Study on mechanical properties of elastomers reinforced by zinc dimethacrylate

In this work, mechanical properties of various elastomers with the representative structural features reinforced by zinc dimethacrylate (ZDMA) were studied. The results showed that there is great difference in reinforcing effects of ZDMA for different elastomers. Strain-stress curves revealed that the tensile-induced crystallization of chains might be the main reason for high strength of ZDMA/rubber composites at room temperature. The saturation and regularity of rubber chains are two essential features to determine the mechanical properties of the composites at room temperature. The kind of ZDMA makes considerable impact on performances of ZDMA/rubber composites, except for ZDMA/hydrogenated nitrile-butadiene rubber (HNBR) composite. The high temperature strengths of ZDMA/rubber composites are not high and are dominated by the polarity and saturation of matrix. Basing on the previous researching, a possible model for microstructure of ZDMA/rubber composites was put forward, which could well interpret the observed phenomenon.     

Solvent‐free fabrication of proton‐conducting membranes based on commercial elastomers

Five different types of elastomers were examined as the matrix materials in the preparation of non‐fluorinated proton exchange membranes utilizing a solvent‐free route via the in situ reaction of sodium 4‐styrenesulfonate (NaSS). The morphology of the elastomer/NaSS vulcanizates was studied to evaluate the effect of polarity, viscosity and saturation degree of the elastomer matrixes. Much better dispersion of NaSS was found in chlorosulfonated polyethylene rubber (CSM) and hydrogenated nitrile butadiene rubber (HNBR) matrixes than in the other three types of elastomer matrixes. For CSM/NaSS and HNBR/NaSS proton exchange membranes, distinctive membrane properties were observed and correlated with their different structure and morphologies. The CSM/NaSS membranes exhibited the proton conductivity as high as ~0.03 S cm^?1 and the selectivity (the ratio of proton conductivity to methanol permeability) higher than that of Nafion. Copyright © 2015 John Wiley & Sons, Ltd.     

Polymer-Filler Interphase Dynamics and Reinforcement of Elastomer Nanocomposites

The effect of polymer-filler interaction on interphase dynamics between filler particles in elastomer nanocomposites and the mechanisms of rubber reinforcement by carbon black (CB) are investigated with different techniques. To determine how polymer-filler interface influences the properties of the system, CB black was modified with the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride (AMIC) and mixed with different, more or less, polar elastomers. For typical diene-elastomers (EPDM, SBR), this modification leads to a decreased polymer-filler coupling strength due to the coverage of active sites at the CB surface by AMIC. This is demonstrated by evaluating the energy site distribution from static gas adsorption isotherms with the polymer analogues gas 1-Butene. However, an improvement of polymer filler coupling was determined in the case of saturated, polar rubbers (HNBR) due to attractive dipolar interactions between the polar units of the polymer and the strongly adsorbed IL at the CB surface. The different couplings affect the polymer-filler interphase dynamics between filler particles, which determines the properties of the filler network and filler-filler bonds. To describe the effect of CB surface modification quantitatively, the Dynamic Flocculation Model (DFM) has been used to calculate polymer- and filler-specific material parameters from cyclic stress-strain measurements. The fitted data deliver a coherent picture of filler-filler- and polymer-filler couplings showing a characteristic dependence on rubber polarity. A confirmation of the effect of surface modification on the strength of filler-filler bonds is obtained by nonequilibrium molecular dynamics (MD) simulations of bond rupture under tension. They also provide indications for a glassy-like behavior of strongly confined polymer layers between attractive walls.     

Activity of fillers in elastomer networks of different structure

The paper deals with interactions between low molecular weight substances and silica. Activity of SiO₂ towards ethylene-propylene-diene rubber (EPDM) also depends on the kind of crosslinking system used. Calcium carbonate, the filler exhibiting low interactions with elastomers does not show any changes in activity, due to application of different crosslinking systems. In our opinion, the observed increase of the fillers activity results from the modification of elastomer chains by crosslinking agents, influence of the latter on the formation of its own network (the so called “structure”) in the elastomer matrix, and above all from nanoheterogeneous distribution of network crosslinks in vulcanizates. The non Gaussian probably bimodal distribution of crosslinks is likely to influence positively properties of elastomers. A similar effect is observed in peroxide vulcanizates of EPM produced with the use of the crosslinking coagents of polar nature. Behaviour of different kinds of carbon black in natural rubber (NR) crosslinked with dicumyl peroxide (DCP), sulphur donors or sulphur with accelerators is discussed. Reinforcing action of carbon black, particularly the active ones, showed to be more effective in sulphur than in peroxide vulcanizates.     

Crystallization and mechanical properties of basalt fiber-reinforced polypropylene composites with different elastomers

In this study, composites based on polypropylene (PP), basalt fiber (BF), polypropylene-graft-maleic anhydride (MAPP) and different elastomers were manufactured by extrusion compounding and injection molding. The main focus of this study was to comparatively investigate the effect of three kinds of elastomers (ethylene–propylene–diene monomer (EPDM), polyethylene–octene (POE) and ethylene–vinyl–acetate (EVA)) on non-isothermal crystallization and mechanical properties of the composites with various BF contents. The tensile test results showed that BF had a reinforcing effect on PP resin, and the addition of MAPP further improved the tensile properties by the enhancement of PP/BF interfacial bonding. Among the elastomers, EPDM was more effective in improving the tensile strength and tensile modulus, while POE significantly toughened the impact strength. Micrographs of scanning electron microscope on the impact fracture surfaces indicated a good dispersion by the addition of POE and EPDM, while some agglomerations were observed in the presence of EVA. The non-isothermal crystallization kinetics were investigated based on Avrami and Mo equations at six different cooling rates by using differential scanning calorimetry. Micrographic images of polarized optical microscopy showed that the spherulite size of PP reduced in the presence of EPDM and EVA.     

PPC／NBR弹性体的结构与性能

本文研究了聚丙撑碳酸酯(PPC)/丁腈橡胶(NBR)弹性体结构形态、动态力学性能、力学性能、耐油、耐热氧老化及耐化学介质稳定性。发现PPC/NBR弹性体呈现IPN结构特征,加入PPC使NBR拉伸强度、扯断伸长率大幅度提高。PPC/NBR弹陸体具有优良的耐油及耐热氧老化稳定性。     

Maleic-anhydride grafted EPM as compatibilising agent in NR/BR/EPDM blends

Incorporation of approximately 30 phr Ethylene-Propylene-Diene rubber (EPDM) into natural rubber (NR)/butadiene rubber (BR) is a means to achieve non-staining ozone resistance for tire sidewall applications. However, due to incompatibility of the elastomers and heterogeneous filler distribution in each of the rubber phases, the mechanical properties deteriorate. In the present work, maleic-anhydride modified EPM (MAH-EPM) is added as a compatibilising agent between NR/BR and EPDM. The addition of 5 phr of MAH-EPM results in significantly improved tensile and tear strength when compared to a straight NR/BR/EPDM blend. These improvements can mainly be attributed to a compatibilising effect of MAH-EPM, resulting in a more homogeneous phase distribution, but in particular a much better homogeneous carbon black distribution over the different rubber phases. In addition, ionic crosslinks are introduced into the blends by interaction of MAH-EPM with zinc oxide.     

The cure of elastomers by dicumyl peroxide as observed in differential scanning calorimetry

Differential scanning calorimetry (DSC) has been used to determine the enthalpy changes accompanying the thermal homolysis and subsequent radical reactions occuring in the dicumyl peroxide (DCP) cure of elastomers (NR, EPDM, SBR, BR, NBR, and EPM). The thermal degradation of DCP alone, dispersed on kaolin clay in a hydrocarbon solvent, was also studied.The degradation of DCP alone results in an exothermic enthalpy change of ～ 215 kJ mole^?1. In elastomer systems, the observed enthalpy exchange can be ordered BR >; SBR ; NBR (34% ACN) > NBR (27% ACN) > NR > EPDM ～ EPM.Low enthalpy values are associated with systems containing predominantly secondary hydrogen atoms (EPDM, EPM). The high enthalpy of cure for BR appears associated with the known ability of the polybutadienyl radicals to propagate a limited chain reaction. The relative extent of cumyloxy radical disproportionation to hydrogen abstraction was determined in each system and this has no apparent effect on the observed enthalpy change.The method of Borchardt and Daniels was used for data reduction and calculation of apparent activation energies. For DCP degradation alone the calculated activation energy is in good agreement with literature values. In elastomer systems, the calculated activation energies must be treated with caution because, as pointed out by Borchardt and Daniels, their method does not apply to solid state reactions.     

Elastomer/LDH nanocomposites: Synthesis and studies on nanoparticle dispersion, mechanical properties and interfacial adhesion

Layered double hydroxides (LDHs) based elastomer nanocomposites have been synthesized and characterized in terms of nanoparticle dispersion, mechanical properties and interfacial adhesion. Since LDH has basic hydroxyl groups on its surface, its potential as reinforcing filler in elastomers and in additionally a crosslinking agent in carboxylated elastomers has been investigated in details. For this purpose, two different elastomers having widely different polarities and functional groups (e.g., ethylene propylene diene terpolymer, i.e. EPDM and carboxylated nitrile rubber, i.e. XNBR) have been used as the matrix. The pristine LDH based on Mg and Al was modified with decane sulfonate by the regeneration method. The morphological analysis of the nanocomposites (done by X-ray diffraction analysis and electron microscopy) shows that in both matrices LDH particles are dispersed in three different forms, i.e. as primary particles, as exfoliated layers and as soft clusters formed by both of them. However, their relative proportion differs drastically in the two matrices. We have shown in this study that the LDH can significantly improve the mechanical properties in both the system. In XNBR/LDH nanocomposites containing no conventional metal oxide curative, this improvement is very prominent due to secondary interaction between LDH and XNBR matrix indicating that LDH can crosslink carboxalated elastomers. It is also observed that LDH particle promotes strain-induced crystallization in XNBR/LDH. The fracture surface analysis shows that in XNBR/LDH nanocomposite very stable polymer-filler interface is formed and tensile failure takes place through the matrix rather than through the interface. In case of EPDM/LDH nanocomposites the opposite is observed and the polymer matrix hardly wets the surface of the LDH particle.     

EFFECT OF COMPATIBILITY ON PHASE MORPHOLOGY AND ORIENTATION OF ISOTACTIC POLYPROPYLENE （IPP） BLENDS OBTAINED BY DYNAMIC PACKING INJECTION MOLDING

The effect of compatibility on phase morphology and orientation of isotactic polypropylene （iPP） blends under shear stress was investigated via dynamic packing injection molding （DPIM）. The compatibility of iPP blended with other polymers, namely, atactic polypropylene （aPP）, octane-ethylene copolymer （POE）, ethylene-propylene-diene rubber （EPDM） and poly（ethylene-co-vinyl acetate） （EVA）, have first been studied using dynamic mechanical analysis （DMA）. These blends were subjected to DPIM, which relies on the application of shear stress fields to the melt/solid interfaces during the packing stage by means of hydraulically actuated pistons. The phase morphology, orientation and mechanical properties of the injection-molded samples were characterized by SEM, 2D WAXS and Instron. For incompatible iPP/EVA blends, a much elongated and deformed EVA particles and a higher degree of iPP chain orientation were observed under the effect of shear. However, for compatible iPP/aPP blends, a less deformed and elongated aPP particles and less oriented iPP chains were deduced. It can be concluded that the compatibility between the components decreases the deformation and orientation in the polymer blends. This is most likely due to the hindering effect, resulting from the molecular entanglement and interaction in the compatible system.     

Aggregation of nitrile-butadiene copolymers in solutions

The nonuniformity of nitrile-butadiene rubber solutions in toluene and chloroform has been studied. Dynamic-light-scattering measurements show that these solutions contain two kinds of scattering particles: small particles 10–16 nm in radius corresponding to the macromolecular coil and large particles 400–500 nm in radius corresponding to aggregates. The aggregates are stable in solutions for at least several days. Such stability may be interpreted in terms of topological factors supposing that the aggregates are formed via noncovalent interactions of tens of thousands of highly branched entangled chains. The chains become disentangled even during slight shear. Thus, the solution of nitrile-butadiene rubber subjected to soft rolling mostly contains small particles. However, in the absence of external fields, such a structure is very stable in solution and even more so in the rubber block. During storage of nitrile-butadiene rubber, formation of a relatively small quantity of covalent crosslinks suffices for fixing the structure of aggregates and prevents the disentanglement of chains. Thus, the crosslinking of the aggregates may be primarily responsible for the natural aging of nitrile-butadiene rubber during storage.     

Elastic recovery after compression in HNBR at low and moderate temperatures: Experiment and modelling

Elastic recovery after compression or compression set is one of the key indicators of elastomer performance in sealing applications, such as O-rings in flange joints. In this work, findings of a study of the compression set property of a hydrogenated nitrile butadiene rubber (HNBR) at temperatures above and below the glass transition temperature T_g are presented. The compression set in the elastomer is found to increase with cooling up to 100% at the glass transition temperature and decrease with time after unloading even at temperatures below T_g. The effects of reinforcing filler (carbon black) and the initial compression time are also considered. Equivalence of time and temperature effects on the compression set of the elastomers is then demonstrated. A viscoelastic model describing the time-temperature variation of the compression set is proposed and verified by finite element analysis (FEA) and experimental results. It is shown that modelling captures well the experimental behaviour of the elastic recovery of the studied HNBR at ambient and low temperatures.     

Toughening of poly(2,6-dimethyl-1,4-phenylene oxide)/nylon 6 alloys with functionalized elastomers via reactive compatibilization: morphology, mechanical properties, and rheology

Blends of poly(2,6-dimethyl-1,4-phenylene oxide)/nylon 6 alloys based on ethylene-propylene-diene elastomer (EPDM) grafted with maleic anhydride (MA) (EPDM-g-MA), EPDM grafted with glycidyl methacrylate (EPDM-g-GMA), and styrene-ethylene-butadiene-styrene block copolymer grafted with MA (SEBS-g-MA) were prepared via melt extruction, and morphology, mechanical properties, and rheology were studied. The compatibilizing effects of functionalized elastomers on the PPO/nylon 6 alloys were proved by DSC analysis and confirmed by the significant improvement in the notched Izod impact strength. Toughening was resulted from the smaller particle size and finer dispersion of EPDM in the PPO/nylon 6 matrix as well as a novel network structure of SEBS-g-MA domain in matrix. The notched Izod impact strength of the blends exhibited an optimum value when the extent of MA or GMA graft ratio of EPDM varied, which was an order of magnitude higher than the non-toughened alloys. The morphology revealed that the size of EPDM particles decreased with an increase in graft ratio of MA or GMA onto EPDM. Rheology investigation indicated that the MA or GMA moieties on EPDM reacted with the amine groups of nylon 6, which increased the molecular weight and the degree of branching, and thus resulted in an increase in the viscosity of the blends. This proved the reactive compatibilization between functionalized EPDM and PPO/nylon 6 matrix.     

Effects of nucleating agents on microstructure and fracture toughness of poly(propylene)/ethylene‐propylene‐diene terpolymer blends

The effects of nucleating agents (NAs) on fracture toughness of injection‐molded isotactic poly(propylene)/ethylene‐propylene‐diene terpolymer (PP/EPDM) were studied in this work. Compared with PP/EPDM blends without any NA, PP/EPDM/NA blends show very small and homogeneous PP spherulites. As we expected, PP/EPDM blends nucleated with β‐phase NA aryl amides compound (TMB‐5) present not only a significant enhancement in toughness but also a promotion of brittle‐ductile transition. However, the addition of α‐phase NA 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) has no apparent effect on the toughness of the blends. The impact‐fractured surface morphologies of such samples were analyzed via scanning electronic microscope (SEM). More detail work about the toughening mechanisms of elastomer and NA based on elastomer particles size and matrix crystal structures were carried out. Our results suggest that, besides the crystal structures of matrix, the elastomer particles size and size distribution plays an important role in controlling the toughening effect of nucleated PP/elastomer blends. The smaller the elastomer particles size and lower the polydispersity, the more apparent the synergistic toughening effect of NA and elastomer is. This investigation provides a fresh insight into the understanding of toughening mechanism of elastomers in PP blends and facilitates to the design of super toughened PP materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 46–59, 2009     

Ductile–brittle‐transition phenomenon in polypropylene/ethylene‐propylene‐diene rubber blends obtained by dynamic packing injection molding: A new understanding of the rubber‐toughening mechanism

For a more complete understanding of the toughening mechanism of polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, dynamic packing injection molding was used to control the phase morphology and rubber particle orientation in the matrix. The relative impact strength of the blends increased at low EPDM contents, and then a definite ductile–brittle (D–B) transition was observed when the EPDM content reached 25 wt %, at which point blends should fail in the ductile mode with conventional molding. Wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to investigate the shear‐induced crystal structure, morphology, orientation, and phase separation of the blends. WAXD results showed that the observed D–B transition took place mainly for a constant crystal structure (α form). Also, no remarkable changes in the crystallinity and melting point of PP were observed by DSC. The highly oriented and elongated rubber particles were seen via SEM at high EPDM contents. Our results suggest that Wu's criterion is no longer valid when dispersed rubber particles are elongated and oriented. The possible fracture mechanism is discussed on the basis of the stress concentration in a filler‐dispersed matrix. It can be concluded that not only the interparticle distance but also the stress fields around individual particles play an important role in polymer toughening. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2086–2097, 2002     

Structure and mechanical properties of SRP/HDPE/POE (EPR or EPDM) composites

The effects of dicumyl peroxide (DCP) and ethylene-octylene copolymer (POE), ethylene-propylene copolymer (EPR) or ethylene-propylene-diene terpolymer (EPDM) on the structure and properties of scrap rubber powder (SRP)/high-density polyethylene (HDPE) composites were studied. Torque and gel content results show that DCP promotes crosslinking of the SRP/HDPE/POE (EPR or EPDM) composites. The SRP/HDPE/POE (EPR or EPDM) composites containing a small amount of DCP have better mechanical properties than their corresponding composites without DCP. Highest tensile strength and elongation at break are found in the dynamically vulcanized SRP/HDPE/POE composite. Scanning electron microscopy (SEM) results show that good bonding between SRP and matrix is formed in the SRP/HDPE/POE (EPR or EPDM) composites with DCP.     

Melt rheology and morphology of thermoplastic elastomers from polyethylene/nitrile‐rubber blends: The effect of blend ratio,reactive compatibilization,and dynamic vulcanization

A study of the melt‐rheological behavior of thermoplastic elastomers from high‐density polyethylene and acrylonitrile butadiene rubber (NBR) blends was carried out in a capillary rheometer. The effect of the blend ratio and shear rate on the melt viscosity reveals that the viscosity decreases with the shear rate but increases with NBR content. Compatibilization by maleic anhydride modified polyethylene has no significant effect on the blend viscosity, but a finer dispersion of the rubber is obtained, as is evident from scanning electron micrographs. The melt‐elasticity parameters, such as the die swell, principal normal stress difference, recoverable shear strain, and elastic shear modulus of the blends, were also evaluated. The effect of annealing on the morphology of the extrudate reveals that annealing in the extruder barrel results in the coalescence of rubber particles in the case of the incompatible blends, whereas the tendency toward agglomeration is somewhat suppressed in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1104–1122, 2000     

Photo-oxidation of elastomers. A fundamental approach based on the study of a series of photo-sensitive elastomeric systems: A review

The photo-oxidation and crosslinking of increasingly complex photo-sensitized elastomers were quantitatively investigated. An ethylene-propenebutadiene terpolymer (EPDM), selected as an elastomeric medium exhibiting reactive unsaturated side chains, was photo-sensitized with various chromophoric groups: grafted phenyl groups (systems I and II), different carbonyl functions (systems III and IV), blended photo-initiators dimethoxyphenylacetophenone (DMPA) (system V) and benzophenone (BP) (system VI). Knowledge of the behaviour of these model systems proves necessary to the understanding of the predominant processes involved in the photo-oxidation of ethylene-propene rubber (EPR or EPM) blended with DMPA (system VII) or BP (system VIII) and of a random styrene-butadiene (SBR) copolymer (system IX).     

Compatibilization of elastomer-based blends

The reactive compatibilization of ethylene-propylene-diene (EPDM)-based dissimilar elastomer blends has been investigated in terms of mechanical properties and swelling degree. The use of mercapto-functionalized copolymers resulted in an improvement of mechanical properties of natural rubber-EPDM blends. The mercapto-groups are able to react with the carbon-carbon double bonds of the high diene rubber, resulting in a good interaction between phases. These interactions were confirmed by the amount of insoluble material obtained in non-vulcanized blends. From dynamic mechanical properties and swelling degree, one can suggest a covulcanization process in these blends cured with sulfur-based system. Blends composed by nitrile rubber with EPDM displayed good results in terms of mechanical properties when mercapto-functionalized EVA was employed instead of functionalized EPDM, probably because of the higher polarity of the former associated to its lower viscosity. Additionally, an improvement on mechanical properties was also achieved by using EPDM functionalized with mercapto or anhydride groups in combination with nitrile rubber functionalized with epoxy or oxazoline groups.     

Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008