDM) and thermoplastic polyurethane (TPU) have been studied to understand the compatibility and morphology. The study was initially done with unmodified EPDM and subsequently with modified EPDM through maleation process. Mechanical properties of unmodified EPDM blends are improved with the addition of TPU. However, the appearance of two T _gs even at lower concentrations of PU in the blends indicates that the blends are incompatible. Blends of maleated EPDM with TPU showed a single T _g and further improvement in mechanical properties which is attributed to the improvement in compatibility as also confirmed by SEM analysis.     

磁性橡胶的制备与性能研究

以聚乙二醇(PEG)6000表面改性的四氧化三铁为磁性填料制备改性四氧化三铁/NR/EPDM磁性橡胶,并对其微观结构、耐老化性能、耐酸碱性能、耐油性能和低温脆性进行研究.结果表明:以NR/EPDM并用胶为基体制备的磁性橡胶耐热老化性能、耐臭氧老化性能、耐酸碱性能和耐油性能均高于以NR为基体的磁性橡胶;基体橡胶种类对磁性橡胶的低温脆性影响不大.     

Photocrosslinking of an ethylene–propylene–diene terpolymer and the characterization of its structure and mechanical properties

An ethylene–propylene–diene terpolymer (EPDM) was photocrosslinked under UV irradiation with benzil dimethyl ketal (BDK) as a photoinitiator and trimethylolpropane triacrylate (TMPTA) as a crosslinker. The efficiency of the photoinitiated crosslinking system EPDM–BDK–TMPTA, various factors affecting the crosslinking process (the photoinitiator and crosslinker and their concentrations, the irradiation time, the temperature, the atmosphere and UV‐light intensity, and the depth of the UV‐light penetration), and the mechanical properties of photocrosslinked EPDM were examined extensively through the determination of the gel contents, infrared spectra, and mechanical measurements. EPDM samples 3 mm thick were easily crosslinked with a gel content of about 90% after 30 s of UV irradiation under optimum conditions. The photoinitiating system of a suitable initiator combined with a multifunctional crosslinker such as BDK–TMPTA enhanced the efficiency of the photocrosslinking reaction, especially by increasing the initial rate of crosslinking. The gel content of photocrosslinked EPDM, which was determined by the content of diene in EPDM, the depth of the UV‐light penetration, and the light intensity, played a key role in increasing the mechanical properties of the photocrosslinked samples in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1837–1845, 2004