Synthesis and Characterization of Conductive Polypyrrole/Montmorillonite Nanocomposites via One-pot Emulsion Polymerization

A series of electrically conductive polypyrrole/clay nanocomposites were synthesized in this work by using one-pot emulsion oxidative polymerization of pyrrole in the presence of unmodified clay and using DBSNa as the surfactant. The effect of surfactant on the morphological and electrical properties of PPy also were investigated and discussed in some extent. Electrical conductivity of the samples was measured by using samples in which the conductive materials was sandwiched between two Ni electrodes at room temperature. PPy/MMT nanocomposites were characterized by using XRD, TEM, TGA and DSC means of investigation. Intercalated structures were determined for the nanocomposites as confirmed by XRD and TEM studies. Electrical conductivity of the nanocomposites was measured to be dependent to the clay content, and the methods of preparation. Measurement also showed that polymerization of pyrrole monomers pre-intercalated between the clay gallery spaces of the clay led to higher conductivity for the nanocomposite in the same level of clay content. Thermal property measurements showed a lower thermal decomposition rate for the PPy/MMT nanocomposites with respect to the PPy.     

Radiation effect on properties of carbon black filled NBR/EPDM rubber blends

Rubber blend of acrylonitrile butadiene rubber (NBR) and ethylene-propylene diene monomer (EPDM) rubber (50/50) has been loaded with increasing contents, up to 100 phr, of reinforcing filler, namely, high abrasion furnace (HAF) carbon black. Prepared composites have been subjected to gamma radiation doses up to 250 kGy to induce radiation vulcanization under atmospheric conditions. Mechanical properties, namely, tensile strength (TS), tensile modulus at 100% elongation (M₁₀₀), and hardness have been followed up as a function of irradiation dose and degree of loading with filler. On the other hand, variation of the swelling number as a physical property, as a function of same parameters, however, in car oil as well as brake oil has been undertaken. In addition, the electrical properties of prepared composites, namely, their electrical conductivity, were also evaluated. The thermal behavior of the prepared composites was also investigated. The results obtained indicate that improvement has been attained in different properties of loaded NBR/EPDM composites with respect to unloaded ones.     

Facile preparation of highly conductive,flexible, and strong carbon nanotube/polyaniline composite films

In general, the high electrical conductivity (EC) comes into conflict with the good flexibility and high strength of carbon nanotube (CNT)/polyaniline (PANI) composites. In other words, a high CNT content will bring about a high EC but lead to a low flexibility and strength due to the CNT‐constrained matrix deformation and CNT aggregation. In this work, a highly conductive, flexible and strong CNT/PANI composite film prepared via a facile solvent‐evaporation method is readily obtained by a cold stretching. The cold stretching is conducted at room temperature for the CNT/PANI film. It is observed that the cold stretching process leads to an unexpectedly enhanced EC. The as‐obtained EC of 231 S/cm is much higher than that (2 – 50 S/cm) of the previously reported CNT/PANI composite films. Meanwhile, the strength is obviously improved over that of the pure PANI film and the good flexibility is maintained to a high degree by the introduction of a proper CNT content. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1575–1585     

Intumescent flame retardation and silane crosslinking of PP/EPDM elastomer

This study deals with the silane crosslinking and intumescent flame retardation of polypropylene/ethylene‐propylene‐diene copolymer (PP/EPDM) elastomers. The effect of silane crosslinking on the flame retardancy of the PP/EPDM composites containing melamine phosphate (MP) and dipentaerythritol (DPER) was studied by limiting oxygen index, UL 94 and cone calorimetry tests. The chemical composition of the silane crosslinked and flame retarded PP/EPDM composites treated at different temperatures was studied by X‐ray photoelectron spectroscopy and real time Fourier transform infrared (FTIR) spectrometry. Thermal decomposition and crystallization behavior of the PP/EPDM composites were investigated using thermogravimetric analysis and differential scanning calorimetry, respectively. Moreover, the mechanical properties of the composites were also studied. It is found that the flame retardancy, mechanical properties, and thermal decomposition behavior of the composites are influenced by silane grafting and crosslinking. Copyright © 2008 John Wiley & Sons, Ltd.     

钴铁氧体/膨胀石墨及其聚吡咯复合物的制备和油水分离性能

用化学共沉淀法和原位乳液聚合法分别制备了钴铁氧体/膨胀石墨复合微粒(CF/EG)和钴铁氧体/膨胀石墨/聚吡咯复合物(CF/EG/PPy)。用现代分析技术表征了样品的组成、结构、形貌、电-磁性能和油水分离性能。结果表明,CF粒子已填嵌入到膨胀石墨的层间,CF/EG/PPy复合物的核(CF/EG)和壳(PPy)之间存在着一定的相互作用,样品的油水分离效果与膨胀石墨的层间空隙成正比,其次序为:EG>CF/EG>CF/EG/PPy。磁性的CF/EG微粒回收容易,重复使用性能优良,循环5次的效率不低于90%。     

Reactive compatibilization of nylon copolymer/EPDM blends: experimental aspects and their comparison with theory

In situ reactive compatibilization was first time applied to a low melting nylon (nylon 6 and 66 copolymer) and EPDM blend system. The effects of in situ compatibilization and concentration of compatibilizer on the morphology and mechanical properties of nylon/EPDM blends have been investigated. The influence of EPM‐g‐MA on the phase morphology was examined by the scanning electron microscopy (SEM) after preferential extraction of the minor phase. The SEM micrographs were quantitatively analyzed for domain size measurements. The compatibilizer concentrations used were 0, 1, 2.5, 5, and 10 wt%. The graft copolymer (nylon‐g‐EPM) formed at the interface showed relatively high emulsifying activity. A maximum phase size reduction was observed when 2.5 wt% of compatibilizer was added to the blend system. This was followed by a leveling‐off at higher loadings indicating interfacial saturation. The conformation of the compatibilizer at the interface was deduced based on the area occupied by the compatibilizer at the blend interface. The experimental compatibilization results were compared with theoretical predictions of Noolandi and Hong. It was concluded that the molecular state of compatibilizer at interface changes with concentration. The in situ compatibilized blends showed considerable improvement in mechanical properties. Measurement of tensile properties shows increased elongation as well as enhanced modulus and strength up on compatibilization. At higher concentrations of compatibilizer, a leveling‐off of the tensile properties was observed. A good correlation has been observed between the mechanical properties and morphological parameters. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of Ionizing Radiation on the Characteristics of EPDM/UHMW-PE Composites

Ultra high molecular weight polyethylene (UHMW-PE) fibers were used in a chopped form and at different concentrations as a reinforcing material in ethylene–propylene–diene terpolymers (EPDM). The effect of radiation dose and fiber concentration on the mechanical properties of the vulcanized rubber composites obtained was measured. It was found that γ-irradiation improves the interfacial adhesion between UHMW-PE fiber (Spectra 1000) and EPDM matrix which was detected by scanning electron microscopy (SEM). In addition, the Young modulus of the composites increases as the irradiation dose increases. Increasing the concentration of the fibers up to 40 phr leads to an enhancement in mechanical properties and swelling resistance of obtained composites, especially in the absence of carbon black. The absolute value of the modulus increased by a factor of at least two with the addition of carbon black. Moreover the tear strength of reinforced and filled EPDM was improved with respect to reinforced rubber. © 1997 John Wiley & Sons, Ltd.     

Electrical and mechanical behavior of filled elastomers. I. The effect of strain

Electrical and mechanical property tests have been used to examine the changes in the carbon black network structure that occur in a filled elastomer at large strains in tension and compression. These changes have been examined both in materials that have no previous loading history and in test pieces that have been subjected to a specific known prestrain. When a previously unstrained, filled elastomer specimen is stretched to moderate extensions, the electrical resistivity increases. This is ascribed to the breakdown of the carbon black network structure. At higher tensile extensions, the resistivity decreases. This reduction in the electrical resistivity is attributed to the alignment of the shaped carbon black aggregates under strain. During unloading, the resistivity behavior is different from that during loading, with the final unloaded electrical resistivity being significantly higher than that measured in the unstrained elastomer. This dramatic change in the electrical properties after unloading is in marked contrast to the relatively modest changes observed in the mechanical behavior. After the first cycle, the electrical behavior becomes much more reversible, and this indicates that the bulk of the damage experienced by the carbon black network is developed during the first cycle. After unloading from a large strain, the electrical anisotropy is small, whereas the mechanical anisotropy is more marked. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2079–2089, 2003     

Interaction of two phases in PP/EPDM polymer blend probed by positron annihilation: CONTIN analysis

Positron annihilation lifetime measurements were performed on pure polypropylene (PP), ethylene-propylene-diene monomer (EPDM) rubber, and their blends PP/EPDM with a series of EPDM volume fraction ϕ (= 10–40%). A numerical Laplace inversion technique (i.e., CONTIN algorithm), was employed to obtain the probability distribution functions (PDF) of free-volume radius. We observed that, first, the average free-volume radius in PP/EPDM blends is generally same as that in PP and is much smaller than that in EPDM. Second, the standard deviation σ_R or the width of the free-volume radius PDF in the blend decreases with ϕ in the region of ϕ = 10ndash;30%, and it increases when ϕ increases from 30% to 40%. The difference in the σ_R of the blend and the calculated value σ^c _R according to the simple-mixing rule of PP and EPDM is interpreted by the existence of the two-phase interaction (i.e., the residual thermal pressure and shear stress between PP and EPDM phases in the PP/EPDM blends). The correlation between σ_R, which indicates the interaction of two phases, and the impact strength of PP/EPDM blends was found and discussed. © 1996 John Wiley & Sons, Inc.     

Gel processing of electrically conductive blends of poly(3-octylthiophene) and ultrahigh molecular weight polyethylene

The mechanical and electrical properties of solution-processed [or gel-spun] blends of poly(3-octylthiophene) and ultrahigh molecular weight polyethylene are discussed. Tensile drawing at elevated temperatures of the phase-separated blends resulted in significant improvements of the mechanical properties, in comparison with those of the neat conducting polymer, with values of the Young's modulus reaching > 40 GPa and tensile strengths in excess of 2 GPa. Doping of the undrawn polyblend fibers with iodine vapor or FeCl₃ resulted in materials of useful levels of electrical conductivity covering the full range of 10^?15 to 10 S/cm. A distinct percolation threshold for electrical conductivity was not observed, even at poly(3-octylthiophene) concentrations as low as 0.5 w/w %; the electrical conductivity of the latter blend, after doping with iodine vapor, was 8 × 10^?8 S/cm.     

Heterogeneity of laser‐irradiated films of polyvinyl alcohol/starch blends: effect of glycerol content

The present paper reports the results of studies on the effect of laser irradiation on the morphology and thermal properties of starch/polyvinyl alcohol (PVA) blend, with varying glycerol concentration. Differential scanning calorimeter results showed that laser irradiation increased the heat of fusion (ΔH_fus), heat of crystallization (ΔH_cry), temperature of melting (T_m), temperature of crystallization (T_cry) and percentage crystallinity as a function of the amount of glycerol. It is believed that breakdown of the intermolecular hydrogen bonding between the starch and PVA causes an increase in the blend heterogeneity. These results are corroborated with the findings from thermogravimetric analysis and scanning electron microscope images. Copyright © 2013 John Wiley & Sons, Ltd.     

Dynamic mechanical properties of isotactic polypropylene/nitrile rubber blends: Effects of blend ratio,reactive compatibilization,and dynamic vulcanization

The effect of blend ratio and compatibilization on dynamic mechanical properties of PP/NBR blends was investigated at different temperatures. The storage modulus of the blend decreased with increase in rubber content and shows two T_g's indicating the incompatibility of the system. Various composite models have been used to predict the experimental viscoelastic data. The Takayanagi model fit well with the experimental values. The addition of phenolic modified polypropylene (Ph-PP) and maleic modified polypropylene (MA-PP) improved the storage modulus of the blend at lower temperatures. The enhancement in storage modulus was correlated with the change in domain size of dispersed NBR particles. The effect of dynamic vulcanization using sulfur, peroxide, and mixed system on viscoelastic behavior was also studied. Among these peroxide system shows the highest modulus. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2309–2327, 1997     

Double yielding in PA6/TPV‐MAH blends: Effect of crosslinking degree of the dispersed phase

Thermoplastic vulcanizates (TPVs) based on PP and EPDM (the ratio is 5:5) with different crosslinking degrees were prepared using different contents of phenolic resins, and then blended with polyamide 6 (PA6). The results indicated that with an increase in crosslinking degree, the double yielding phenomenon in PA6/TPV blends became more distinct, the yield stress of the first yield point and the yield stress difference of the two yield points decreased; however, the yield strain of the first yield point did not change with the increasing crosslinking degree of the TPV, but the yield strain of the second yield point increased, resulting in a more broadened yield region. The SEM results showed that with an increase in the crosslinking degree of TPV, the diameter of TPV increased in the core layer, and the orientation degree of TPV in the skin and subskin layer deceased, accompanying with a decrease of the ratio of length to diameter (L/D) of the droplets. The morphology evolution of the PA6/TPV blend during the tensile test was also studied, and the results agreed well with the model we proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 912–922, 2009     

Ternary blends based on poly (ethylene-naphthalate)/glass fibers/nitrile rubber: Preparation,properties and effect of dynamic vulcanization

This work studied the possibility of utilizing nitrile rubber (NBR) to modify the impact properties of poly (ethylene-naphthalate) (PEN). The PEN/NBR ratio used changed from 100/0 to 60/40. At the same time, glass fibers (GF), 40% weight of the PEN component, were used to reinforce the blends to compensate for the loss of mechanical properties of PEN by incorporation of NBR. The results showed that the impact strength of the PEN/GF/NBR blend (PEN/NBR = 60/40) was increased up to 27.6J/m, nearly 5 times higher than that of the neat PEN. Meanwhile, the tensile strength and flexural strength were still maintained at as high as 66.1 MPa and 98.2 MPa, respectively. Dynamic vulcanization further improved the mechanical properties of the PEN/GF/NBR blends, which provided routes to the design of new PEN/elastomer blends. Other properties of the PEN/GF/NBR blends were also investigated in terms of morphology of fractured surface, dynamic mechanical behavior, thermal stability and crystallization, by scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively.     

Synthesis of electrically conductive polypyrrole-polystyrene composites using supercritical carbon dioxide: I. Effects of the blending conditions

The electrical conductivity for a polymer composite consisting of polypyrrole (PPy) and an insulating host polystyrene (PS) is reported in this study. The host polymer was blended with pyrrole monomer using either supercritical carbon dioxide (SCCO₂) or high-pressure liquid carbon dioxide (HPLCO₂) as the carrying solvent. After the blending process, the blended host polymer was soaked in an oxidant solution. This process is compared with that of oxidant impregnation. With the same processing conditions, a polymer composite with much higher conductivity was obtained when the blending process was carried out before doping in an oxidant agent. Scanning electron microscope (SEM) and elemental analysis reveal that polymerization proceeded when the blended host polymer was soaking in the oxidant solution. It is observed that SCCO₂ provides better conditions for blending the host polymer with pyrrole monomer than HPLCO₂ at the same density. The maximum conductivity of the polymer composites also increases with temperature and pressure at the same SCCO₂ density.     

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     

Influence of preparation methods on structure and properties of PA6/PA66 blends: A comparison of melt‐mixing and in situ blending

The blends composed of polyamide 6 (PA6) and polyamide 66 (PA66) were obtained using two different preparation methods, one of which was the melt‐mixing through a twin‐screw extruder and the subsequent injection molding; and the other, the in situ blending through anionic polymerization of ε‐caprolactam in the presence of PA66. For the former, there existed a remarkable improvement in toughness but a drastic drop in strength and modulus; however, for the latter, a reverse but less significant trend of mechanical properties change appeared. Various characterizations were conducted, including the analyses of crystalline morphology, crystallographic form, and crystallization and melting behaviors using polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively; observation of morphology of fractured surface with scanning electron microscope (SEM); measurement of glass transition through dynamic mechanical analysis (DMA); and the intermolecular interaction as well as the interchange reaction between the two components by Fourier transform infrared spectrometry (FT‐IR) and ¹³C solution NMR. The presence and absence of interchange reaction was verified for the in situ and melt‐mixed blends, respectively. It is believed that the transreaction resulted in a drop in glass transition temperature (T_g) for the in situ blends, contrary to an increase of T_g with increasing PA66 content for the melt‐mixed ones. And the two kinds of fabrication methods led to significant differences in the crystallographic form, spherulite size and crystalline content and perfection as well. Accordingly, it is attempted to explain the reasons for the opposite trends of changes in the mechanical properties for these two blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1176–1186, 2007     

Multipurpose nonwoven viscose/polypropylene fabrics: Effect of fabric characteristics on sorption and dielectric properties

In this work, sorption and dielectric properties of viscose/polypropylene multipurpose nonwoven fabrics were examined. The analysis of sorption behavior showed that the changes of the water absorptive capacity, the height of capillary rise and water retention value are in a function of viscose fiber content, total porosity, the pore size and used web bonding process. It is observed that dielectric properties at frequencies from 30 Hz to 140 kHz, for samples exposed to different relative air humidity and wet samples, are dependent on viscose fiber content, web bonding process, frequency of electric field and bulk free water content. The effective dielectric permeability of wet samples rapidly decreases with an increase in frequency up to 3 kHz while spectra of the AC specific electrical conductivity showed a plateau above 13 kHz. It is also observed that the dielectric properties of wet samples increase by several orders of magnitude compared to dry samples. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 947–957     

Fe2O3/Al2O3氧载体用于甲烷化学链燃烧：负载量与制备方法的影响

以不同方法制备了系列Fe₂O₃/Al₂O₃氧载体,采用XRD、H₂-TPR、CH₄-TPR、O₂-TPD和BET等分析技术对氧载体进行了表征。研究了不同Fe₂O₃负载量氧载体的甲烷化学链燃烧性能,考察了不同制备方法对Fe₂O₃/Al₂O₃氧载体结构、反应性和产物选择性的影响。结果表明,Fe₂O₃负载量对氧载体活性及产物中CO₂选择性的影响较大,负载量较低时氧载体活性较低且引起甲烷部分氧化产物CO含量增加。制备方法亦对氧载体与甲烷的反应活性有所影响,整体上共沉淀法制备的质量分数60％Fe₂O₃/Al₂O₃氧载体具有较高的氧化活性和化学链循环稳定性。其在反应温度850℃、反应时间15 min、30次循环后甲烷转化率及产物中CO₂选择性均未见明显降低。     

Formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber blends: Effects of preparation method,composition, and thermal condition

The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007