Effect of electron beam irradiation on the properties of ethylene‐(vinyl acetate) copolymer/natural rubber/organoclay nanocomposites

The effects of electron beam (EB) irradiation on the morphology, crosslink density, and tensile properties of EVA/SMR L (Standard Malaysian Rubber)/organoclay nanocomposites prepared by a melt‐blending technique were investigated. All the samples were irradiated by using a 3.0‐MeV EB apparatus with doses ranging from 50 to 200 kGy. Organoclay loading was varied from 0 to 10 phr (parts by weight per hundred parts of resin). X‐ray diffraction results and transmission electron microscopy images proved that the dispersion of organoclay in the nanocomposites was slightly improved by EB irradiation. The gel fraction yield for the nanocomposites increased with irradiation dose but decreased with organoclay loading. However, at 200 kGy, the gel fraction yield was almost the same at all organoclay loadings. Tensile strength and stress at 100% elongation increased proportionally with the irradiation dose. Elongation at break of the nanocomposites increased up to 100 kGy but then decreased at higher irradiation doses. The intercalation and exfoliation of the organoclay, the barrier effect, and the Hofmann degradation of the modification agent are the three major factors leading to the improvement of the properties of the irradiated nanocomposites. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Irradiation Crosslinking of PVC/ENR Blend: A Comparative Study with the Respective Homopolymers

Electron beam initiated crosslinking on a 50/50 poly(vinyl chloride)/epoxidized natural rubber blend was studied in the absence and presence of 3 phr trimethylolpropane triacrylate (TMPTA). Comparative studies were made on PVC and ENR homopolymers. The samples were irradiated by using a 3.0 MeV electron beam machine at doses ranging from 20 to 200 kGy in air and room temperature. The changes in tensile strength, gel fraction and tan δ curves of the samples were investigated. The enhancement in tensile strength, gel fraction, glass transition temperature together with a concomitant decline tan δ peak revealed that under the irradiation conditions employed, the PVC/ENR blend crosslinked by electron beam irradiation. Addition of 3 phr TMPTA found to be effective in increasing the degree of crosslinking. Similar observations were also noted for the homopolymers PVC and ENR, implying that both PVC and ENR in the blend undergo crosslinking to a certain extent.     

Effects of different preparation methods on the properties of poly[ethylene‐co‐(vinyl acetate)]/(Standard Malaysian natural rubber)/organoclay nanocomposites

Poly[ethylene‐co‐(vinyl acetate)] (EVA)/(Standard Malaysian natural rubber) (SMR L)/organoclay nanocomposites were prepared by using melt intercalation and solution blending methods. In both preparation methods, the EVA: (SMR L) ratio was prefixed at 50:50, while the organoclay loading was varied from 0 to 10 phr. The effects of two different processing routes and organoclay loading on the morphology, tensile, properties thermal properties, and flammability of the nanocomposites were studied. X‐ray diffraction results and transmission electron microscopy images proved that solution blending promotes better dispersion of organoclay than melt intercalation. Thus, the nanocomposites prepared by the solution‐blending method exhibited higher values of tensile strength, stress at 100% elongation (M100), and thermal stability. The M100 value and thermal stability improved proportionally with the increase of organoclay content, owing to the demobilizing effect and the barrier properties of the organoclay. The optimum tensile strength value was achieved at a 2‐phr organoclay loading. Further increases in loading decreased the strength of the nanocomposites. Tensile fracture surfaces of the nanocomposites prepared by both methods showed different fracture behavior, as evidenced by scanning electron microscopy images. Flammability decreased when the organoclay loading increased for the nanocomposites prepared by both methods. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

亚乙基硫脲对PVC和PVC/ENR共混物的交联作用

从交联速率、压缩永久变形、凝胶质量分数、强伸性能和耐热性能等方面考察了亚乙基硫脲（ＥＴＵ）和ＥＴＵ／硫黄对ＰＶＣ及其与环氧化天然橡胶（ＥＮＲ）共混物的交联作用。结果表明,ＥＴＵ和ＥＴＵ／硫黄对ＰＶＣ及其与ＥＮＲ的共混物有明显的交联作用;交联后共混物的物理性能和耐热性能均有较大提高;适当增大ＥＮＲ用量,有利于提高共混物的热变形性能;ＰＶＣ／ＥＮＲ的共混比为７０／３０时,硫黄的最佳用量为１５份,促进剂选择促进剂ＤＭ／ＴＭＴＤ体系为佳。     

Biodegradable PBAT/Starch Nanocomposites

Starch-based biodegradable banocomposites of poly(butylene adipate-co-terephthalate) [PBAT] and organically modified nanoclays were prepared using melt intercalation technique in Haake Torque Rheocord 9000. Two different organically modified nanoclays Cloisite C20A and Cloisite C30B at various wt% (1, 3, 5) have been used for fabrication of nanocomposites. Starch was gelatinized to prepare thermoplastic starch (TPS) for increasing the compatibility with the PBAT matrix. Subsequently, films of PBAT/TPS blends at various TPS contents (10, 20, 30, 40) wt% and PBAT/TPS Organoclay biodegradable blend nanocomposites at different wt% of nanoclays were prepared using solvent casting method. The interfacial region between the biodegradable polymer matrix and the clays were also modified with grafting of Maleic anhydride (MA) with PBAT chains, during melt blending through two stage reactive extrusion process. Mechanical tests revealed an increase in tensile modulus and elongation at break with the incorporation of 30 wt% TPS and C30B nanoclay to the tune of 44.45% and 776.9% as compared with PBAT matrix. PBAT/TPS30 wt%/C30B3wt% shows maximum tensile modulus and elongation at break due to intercalation of silicate layers resulting from similarity in the surface polarity and interactions of C30B with TPS. Morphology of PBAT/TPS30%/C30B3% biodegradable blend nanocomposite studied using WAXD and SEM indicated intercalation and improved dispersion of TPS within PBAT with incorporation of C30B. Dynamical mechanical analysis of PBAT/TPS/C30B biodegradable blend nanocomposite revealed an increase of storage modulus and glass transition temperatures of PBAT with addition of nanoclays. Further Biodegradation test also confirmed higher biodegradability of PBAT in presence of TPS and C30B.     

Electrical and mechanical properties of acrylonitrile‐butadiene‐styrene/multiwall carbon nanotube nanocomposites prepared by melt‐blending

The electrical properties in polymer/carbon nanotube (CNT) nanocomposites are governed not only by the degree of dispersion but also to a greater extent on the aspect ratio of the CNTs in the final composites. Melt‐mixing of polymer and CNTs at high shear rate usually breaks the CNTS that lowers the aspect ratio of the nanotubes. Thus, homogeneous dispersion of CNTs while retaining the aspect ratio is a major challenge in melt‐mixing. Here, we demonstrate a novel method that involves melt‐blending of acrylonitrile‐butadiene‐styrene (ABS) and in situ polymerized polystyrene (PS)/multiwalled CNT (MWCNT) nanocomposites, to prepare electrically conducting ABS/MWCNT nanocomposites with very low CNT loading than reported. The rationale behind choosing PS/MWCNT as blending component was that ABS is reported to form miscible blend with the PS. Thus, (80/20 w/w) ABS/(PS/MWCNT) nanocomposites obtained by melt‐blending showed electrical conductivity value ≈1.27 × 10^?6 S cm^?1 at MWCNT loading close to 0.64 wt %, which is quite lower than previously reported value for ABS/MWCNT system prepared via solution blending. Scanning electron microscopy and differential scanning calorimetry analysis indicated the formation of homogenous and miscible blend of ABS and PS. The high temperature (100°C) storage modulus of ABS (1298 MPa) in the nanocomposites was increased to 1696 MPa in presence of 0.64 wt % of the MWCNT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of epoxy resin on morphology and physical properties of PVC/organophilic montmorillonite nanocomposites

Poly(vinyl chloride)/organophilic montmorillonite (PVC/OMMT) nanocomposites were prepared by means of melt blending. A liquid epoxy resin was used to aid PVC chains in intercalating into silicate layers. The effects of the preparation methods and epoxy resin contents on the melt intercalation of PVC were investigated. The morphology development, mechanical properties and optical properties of the PVC/OMMT composites were tested as functions of epoxy resin content and OMMT content. Wide‐angle X‐ray diffraction, transmission electron microscopy and scanning electron microscopy were used to characterize the morphology of the resulting composites. After being pretreated by the epoxy resin, the OMMT layers were largely intercalated into the PVC matrix, and even exfoliated at high epoxy resin content. The addition of epoxy resin led to a decrease in optical clarity of the composites but improved the processing stability, as indicated by yellowness index and haze measurement. However, the optical clarity of the composites containing 4 phr of epoxy resin (PVC/E‐OMMT) was improved by increasing the OMMT content, as shown by light transmission. Both the tensile strength and notched Izod impact strength of the PVC/E‐OMMT composites reached their maximum values when the OMMT content was 0.5 phr and the epoxy resin content was 2 phr. With further increase of the OMMT content and the epoxy resin content, the tensile strength decreased but was still higher than that of original PVC. The method of addition of epoxy resin had little effect on the physical properties but mainly influenced the morphology of PVC/OMMT nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2184–2191, 2003     

Morphology,mechanical properties,and thermal stability of rigid PVC/clay nanocomposites

PVC/Poly(ε‐caprolactone) (PCL)/organophilic‐montmorillonite (OMMT) and PVC/Polylactide (PLA)/OMMT nanocomposites were prepared by a two‐step process. PCL/OMMT and PLA/OMMT master batches were prepared by melt blending using a two‐roller mill first, and then they were blended with PVC via extrusion. PVC/OMMT nanocomposites were also prepared using a two‐roller mill. Morphology, mechanical properties, and thermal stability were investigated. The formation of exfoliated or intercalated nanocomposites was confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Only the PVC/PCL/OMMT nanocomposite showed both higher tensile strength and stiffness than unfilled PVC. Atomic force microscopy (AFM) indicated dependency of this behavior not only on the clay dispersion, but also on the adhesion between the OMMT and the polymer matrix. Furthermore, scanning electron microscopy (SEM) showed that the large plastic deformation of the PVC/PCL matrix also contributed to the strength increase of the PVC nanocomposites. The effect of PCL/OMMT on the improvement of the thermal stability of PVC was remarkable while the effect of PLA/OMMT was moderate. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of ε-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).     

Modification of PVC/ENR blends by electron beam irradiation

The effects of electron irradiation, with doses ranging from 20 to 100 kGy on the physical properties of poly(vinyl chloride)/epoxidised natural rubber blends (PVC/ENR50 blends) were investigated. The enhancement in tensile strength, elongation at break, hardness, and aging properties of the blends have confirmed the positive effect of irradiation on the blends. Crosslinking of the ENR50 phase proved to play a major role in the improvement of mechanical properties of blends. The results also revealed that at any blend composition the enhancement in properties depends on the irradiation dose which controls the degree of radiation-induced crosslinking. The single glass transition temperature obtained confirms that the blends remain miscible upon irradiation.     

The role of rubber characteristics in preparing rubber/clay nanocomposites by melt compounding

Rubber/organic clay (OC) nanocomposites were produced by melt blending. Polar or unsaturated matrices (e.g., NBR and SBR) could easily enter into OC layers, whereas using nonpolar unsaturated rubber (EPDM), without other additives' help, intercalation structure could not be directly obtained. For the EPDM system, an intercalated structure was observed in presence of stearic acid (SA) for composites composed of SA and OC. Transmission electron microscopy observation showed that the dispersion of clay in nonpolar saturated rubber matrix was much poorer than that in polar or unsaturated matrix. The same effect of polar matrix was confirmed by comparison between IIR/OC and BIIR/OC systems. Moreover, using OC pretreated by SA (S‐OC), the dispersion of clay was obviously improved in the investigated nanocomposites, due to the intercalation of SA into OC interlayers. Especially in the nonpolar saturated EPDM system, the intercalation structure could be easily observed. Relative to the corresponding nanocomposites using OC, tensile strengths and the stresses at low strain of NBR and SBR based nanocomposites with S‐OC were significantly improved; while with EPDM nanocomposite, using S‐OC, only tensile strengths were improved but the stresses at low strain were almost the same, which should be related to the different interfacial force between OC and different rubber matrices. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚氯乙烯纳米复合材料研究进展

阐述了共混法、原位聚合法和插层聚合法等聚氯乙烯(PVC)纳米复合材料的制备方法,介绍了PVC/无机粒子、PVC/黏土等几种纳米复合材料的性能,指出了PVC纳米复合材料的发展方向。     

Oxygen Barrier Properties of New Thermoplastic Natural Rubber Nanocomposites

Nanocomposites of linear low-density polyethylene (LLDPE)/natural rubber (NR)/liquid natural rubber (LNR) blend denoted as TPNR with montmorillonite-based organoclay (OMMT) were prepared using melt blending method. The melt blending of LLDPE/NR/LNR with a composition of 70:20:10 formed blends. For better dispersion of nanoclay in the TPNR blend, MA-PE was used as a coupling agent. The nanoclay dispersion was investigated by X-ray diffraction (XRD), and a novel method using permeability measurements data in a permeability model. The measured d-spacing data proved a good dispersion of nanoclay at low clay contents. The permeability model for flake-filled polymer was used to estimate the aspect ratio of nanoclay platelets in the blend nanocomposites. The oxygen barrier property of the TPNR blend improved about two-fold by adding only 2 wt% of organoclay. Differential scanning calorimetry showed an increase in cystallinity up to 20% suggesting an increase in spherulite growth, by the increased in melting temperature. The increase in the barrier property of the blend with the induction in crystallinity indicates the dominant role of organoclay platelets in barrier improvement. Scanning electron micrographs of tensile fracture surface of the nanocomposite, exhibited a very ductile surface indicating a good compatibility of LLDPE and NR and also, a possible contribution of nanoparticles to the deformation mechanism, such as extensive shear yielding in the polymer blend. The transmission electron micrograph, showed an intensive intercalation structure and exfoliation structure with the presence of MA-PE.     

Hybrid polyvinyl alcohol/polyvinyl chloride nanocomposites reinforced with graphene-carbon nanotube for acid red environmental treatments

ABSTRACT

Hybrid polyvinyl alcohol and polyvinyl chloride/graphene and carbon nanotube nanocomposites PVA–PVC/Gr–CNTs_a-e were successfully synthesized by a solution-casting method. Mixed Gr–CNTs ratio (50%:50%) was prepared in 2, 5, 10, 15, and 20 wt% and added to the host polymers (PVA/PVC). The characterization tools for the fabricated nanocomposites show homogenous interaction between the fillers and PVA/PVC polymer matrix. A significant improvement in the thermal properties of the (PVA/PVC) matrix was observed by adding mixed fillers, even at low loadings of mixed Gr–CNTs on to the matrix. Scanning electron microscopy and transmission electron microscopy images of the prepared composites show a good dispersion of PVA–PVC and mixed Gr–CNTs and present core-shell morphology. Impressive improvement in the percentage of acid red removal using PVA–PVC/Gr–CNTs_a–e was achieved and improved with time, solution temperature, and composites mass. The process of removing acid red was described kinetically and thermodynamically. The pseudo-second-order kinetic model is the most appropriate kinetic model to describe the adsorption of acid red by PVA–PVC and PVA–PVC/Gr–CNTs_d nanocomposites from an aqueous solution. Our results offer a facile method for the removal of acid red from three types of water: red sea, tap water, and distilled water.     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

Nitrile rubber/organomontmorillonite nanocomposites produced by solution and melt compounding: Effect of the polarity of the quaternary ammonium intercalants

A comparative study of the development of nitrile rubber (NBR) based nanocomposites was performed; two organomontmorillonites (Cloisite 15A and Cloisite 30B) and two procedures for clay dispersion (melt blending and solution intercalation) were used. The nanocomposites were cured with a system based on dicumyl peroxide in the presence of m‐phenylenebismaleimide as a coagent for curing. The dispersion of the organoclay inside the NBR matrix was investigated with transmission electron microscopy and X‐ray diffraction. All the cured systems displayed a combination of intercalated, partially exfoliated clay platelets and confined, deintercalated clay; the degree of dispersion depended on the amount of clay, the type of intercalant, and the intercalation procedure. The highest amount of intercalated/exfoliated clay was obtained with a previous dispersion of the clay (Cloisite 30B) in an NBR solution. All the nanocomposites presented outstanding tensile strength and creep response, and this indicated a reinforcing effect of the layered silicates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of trimethylolpropane triacrylate (TMPTA) on the properties of irradiated epoxidized natural rubber (ENR‐50), ethylene‐(vinyl acetate) copolymer (EVA), and an ENR‐50/EVA blend

The effect of trimethylolpropane triacrylate (TMPTA) monomer on the tensile properties, dynamic mechanical properties, and morphology of irradiated epoxidized natural rubber (ENR‐50), ethylene‐(vinyl acetate) copolymer (EVA), and an ENR‐50/EVA blend was investigated. The ENR‐50, EVA, and ENR‐50/EVA blend were irradiated by using a 3.0‐MeV electron‐beam apparatus at doses ranging from 20 to 100 kGy. The improvement of tensile properties and morphology with irradiation indicated the advantage of having irradiation‐induced crosslinks in these materials. Observation of the properties studied confirmed that TMPTA was efficient in enhancing the irradiation‐induced crosslinking of ENR‐50, EVA, and the ENR‐50/EVA blend. Addition of TMPTA improved the adhesion between the ENR‐50/EVA blend phases by forcing grafting and crosslinking at a higher irradiation dose (100 kGy). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers.     

Melt elasticity behavior and extrudate characteristics of rigid poly(vinyl chloride)/epoxidized natural rubber miscible blends

A study on the melt elasticity behavior and extrudate characteristics of melts of rigid poly(vinyl chloride), PVC, and rigid poly(vinyl chloride)/epoxidized natural rubber (ENR) miscible blends were conducted. Extrusion studies were carried out in a capillary rheometer and examinations of the surface characteristics of the extrudate were made by taking photomicrographs in a scanning electron microscope. The anomalous behavior in the die swell ratio of rigid PVC arising from the particle agglomerates continued in its blends up to 50 wt% composition of ENR. Temperature independence for high ENR blends was noted for the principal normal stress difference and elastic shear modulus, when shear stress was held constant. Recoverable shear strain and die swell ratio behaved identically in terms of blend composition and processing temperature. Factors which control the extrudate distortion and melt fracture of the melts of rigid PVC/ENR systems were fusion of particle agglomerates and strength of melts. Diamond cavitations were typical of the extrudate surface of PVC melts as those of the fracture surface of the tensile failure of PVC. Conditions to obtain a smooth extrudate surface of rigid PVC melts in blends with ENR have been found to be the low ENR content, low shear rate, or stress and high processing temperature.     

Mechanical and physicochemical properties of electron beam irradiated rubber/clay nanocomposites

Effect of electron beam irradiation on the mechanical and physicochemical properties of both styrene butadiene rubber (SBR)/clay and ethylene propylene diene monomer (EPDM)/clay nanocomposites containing clay contents from 3 to 10 phr prepared by melt blending method has been investigated. The prepared composites were subjected to electron beam irradiation doses of up to 150 kGy to induce radiation curing, whereas the mechanical properties in terms of tensile strength (TS), tear strength (Ts), and elongation at break (E_b) were studied as a function of irradiation dose and clay content. TS and Ts increased with increasing irradiation dose up to 100 kGy, they were decreased with further increase in dose. An increase in TS and Ts for SBR and EPDM nanocomposites containing various organomodified montmorillonite (OMMT) contents (3–5 phr) was noticed, whereas a decrement behavior was observed at higher OMMT content. The elongation at break decreased continuously with both irradiation dose and OMMT content. The crosslink density for either EPDM or SBR samples increases with increasing irradiation dose up to 150 kGy and by increasing clay content up to 5 phr, whereas it decreases at higher clay content (7–10 phr). At 5 phr OMMT and 100 kGy irradiation, SBR nanocomposites showed higher TS and Ts than EPDM nanocomposites, while the crosslink density of SBR is lower. POLYM. COMPOS., 34:1600–1610, 2013. © 2013 Society of Plastics Engineers     

不同改性蒙脱土对ENR/PVC共混型TPV填充效果的研究

采用熔融插层法制备了聚氯乙烯/蒙脱土(PVC/MMT)插层产物,再将该产物与环氧化天然橡胶(ENR)在密炼机中进行熔融共混制备ENR/PVC/MMT共混型热塑性弹性体(TPV),研究了不同改性MMT对共混物力学性能、热稳定性以及动态力学性能的影响。结果表明:二甲基双十八烷基铵改性蒙脱土(MMT-2C18)能显著提高ENR/PVC共混型TPV的拉伸强度,无机MMT能显著提高ENR/PVC的断裂伸长率,十八烷基铵改性蒙脱土(MMT-C18)会降低TPV的拉伸强度和断裂伸长率;有机改性MMT会促进TPV中PVC的降解,使得复合材料的热稳定性降低;动态热力学分析显示,MMT可使复合材料的储能模量增加,其中有机改性MMT使材料的损耗因数(tanδ)曲线峰强降低,峰宽变宽。