Comparison of ethylene‐propylene diene terpolymer composites filled with natural and synthesized micas

In this paper, EPDM/mica composites were prepared by filling synthesized mica and natural mica separately into ethylene‐propylene diene terpolymer (EPDM) using melt blending technique. Microstructures, electrical properties, gas resistance, and mechanical properties of two EPDM/mica composites were investigated systematically. FTIR show that hydroxyl groups exist on the surface of the micas. These structural hydroxyls could be active sites conducive to the surface modification of mica. XRD analyses reveal that the natural mica is crystalline and the synthesized mica is amorphous. After being modified with silane coupling agent Si69, mica was only exfoliated into smaller micron agglomerates dispersing in EPDM, but the dispersion of amorphous synthesized mica was better. So the EPDM/synthesized mica composite possessed better mechanical property, electrical insulation property, and gas permeability resistance. It is expected that better improvement would be achieved, if mica is exfoliated further into nanosheets dispersing in the rubber matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effects of dynamic vulcanization and compatibilizer on properties of paper sludge‐filled polypropylene/ethylene propylene diene terpolymer composites

The effects of dynamic vulcanization (DV) and dynamic vulcanization plus compatibilizer (DVC) of paper sludge (PS) filled polypropylene/ethylene propylene diene terpolymer (PP/EPDM) composites on torque development, mechanical properties, water absorption, morphology, and thermal properties were studied. Results show that DV and DVC composites exhibit higher stabilization torque than unvulcanized composites (UV). The dynamic vulcanized (DV) and dynamic vulcanized plus compatibilizer (DVC) composites exhibit higher tensile strength, elongation at break, and Young's modulus but lower water absorption than unvulcanized composites. The scanning electron microscopy (SEM) study of tensile fracture surface of DV and DVC composites shows the improved interfacial interaction between PS and PP/EPDM matrix. The DV and DVC composites also exhibit better thermal stability and higher crystallinity than unvulcanized PP/EPDM/PS composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility of blends of ethylene‐propylene‐diene terpolymer and polypropylene

The miscibility of polymers is not only an important basis for selecting a proper blending method, but it is also one of the key factors in determining the morphology and properties of the blends. The miscibility between ethylene‐propylene‐diene terpolymer (EPDM) and polypropylene (PP) was explored by means of dynamic mechanical thermal analysis, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results showed that a decrease in the PP content and an increase of the crosslinking density of EPDM in the EPDM/PP blends caused the glass‐transition temperature peaks of EPDM to shift from a lower temperature to higher one, yet there was almost no variance in the glass‐transition temperature peaks of PP and the degree of crystallinity of PP decreased. It was observed that the blends prepared with different mixing equipment, such as a single‐screw extruder and an open mill, had different mechanical properties and blends prepared with the former had better mechanical properties than those prepared with the latter. The TEM micrographs revealed that the blends were composed of two phases: a bright, light PP phase and a dark EPDM phase. As the crosslinking degree of EPDM increased, the interface between the phases of EPDM and PP was less defined and the EPDM gradually dispersed in the PP phase became a continuous phase. The results indicated that EPDM and PP were both partially miscible. The mechanical properties of the blends had a lot to do with the blend morphology and the miscibility between the blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 315–322, 2002     

乙丙橡胶生产工艺与技术

乙丙橡胶以其独特的性能,在汽车工业、建筑行业、油品添加剂、塑胶跑道等领域有广泛的应用。本文主要介绍了乙丙橡胶生产技术、乙丙橡胶产品牌号、性能以及应用领域,结合现有的乙丙橡胶科研情况,阐述了乙丙橡胶催化剂的研发、核壳型球状乙丙橡胶、原位聚合法合成长链支化乙丙橡胶、乙烯、丙烯与其他二烯烃的共聚物研究进展;详细研究了乙丙橡胶溶液聚合工艺技术中的聚合技术、单体回收技术、失活洗涤技术、闪蒸提浓技术以及国外公司在中国建设装置的生产技术情况。提出了乙丙橡胶的关键生产技术是乙丙橡胶聚合所采用的催化剂体系,通过催化体系的更新换代,开发不同用途的乙丙橡胶,以满足开发高性能材料的要求。在此基础上,指出了今后乙丙橡胶新的催化体系开发将成为未来的研究重点。     

Pulsed‐plasma‐polymerized aniline thin films

An inductively coupled pulsed‐plasma reactor was used to synthesize polyaniline thin films on several substrates positioned at various distances from the center of the radio frequency (RF) coil. The samples were characterized with Fourier transform infrared (FTIR), cyclic voltammetry, and microscopic techniques. Impedance spectroscopy was used to determine the electrical characteristics of three‐layer structures with polyaniline as the middle layer between top and bottom metal electrodes. FTIR results indicated that the chemical composition and structure of the films were very dependent on the substrate's position with respect to the RF coil, there being considerably less aromatic character closer to the coil. The electrochemical behavior of the films in acidic electrolytes was similar to that of small‐molecule aniline oxidation products; the number of peaks in the cyclic voltammograms varied with the substrate. Scanning electron microscopy indicated that as the films became thicker, they developed nodules atop a somewhat smoother underlayer. Results from transmission electron microscopy and optical birefringence suggested that the films were not completely homogeneous. The impedance measurements were consistent with relatively rough films possibly containing pinholes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93:1317–1325, 2004     

Flow‐injection polymer analysis of ethylene propylene diene monomer elastomers. I

A rapid, flow‐injection polymer analysis (FIPA) method for the solution characterization of EPDM elastomers, with a wide range of ethylene comonomer content, was developed. Solutions of the polymer were introduced into a flowing mobile phase which was monitored by an array of three detectors: a right‐angle laser light‐scattering unit, a differential refractive index detector, and a differential pressure viscometer. To adequately characterize a wide range of comonomer composition, it was found that a nominal temperature of 90°C and a solvent (e.g., 1,2,4‐trichlorobenzene) capable of high‐temperature sample dissolution was needed for the analysis. Polymer association or aggregation was observed in cyclohexane at lower analysis temperatures. With an analysis time of a few minutes, information on molecular weight, molecular size, and comonomer composition can be obtained directly. Information regarding polydispersity and properties such as melt viscosity may be obtained indirectly or through correlation to other, independent property measurements. The data were also compared to a high‐temperature GPC analysis method already in use. The combination of rapid analysis time and measurement of fundamental molecular properties suggests the usefulness of the instrumentation and method to plant process control. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2178–2189, 2002     

Mechanical and morphological properties of white rice husk ash filled polypropylene/ethylene‐propylene‐diene terpolymer thermoplastic elastomer composites

The performance of white rice husk ash (WRHA) as filler for polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) thermoplastic elastomer (TPE) composites was investigated. The composites with different filler loadings were prepared in a Brabender plasticorder internal mixer. Both unvulcanized and dynamically vulcanized composites were prepared. Mixing and vulcanization processes of the composites were monitored through the typical Brabender torque‐time curves. The mechanical properties and morphology of the composites were also studied. The Brabender torque curves revealed that the dynamic vulcanization process employed was successful and incorporation of filler has no adverse effect on the processibility of the composites. Incorporation of WRHA improves the tensile modulus and flexural modulus and lowers tensile strength, elongation at break, tear strength, and toughness of both types of composites. Dynamic vulcanization significantly enhances the mechanical and TPE properties of the composites. Dynamic mechanical analysis (DMA) study revealed the existence of two phases in both types of composites. It further shows that neither dynamic vulcanization nor filler agglomeration has played a prominent role in the compatibility of the composites. Thermogravimetric investigation shows that dynamic vulcanization or WRHA loading has not adversely affected the thermal stability of the composites. The scanning electron micrographs provide evidence for the tendency to form filler agglomerates with increasing filler loading, better filler dispersion of dynamically vulcanized composites over unvulcanized composites, and effective vulcanization of elastomer phase of the composites in the presence of filler. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 438–453, 2002     

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

(Ind)₂ZrCl₂ catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5‐ethyldiene‐2‐norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60°C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the catalyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70°C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T_g) of the obtained terpolymers were between ?64 and ?52°C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Determination methods of the grafting yield in glycidyl methacrylate‐grafted ethylene/propylene/diene rubber (EPDM‐g‐GMA): Correlation between FTIR and 1H‐NMR analysis

A normalized and universally applicable calibration function for the Fourier‐transformed infrared (FTIR) quantification of the glycidyl methacrylate (GMA) grafting yield in polymers of known compositions having ethylene block sequences was established. The ¹H nuclear magnetic resonance (¹H‐NMR) spectroscopy results achieved on different GMA‐grafted ethylene/propylene/diene rubber (EPDM‐g‐GMA) and ethylene/GMA copolymers were correlated to their FTIR data to calibrate the relative determination of the FTIR method. Both direct and indirect standardization approaches were followed and evaluated. The calibration deduced was used to investigate the free radical grafting reaction of GMA on EPDM rubber in the melt phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2616–2624, 1999     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Evidences of solvent‐induced miscibility in polychloroprene‐co‐ethylene‐propene diene terpolymer blends

Solvent dependent changes in the compatibility behavior of Polychloroprene/Ethylene–propylene–diene terpolymer blends (CR/EPDM) have been investigated using dilute solution viscometry and solvent permeability analysis. To predict the compatibility of rubber blends of different compositions in solvents of different cohesive energy densities, Huggins interaction parameter (ΔB), hydrodynamic interaction (Δη) and Sun's parameter (α) were evaluated from the analysis of the specific and reduced viscosity data of two and three‐component polymer solutions. Miscibility criteria were not satisfied for CR/EPDM blends over the entire composition range in toluene, xylene, and carbon tetrachloride (CCl₄), however, a narrow miscibility domain was observed in chloroform (CHCl₃) for CR/EPDM/CHCl₃ system. These results were further corroborated with the analysis of heat of mixing (ΔH_m) and polymer–polymer interaction parameter (χ₁₂), for all rubber blend compositions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modification of fast-cure ethylene–propylene diene terpolymer rubber by maleic anhydride and effect of electron donor

Grafting of maleic anhydride (MA) onto fast-cure ethylene–propylene diene terpolymer rubber was studied. The effect of the amount of the MA, initiator (dicumyl peroxide), and electron donor (stearamide) on graft content are described. The potentiometric method and Fourier transform infrared spectroscopy are used to obtained the graft content. The stearamide suppresses the side reactions, such as crosslinking and chain scission. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1–5, 1998     

Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

Thin‐film plasma‐polymerized iso‐t‐pentinol and its postpolymerization properties

Thin films of plasma polymer were prepared from unsaturated precursor with one triple bond, iso‐t‐pentinol. This precursor was injected either in a vapor state itself or using argon as a carrier gas, bubbled through a precursor. These polymers were prepared under different fixed conditions when only one parameter of plasma polymerization among all the others was changed in each measurement during the process of polymerization (i.e., power in a matched reactor, precursor partial pressure, total pressure in reactor, electrode gap, and polymerization time). The samples were deposited on thin solid substrate having oxygenless molecules. Infrared Spectroscopy, IRS, Electron Spectroscopy for Chemical Analysis, ESCA (XPS), and Electron Paramagnetic Resonance (EPR) were used for analyses of these samples. The results of analyses proved generation and growth of oxygen‐containing groups by plasma polymerization (IRS); they also proved that C O group concentration increased and CO group concentration decreased in polymer surface layers during 24 h after plasma polymerization (ESCA). A drop of free radical concentration (measured by EPR) was steep from the end of plasma polymerization to 60 min and mild later on (to approximately 215 h). Amount of free radicals depended on the power in reactor. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 677–686, 1999     

动态硫化对三元乙丙橡胶/聚丙烯共混体系等温结晶行为和形态结构的影响

研究了三元乙丙橡胶/聚丙烯(EPDM/PP)共混物和动态硫化EPDM/PP热塑性弹性体(TPV)的等温结晶行为及形态结构,并用Avrami方程对其进行等温结晶动力学分析。结果表明,EPDM/PP共混物和EPDM/PP TPV的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV比共混物的Avrami指数小,半结晶时间短,结晶速率常数大;EPDM/PP共混物为双连续相结构,而EPDM/PP TPV是以硫化的细小橡胶颗粒为分散相、PP为连续相的"海-岛"结构,橡胶颗粒尺寸约为0.5μm。     

Studies on blends of natural rubber and ethylene propylene diene rubber modified with phosphorylated cardanol prepolymer: Processability,physico‐mechanical properties,and morphology

The melt processability and physico‐mechanical properties of blends of natural rubber (NR) and ethylene propylene diene rubber (EPDM) containing different dosages (0–10 phr) of phosphorylated cardanol prepolymer (PCP) were studied in unfilled and china‐clay‐filled mixes. The plasticizing effect of PCP in the blends was evidenced by progressive reduction in power consumption of the mixing and activation energy for melt flow with an increase in the dosage of PCP. The PCP‐modified blend vulcanizates showed higher tensile properties and tear strength despite a decrease in the chemical crosslink density (CLD) index. This is presumably due to the formation of a crosslinked network structure of PCP with the rubbers and improved dispersion of the filler particles in the rubber matrix, as evidenced by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Thermogravimetric analysis showed an increase in thermal stability of the blend vulcanizate in presence of 5 phr of PCP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5123–5130, 2006     

Surface modification of carbon nanofibers via deposition of an ultrathin coating of plasma‐polymerized poly(acrylic acid) and its effect on the properties of polyamide 6/CNF nanocomposites

Carbon nanofibers (CNFs) were coated with an ultrathin layer of poly(acrylic acid) (PAA) via plasma polymerization. The effect of the plasma reactor parameters on the extent of the CNF modification was studied. SEM micrographs showed that surface roughness increased with the plasma treatment. The thickness of the ultrathin PAA layer deposited on the CNF was determined by STEM to be ca. 8 nm. Untreated and treated CNF were melt‐mixed with polyamide 6 (PA6) in a Brabender mixing chamber to obtain PA6/CNF nanocomposites. The effect of the plasma treatment on the dispersion and compatibility was examined and found to improve markedly. Fractured tensile specimens showed that the CNF seemed to be completely embedded in the polymer matrix, indicating high compatibility between the PA6 and the PAA‐coated CNF. Tensile stress and tensile modulus of PA6 nanocomposites with treated CNF were found to increase by 30 and 48%, respectively, when compared with those with untreated CNF. However, the increase in tensile stress and modulus with respect to pure PA6 was 52 and 88%, respectively. Finally, XRD showed that the CNF induce the formation of the α (alpha)‐crystalline phase in PA6. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

超细全硫化粉末丁苯橡胶/三元乙丙橡胶共混物的结构与性能

制备了超细全硫化粉末丁苯橡胶(UFPSBR)/三元乙丙橡胶(EPDM)共混物,研究了其硫化特性、相态结构、动态力学性能及物理机械性能。透射电镜观察表明,无论UFPSBR与EPDM共混比如何,UFPSBR粒子始终保持为分散相。当UFPSBR用量为10份(质量)时,它在EPDM中的分散相尺寸为200 nm左右;用量较高时其分散相尺寸较大,存在大量的聚集体。动态力学分析结果显示共混物存在2个玻璃化转变温度,说明共混物存在两相结构。加工性能分析结果表明,UFPSBR粒子在EPDM基质中形成了网络结构,对EPDM基质起到了较好的增强作用,当UFPSBR与EPDM的质量共混比为50/50时,共混物的拉伸强度可达13.4 MPa。UFPSBR对EPDM的硫化特性有明显影响。     

Effect of treated mica on rheological,cure, mechanical,and dielectric properties of ethylene propylene diene monomer (EPDM)/barium titanate (BaTiO3)/mica

In this study, mica, treated by three types of coupling agents, isopropyl trioleic titanate (NDZ105), 3‐aminopropyltriethoxysilane (KH550), and vinyltrimethoxysiloxane homopolymer (SG‐Si6490), were utilized to improve the properties of ethylene propylene diene monomer (EPDM)/barium titanate (BaTiO₃) composites. It is found that the addition of untreated mica can increase the complex viscosity, while the KH550 modified mica can reduce the complex viscosity. Compared to single usage of coupling agent SG‐Si6490, the hybrid usage of KH550 and SG‐Si6490 can further increase the tensile strength of EPDM/BaTiO₃/SG‐Si6490 treated mica (70/20/10) from 9.10 to 11.01 MPa (22% increase). The untreated mica can increase the interfacial polarity and improve the dielectric constant of EPDM/BaTiO₃ (70/30) from 7 to 9 at 40 MHz (28% increase). Moreover, the KH550 treated mica can enhance the thermal conductivity of EPDM/BaTiO₃ (70/30) from 0.323 W m^?1 K^?1 to 0.446 W m^?1 K^?1 (38% increase). In the meantime, the increased crosslink density caused by coupling agents can increase the volume resistivity of EPDM composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44833.     

Optical characterization of plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline bilayer thin films

A capacitively coupled parallel‐plate reactor has been used to deposit plasma‐polymerized pyrrole (PPPy), plasma‐polymerized N,N,3,5‐tetramethylaniline (PPTMA), and plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline (PPPy‐PPTMA) bilayer thin films on to glass substrates at room temperature. To deposit the bilayer films, pyrrole monomer has been used as the mother material and N,N,3,5‐tetramethylaniline monomer has been deposited in different deposition time ratios after the pyrrole films were formed. Fourier transform infrared (FTIR) and ultraviolet–visible (UV–vis) spectroscopy techniques have been used to characterize the as‐grown thin films of about 500‐nm thick. The structural analyses by FTIR spectroscopy have indicated that the monomer has undergone the reorganization and the ring structure is retained during the plasma polymerization. From the UV–vis absorption spectra, allowed direct transition (E_qd) and allowed indirect transition (E_qi) energy gaps were determined. The E_qd for PPPy, PPTMA, and PPPy‐PPTMA bilayer films are found to be 3.30, 2.85, and 3.65 eV respectively. On the other hand, the E_qi for the same series are 2.25, 1.80, and 2.35 eV, respectively. From these results, it is seen that the energy gaps of the PPPy‐PPTMA bilayer films have been increased compared with the PPPy and PPTMA films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011