Effect of organoclay loading and electron beam irradiation on the physico‐mechanical properties of low‐density polyethylene/ethylene‐vinyl acetate blend

The influence of electron beam (EB) irradiation and organoclay (OC) loading on the properties of low‐density polyethylene (LDPE)/ethylene‐vinyl acetate (EVA) blends was investigated. The samples were subjected to the EB irradiation with the dose values of 50 and 250 kGy. X‐ray diffraction (XRD), gel content, mechanical, thermal, and electrical properties were utilized to analyze the characteristics of the LDPE/EVA blends with and without OC at different irradiation dosages. Gel content analysis showed that the OC promotes considerably the insoluble part so that the LDPE/EVA blends filled with OC become fully crosslinked at 250 kGy; possibly through the formation of further crosslinks between OC and polymer chains. The samples irradiated by EB showed enhanced mechanical properties due to the formation of three‐dimensional networks. In addition, thermogravimetric analysis indicated that combined OC loading and radiation‐induced crosslinking improved thermal stability of LDPE/EVA blends considerably. Copyright © 2011 John Wiley & Sons, Ltd.     

The effect of high-energy electron beam irradiation and content of ATH upon mechanical and thermal properties of EVA copolymer

Mechanical and thermal properties of ethylene vinyl acetate (EVA) mixed with various amounts of alumina trihydrate (ATH), irradiated with 5 MeV electron beam at dose range varied from 38 to 190 kGy, have been studied. A small amount (1%) of triallyl cyanurate has been used as a radiation sensitizer. It has been found that (i) EVA samples with various contents of ATH are crosslinked, (ii) crosslinking increases with irradiation dose, (iii) the mechanical properties of samples improve by irradiation and (iv) decomposition of samples takes place at two stages and due to irradiation, decomposition temperatures shift to higher values. These studies were carried out in order to obtain a suitable compound for wire and cable insulation.     

Some effects of foaming of the poly(butylene adipate‐co‐terephthalate) modified by electron radiation

Investigation of the effect of electron radiation and foaming agent on some properties of poly(butylene adipate‐co‐terephthalate) (PBAT) was the aim of the present paper. The mass flow rate, weight‐average molecular weight of irradiated PBAT as well as the morphological structure of foamed samples, their density, tensile strength, and specific strength were determined. It was found that irradiation of PBAT induces growth in weight‐average molecular weight and decrease in mass flow rate, and as a consequence of this increase in viscosity of this polymer. It was also found that foaming of irradiated PBAT causes formation of homogeneous cellular structure or structure with a clear separation of large and small cells. Simultaneously, the irradiated and foamed PBAT shows smaller density than that of non‐irradiated and foamed PBAT. Moreover, electron radiation does not influence tensile strength of the foamed PBAT; however, it increases its specific strength, although only if the content of foaming agent is 1 wt%.     

Towards novel super‐elastic foams based on isoperene rubber: Preparation and characterization

A novel and conventional closed cell polyisoprene rubber (IR) foams were produced by a single step limited‐expansion and two step unlimited‐expansion foaming process, respectively. The effect of 3 to 12 part per hundred rubber (phr) of azodicarbonamide (ADC) foaming agent on their structure and properties of developed novel foams were studied. In developed novel foams, the density was strangely independent of ADC content; however, the cell sizes conversely related to ADC content and it decreased by 60% (555‐330 μm) and the internal cell pressure build up from 1 to 3.7 atm, which was related to pressure‐free foaming method. The both reasons of compressed gas trapped inside cells and constant density not only caused unique enhancement in novel foams mechanical properties as hardness and modulus but also improved their dynamic properties as hysteresis and elasticity. Results of conventional IR foams showed that, their foam density as well as dynamic and mechanical properties sharply decreased with increasing ADC content from 3 to 12 phr. For clear expression, in samples with 12 phr of ADC, novel developed foams have more foam density (180%), more hardness (240%), more modulus (290%), and smaller cell size (75%) than conventional foams. Finally, novel developed foams were super‐elastic material with no hysteresis and no plastic deformation while conventional foams had 40% hysteresis and 10% plastic deformation under the same compression conditions.     

Foaming of trans‐polyisoprene using N2 as the blowing agent

Foaming of trans‐1,4‐polyisoprene (TPI) polymer was carried out through a batch process using nitrogen (N₂) as the blowing agent. TPI vulcanizates having varying crosslink densities were prepared by varying crosslinking agent content and curing time. The vulcanizates were then saturated with N₂ inside a pressure vessel at a pressure of 14 MPa and varying temperatures for 5 hours before effecting the foaming by rapidly quenching the pressure. The effects of varying the crosslinking agent content, silica filler content, and precuring time of the vulcanizates and the effects of varying the gas saturation temperature of foaming on the cell characteristics and physical properties of the foam prepared were investigated. The cells of the TPI foams had a spherical, closed structure. The density, expansion ratio, cell size, cell density, and tensile properties of the foams varied with varying crosslink density of the TPI vulcanizates as well as the saturation temperature of foaming. The important effects of crosslink density and saturation temperature on the N₂ solubility in the TPI matrix and thus on the foam expansion were discussed. The silica filler was found to be acting as a cell nucleating agent and reinforcing filler for the TPI foams.     

Combining foam injection molding with batch foaming to improve cell density and control cellular orientation via multiple gas dissolution and desorption processes

In contrast to solid parts fabricated through conventional injection molding (CIM), foamed parts manufactured via foam injection molding (FIM) exhibit substantial variations in mechanical properties, which are attributed to differences in the cellular structure. In this study, parts with different cellular structures are fabricated via FIM, during which the gas dissolution and desorption processes are controlled by subjecting the gas‐laden melt to reciprocating compression and expansion operations. The results suggest that the cell density can be drastically improved by rapidly decreasing the pressure caused by the mold opening and that the cell orientation obviously occurs in the direction perpendicular to the mold‐opening direction. Moreover, the cell density and cellular orientation can be adjusted by utilizing appropriate mold opening and closing operations, leading to improvements in the resultant ultimate mechanical properties. In particular, the foamed samples fabricated with controlled mold opening‐closing operations exhibit excellent tensile strength and strain‐at‐break, indicating that samples containing a high density of cells oriented along the tensile test direction facilitate the formation of superductility and an increase in tensile strength. Hence, a method that combines FIM with batch foaming has been proposed for improving the cellular structure and controlling the cellular orientation.     

Synthesis and properties of methacrylate‐based networked polymers having ionic liquid structures

Methacrylate‐based networked polymers having ionic liquid structures were prepared by radical copolymerization of methyl methacrylate (MMA) with multifunctional crosslinkers: ethyleneglycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TMPTMA), or triethyleneglycol dimethacrylate (TEGDMA), in the presence of 1‐ethyl‐3‐methylethyl‐1‐imidazolium bis(trifluoromethane)sulfonyl imide (EMImTFSI). The fundamental physical properties of several film samples prepared by varying the monomer composition and ionic liquid content were investigated. The obtained materials became turbid with increasing crosslinker content and ionic liquid content. Their ionic conductivity increased with increasing ionic liquid content, while it was almost independent of the crosslinker content. EGDMA‐derived materials and TMPTMA‐derived materials showed higher ionic conductivity than TEGDMA‐derived materials. TMPTMA‐derived materials showed higher thermal stability than EGDMA or TEGDMA‐derived materials. EGDMA and TMPTMA‐derived materials were stiffer than the TEGDMA‐derived materials. The elastic modulus of the film samples increased but the film became more brittle with the increase of crosslinker content. Scanning electron microscopy and atomic force microscopy observation revealed that phase separation of networked polymers and ionic liquid occurred in the highly crosslinked samples, and the phase separation structures became larger in scale with the increase of crosslinking density. This phase separation was considered to have a strong effect on the mechanical properties of the film samples. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系

用高压CO2流体通过升温发泡法制备了一系列不同表观密度的热塑性聚氨酯(TPU)微孔发泡材料,探究了TPU发泡材料的表观密度与其力学性能的关系.微孔发泡材料的泡孔结构和表皮结构由扫描电子显微镜表征;不同表观密度材料的力学性能利用万能材料试验机和旋转流变仪表征.研究发现:TPU微孔发泡材料的表观密度主要是由材料皮层厚度占比和泡孔层密度决定的,皮层厚度占比越小和泡孔面积占有率越高,泡沫的表观密度越小;微孔发泡材料在线性应变区的压缩模量E与材料表观密度ρ的关系为:E∝ρ1.7,符合泡沫材料压缩模量与表观密度呈指数关系的基本结论;循环压缩实验中,随微孔发泡材料表观密度减小,损耗百分比增大,残余应变减小;流变实验中,微孔发泡材料的模量随表观密度变化没有明显的变化,阻尼因子tanδ随泡沫表观密度变化不呈单一的规律性.同时,阐明了微孔发泡材料的压缩模量E和损耗百分比随表观密度变化的机理.     

Constitutive modeling for characterizing the compressive behavior of PMMA open‐cell foams

A constitutive model for evaluating the compressive behavior of Poly(methyl‐methacrylate) (PMMA) open‐cell foams is herein proposed. Specifically, the study investigates the viscoelastic and viscoplastic behaviors of the PMMA open‐cell foams. The constitutive equation is expressed in terms of the following polymer and foam properties: elastic modulus, relative density, as well as the relaxation and densification constants. PMMA open‐cell foams are manufactured using a gas foaming/particulate leaching method and uniaxial compression tests are performed. The mechanical properties and compressive stress‐strain responses obtained from the experiments are compared with those predicted by the proposed constitutive model. The results suggest that the constitutive model is an apt one for assessing and evaluating the compressive behaviors of PMMA open‐cell foams. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 436–443, 2007     

Effects of Oil on Aqueous Foams: Electrical Conductivity of Foamed Emulsions

Three‐phase foams containing dispersed oils (also called foamed emulsion) are usually encountered in such areas as enhanced oil recovery, food foams, and in foams containing antifoams. The presence of oil causes these complex fluids to exhibit extraordinary properties in contrast to aqueous foams. We experimentally investigated, for the first time, the conductive properties of the foamed emulsions and found that the electrical conductivity increases monotonically with the volumetric liquid fraction, presenting a linear relationship. Combined with the analysis on the foaming capacity and microstructure of this complex fluid, the conductive mechanism is revealed. In these foamed emulsions, the whole conductive network is comprised of two levels of structural hierarchy, which displays a different mechanism from those of the conventional aqueous foams. The lamella of emulsions is taken as primary electrical channel, whereas the secondary electrical channel occurs in the lamella between two bubbles. This conductive behaviour is attributed to the microstructure properties of the foamed emulsions. We believe that such findings are potentially important for a better understanding of the fundamentals of these tri‐phase dispersion systems.     

Foaming behavior,cellular structure and physical properties of polybenzoxazine foams

In this paper, polymer foams based on a benzoxazine resin have been successfully prepared using azodicarbonamide (ADC) as a chemical blowing agent and have been characterized regarding their foaming behavior, cellular structure, and physical properties. The effect of the ADC on the curing process of the resin was analyzed using differential scanning calorimetry and blowing agent decomposition was followed by thermogravitmetric analysis (TGA). The characterization of the cellular structure of the foamed samples was done using scanning electron microscopy. The mechanical properties of the foams were determined using compression tests and the thermal conductivity was assessed using the transient plane source method. The results indicated that the curing process and gas release took place in a similar time interval. The foams showed an isotropic cellular structure with relative densities in the range 0.35–0.60, and showed compressive strengths and compressive moduli in the range of 10–70 MPa and 400–1100 MPa, respectively. Thermal conductivities were in the range of 0.06–0.12 W m^?1K^?1. The findings in this paper demonstrate the possibility of producing polybenzoxazine foams using a simple process in which curing and foaming take place simultaneously. In addition, the mechanical characterization of these materials indicates that they are suitable for structural applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Photocrosslinking and related properties of intumescent flame‐retardant LLDPE/EVA/IFR blends

The photoinitiated crosslinking of halogen‐free flame retarded linear low density polyethylene/poly(ethylene‐co‐vinyl acetate) blends (LLDPE/EVA) with the intumescent flame retardant (IFR) of phosphorous‐nitrogen compound (NP) in the presence of photoinitiator and crosslinker and their characterization of related properties have been investigated by gel determination, heat extension test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), Fourier transfer infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), mechanical properties measurements, limiting oxygen index (LOI), UL‐94, and water resistance test. The data from the gel content and heat extension rate (HER) show that the LLDPE/EVA/IFR blends filled with NP are readily crosslinked to a gel content of above 75% and the HER values reach about 50% by UV‐irradiation of 5 sec under suitable amount of photoinitiator and crosslinker. The data obtained from the CCT and LOI indicate that photocrosslinking can considerably decrease the heat release rates (HRR) by 10–15%, prolongate the combustion time, and increase two LOI values for the LLDPE/EVA/NP blends UV irradiated for 5 sec. The results from TGA and the dynamic FTIR spectra give the evidence that the photocrosslinked LLDPE/EVA/NP samples show slower thermal degradation rate and higher thermo‐oxidative degradation temperature than the uncrosslinked LLDPE/EVA/NP samples. The morphological structures of charred residues observed by SEM give the positive evidence that the compact charred layers formed from the photocrosslinked LLDPE/EVA/NP samples play an important role in the enhancement of flame retardant and thermal properties. The data from the mechanical tests and water‐resistant measurements show that photocrosslinking can considerably improve the mechanical and water‐resistant properties of LLDPE/EVA/NP samples. Copyright © 2011 John Wiley & Sons, Ltd.     

Glass transition temperature of polyurethane foams derived from lignin by controlled reaction rate

Sodium ligninosulfonate (LS)-based polyurethane (PU) foams were prepared using three kinds of ethylene glycols, diethylene glycol, triethylene glycol or polyethylene glycol. Two kinds of industrial NaLS, acid-based and alkaline-based NaLS, were mixed with various ratios, and foaming reactions were controlled. Mixing, cream, and rise time were used as an index of foaming reaction. Mixing time was defined as the time interval from adding isocyanate to detection of evolved heat under stirring, cream time as the time interval from termination of stirring to starting of foaming, and rise time as the time interval from starting to completion of foaming. The above reaction time increased with increasing amount of acid base NaLS content in polyols. Apparent density, compression strength and compression modulus of PU foams linearly increased with reaction time. Thermal decomposition temperature was measured by thermogravimetry and glass transition temperature by differential scanning calorimetry. Glass transition temperature can be controlled in a temperature range from 310 to 390 K by changing the mixing rate of two kinds of LS and molecular mass of ethylene glycols. It was found that mechanical and thermal properties of PU foams are controllable through the foaming reaction rate using two kinds of industrial lignin.     

Processing window for extrusion foaming of hydroxypropyl methylcellulose

Foamed materials are gaining an increased interest due to their good mechanical properties in relation to their low densities and an increased industrial demand can be expected. A few less attractive issues can however be associated with commodity foamed products. For instance the raw-material often originates from non-renewable, fossil-based, sources. Furthermore, degradation in nature is slow, therefor the disposed product is burned or end up in landfills. One possibility to reduce the impact on nature could be to produce foams from natural polymers such as starch or cellulose. In this study the possibility to produce foams from hydroxypropyl methylcellulose (HPMC) with water as blowing agent, by continuous extrusion, was investigated. A pre-study using a capillary viscometer, batch-extruder, was conducted to evaluate the foamability of HPMC. Due to promising results further experiments were conducted with a single-screw extruder. The goal was to find an adequate processing window for foaming. It was concluded that HPMC could successfully be foamed by continuous extrusion, although a careful tailoring of the processing parameters was required. Crucial parameters were here the temperature, pressure and residence time distribution in the extruder. Regions of the extruded foams were examined using optical and scanning electron microscopy and HPMC foams with a density in the range of that of fossil-based polymeric foams could be produced.     

Rheological properties and foam processability for blends of linear and crosslinked polyethylenes

The effect of blending crosslinked linear low‐density polyethylene (cLLDPE) on the rheological properties and foam processability of linear low‐density polyethylene was studied. A small addition of cLLDPE, which had a low density of crosslink points, enhanced strain‐hardening behavior in the elongational viscosity to a great degree, although it had little effect on the steady‐state shear viscosity. The enhanced strain hardening reduced heterogeneous deformation during foaming. As a result, a foam with a uniform cell size distribution was obtained. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2159–2167, 2001     

Dynamic mechanical behavior of acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The dynamic mechanical behavior of uncrosslinked (thermoplastic) and crosslinked (thermosetting) acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends was studied with reference to the effect of blend ratio, crosslinking systems, frequency, and temperature. Different crosslinked systems were prepared using peroxide (DCP), sulfur, and mixed crosslink systems. The glass‐transition behavior of the blends was affected by the blend ratio, the nature of crosslinking, and frequency. sThe damping properties of the blends increased with NBR content. The variations in tan δ_max were in accordance with morphology changes in the blends. From tan δ values of peroxide‐cured NBR, EVA, and blends the crosslinking effect of DCP was more predominant in NBR. The morphology of the uncrosslinked blends was examined using scanning electron and optical microscopes. Cocontinuous morphology was observed between 40 and 60 wt % of NBR. The particle size distribution curve of the blends was also drawn. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends, and it decreased with an increase in the NBR content. Various theoretical models were used to predict the modulus of the blends. From wide‐angle X‐ray scattering studies, the degree of crystallinity of the blends decreased with an increasing NBR content. The thermal behavior of the uncrosslinked and crosslinked systems of NBR/EVA blends was analyzed using a differential scanning calorimeter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1556–1570, 2002     

Effect of the crosslink density on the morphology and properties of reaction‐injection‐molding poly(urethane urea) elastomers

The effect of the crosslink density on the morphology and properties of reaction‐injection‐molding poly(urethane urea) (PUU) elastomers was investigated. Fourier transform infrared spectroscopy data showed that the linear and crosslinked PUU had entirely different hard‐domain sizes and hard‐segment ordering. A study of the morphology indicated that an increase in the crosslink density increased microphase mixing. Differential scanning calorimetry studies indicated that the hard‐segment initial glass‐transition temperature was independent of the crosslink density. The glass‐transition temperature of the soft segment was highest when the network was perfect. The tensile‐strength behavior showed that the mechanical properties of PUU reached a maximum when the network was perfect. The increase in the resilience of the crosslinked PUU elastomer was higher than that of the linear PUU elastomer with an increase in temperature, and the reduction of the hardness of the former was also higher than that of the latter. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1126–1131, 2004     

Radiation grafting of styrene onto polypropylene fibres by a 10 MeV electron beam

The radiation-induced graft copolymerization is an effective method for modification of the chemical and physical properties of polypropylene. Graft copolymerization of styrene onto polypropylene fibers has been studied by simultaneous irradiation method, using a 10 MeV electron beam. Samples were irradiated in an environment of nitrogen gas. The effects of radiation dose and styrene concentration in methanol, on the grafting yield were investigated. The effects of polyfunctional monomer, i.e., trimethylopropane trimethacrylate (TMPTMA) and acid (sulfuric acid) on the grafting yield were also examined. The grafted samples were then sulfonated and allowed to react with solution of a basic dye. The samples were characterized by mechanical properties and thermal stability. The mechanical properties of the radiated samples were reduced and the grafted samples had lower mechanical properties.     

The physical properties of pressure sensitive rubber composites

Nitrile butadiene rubber, NBR, structural foam of different apparent densities was obtained by using different concentrations of foaming agent, azodicarbonamide, ADC/K. The true stress-strain characteristics, in case of compression, of foamed samples after the application of cyclic stress-strain were measured. The effect of the cyclic stress-strain on strain energy density of ADC/K foaming agent-filled NBR rubber composites was studied. The mechanical parameters were found to depend on the foaming agent concentration and on the pre-cyclic fatigue number. Results also indicated that the strain energy decreased with filler concentration.The effects of the cyclic stress-strain on the conductivity of ADC/K foaming agent-filled NBR rubber composites were studied. The electrical properties were found to depend on the foaming agent concentration, the strain amplitude and the number of stress-strain cycles of pre-strain. This study was assisted by the current-voltage characteristics which were measured under the effect of different compression ratios: 0%, 5%, 10%, 15%, 20%, 25% and 30%. The free current carrier mobility and the equilibrium concentration of charge carriers in the conduction band were produced as functions of compressive strain. Results also indicate that there is a linear variation between pressure and conductivity for all samples, which means that these samples can be used as a pressure sensor.     

Compression set in gas-blown condensation-cured polysiloxane elastomers

Accelerated thermal ageing studies on foamed condensation cured polysiloxane materials have been performed in support of life assessment and material replacement programmes. Two different types of filled hydrogen-blown and condensation cured polysiloxane foams were tested; commercial (RTV S5370), and an in-house formulated polysiloxane elastomer (Silfoam). Compression set properties were investigated using Thermomechanical (TMA) studies and compared against two separate longer term ageing trials carried out in air and in dry inert gas atmospheres using compression jigs. Isotherms measured from these studies were assessed using time-temperature (T/t) superposition. Acceleration factors were determined and fitted to Arrhenius kinetics. For both materials, the thermo-mechanical results were found to closely follow the longer term accelerated ageing trials. Comparison of the accelerated ageing data in dry nitrogen atmospheres against field trial results showed the accelerated ageing trends over predict, however the comparison is difficult as the field data suffer from significant component to component variability. Of the long term ageing trials reported here, those carried out in air deviate more significantly from field trials data compared to those carried out in dry nitrogen atmospheres. For field return samples, there is evidence for residual post-curing reactions influencing mechanical performance, which would accelerate compression set. Multiple quantum-NMR studies suggest that compression set is not associated with significant changes in net crosslink density, but that some degree of network rearrangement has occurred due to viscoelastic relaxation as well as bond breaking and forming processes, with possible post-curing reactions at early times.