Characterization and electrical conductivity of poly(ethylene glycol)/polyacrylonitrile/multiwalled carbon nanotube composites

Poly(Lactic acid) (PLA)‐layered silicate nanocomposite films were prepared by solvent casting method. The films were irradiated with Co⁶⁰ radiation facility at dose of 30 kGy. The effect of γ irradiation on mechanical properties of the neat PLA and nanocomposites was evaluated by data obtained from tensile testing measurements. The tensile strength of the irradiated PLA films increased with addition of 1 wt % triallyl cyanurate indicating crosslink formation. Significant ductile behavior was observed in the PLA nanocomposites containing 4 pph of nanoclay. Incorporation of nanoclay particles in the PLA matrix stimulated crystal growth as it was studied by differential scanning calorimetry. The morphology of the nanocomposites characterized by transmission electron microscopy and X‐ray diffraction revealed an exfoliated morphology in the PLA nanocomposite films containing 4 pph of nanoclay. Only very small changes were observed in the chemical structure of the irradiated samples as it was investigated by Fourier transform infrared spectroscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and optical investigation of the effect of electron beam‐irradiation in poly‐allyl‐diglycol‐carbonate

The effect of electron beam irradiation on the structural and optical properties of Poly‐Allyl‐Diglycol‐Carbonate CR‐39 solid state nuclear track detector was investigated. Samples from CR‐39 detector were irradiated with electron beam with doses at levels between 10 and 140 kGy. The structural and optical modifications in the electron beam irradiated CR‐39 samples have been studied as a function of dose using different characterization techniques such as FTIR spectroscopy, Vickers hardness, refractive index and color difference measurements. The electron beam irradiation in the dose range 25–140 kGy led to a more compact structure of CR‐39 polymer, which resulted in an improvement in its hardness with an increase in the refractive index. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Gamma radiation induced property modification of poly(lactic acid)/hydroxyapatite bio‐nanocomposites

Poly(lactic acid)/hydroxyapatite (PLA/HAP) nanocomposite films with various compositions, 2 ? 70 parts HAP per 100 of the PLA polymer (pph), were made via the solution casting method. Transmission electron microscopy images of the PLA/HAP films exhibited spherical particles in the size range from nearly 10 nm to 100 nm dispersed within the polymeric matrix. Fourier transform infrared spectra of the nanocomposites revealed an interaction between PLA and HAP nanoparticles by carbonyl group peak shift. Incorporation of HAP nanoparticles in the PLA matrix stimulated crystal growth verified by differential scanning calorimetry. The films irradiated with γ‐rays at a dose of 30 kGy also showed an increase in crystallinity. The X‐ray diffraction patterns of the irradiated PLA exhibited two new peaks at around 16° and 19°, assigned to the α crystalline phase of PLA; these were absent in the unirradiated nanocomposites. Significant ductile behavior was observed in both irradiated and unirradiated PLA nanocomposites containing 2 and 10 pph of HAP. However, the irradiated nanocomposites had higher tensile strength. © 2013 Society of Chemical Industry     

A new approach for the preparation of chitosan from γ‐irradiation of prawn shell: effects of radiation on the characteristics of chitosan

Chitosan is a biodegradable polymer composed of randomly distributed β‐(1,4)‐linked D ‐glucosamine (deacetylated unit) and N‐acetyl‐D ‐glucosamine (acetylated unit). It is produced commercially by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans (such as crabs and shrimps) and the cell walls of fungi. In the work reported, we developed a facile technique for the preparation of chitosan by irradiating prawn shell at various intensities from 2 to 50 kGy. It was observed that γ‐irradiation of prawn shell increased the degree of deacetylation (DD) of chitin at a relatively low alkali concentration during the deacetylation process. Among the various irradiation doses applied to prawn shell, a dose of 50 kGy and 4 h heating in 50% NaOH solution yielded 84.56% DD while the chitosan obtained from non‐irradiated prawn shell with the same reaction conditions had only 74.70% DD. In order to evaluate the effect of γ‐irradiation on the various physicochemical, thermomechanical and morphological properties, the chitosan samples were again irradiated (2–100 kGy) with γ‐radiation. Molecular weight, DD, thermal properties with differential scanning calorimetry and thermogravimetric analysis, particle morphology by scanning electron microscopy, water binding capacity (WBC), fat binding capacity (FBC) and antimicrobial activity were determined and the effects of various γ‐radiation doses were assessed. The DD, WBC, FBC and antimicrobial activity of the chitosan were found to improve on irradiation. It was obvious that irradiation caused a decrease of molecular weight from 187 128 to 64 972 g mol^?1 after applying a radiation dose of 100 kGy which occurred due to the chain scission of chitosan molecules at glycosidic linkages. The decrease of molecular weight increased the water solubility of the chitosan, the extent of which was explored for biomedical applications. Copyright © 2012 Society of Chemical Industry     

Degradation of poly(L‐lactide) films under ultraviolet‐induced photografting and sterilization conditions

The degradation of polymers under ultraviolet (UV) irradiation has been a great concern for biomaterial and agricultural applications. The major objective of this research was to study the effect of UV irradiation on the representative bulk and surface properties of poly (L ‐lactide) (PLA) films. Two UV sources with different spectral outputs and intensities were chosen so that one of them could be used for surface modification and the other could be used for UV sterilization of the PLA films. The results established that the molecular weight of PLA decreased significantly during irradiation from the photografting lamp under atmospheric conditions. Irradiation through a Pyrex container was shown to minimize polymer degradation during UV exposure from the photografting lamp. The PLA films UV‐irradiated under the sterilization lamp for 12 h revealed a similar reduction in the molecular weight and no change in the surface hydrophilicity. However, significantly less photodegradation was observed under the sterilization lamp when the samples were held in a Pyrex container. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid) copolymer by electron beam radiation

This article investigates the effects of electron beam (EB) radiation on poly(D ,L ‐lactic acid)‐b‐poly (ethylene glycol) copolymer (PLA‐b‐PEG‐b‐PLA). The copolymer films were EB irradiated at doses from 0 to 100 kGy. The degradation of these films was studied by measuring the changes in their molecular weight, mechanical and thermal properties. The dominant effect of EB radiation on PLA‐b‐PEG‐b‐PLA is chain‐scission. With increasing irradiation dose, recombination reactions or partial crosslinking may occur in addition to chain scission. The degree of chain scission G_s and crosslinking G_x of sample are calculated to be 0.213 and 0.043, respectively. A linear relationship is also established between the decreases in molecular weight with increasing irradiation dose. Elongation at break of the irradiated sample decreases significantly, whereas its tensile strength decreases slightly. The glass transition temperature (T_g) is basically invariant as a function of irradiation dose. Thermogravimetric analysis shows that its thermal stability decreases with increasing dose. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparative investigations of radiation‐grafted proton‐exchange membranes prepared using single‐step and conventional two‐step radiation‐induced grafting methods

Proton‐exchange membranes containing poly(styrene sulfonic acid) grafts hosted in poly(vinylidene fluoride) (PVDF) films were prepared using two radiation‐induced grafting methods: a single‐step grafting method (SSGM) involving grafting of sodium styrene sulfonate onto electron beam (EB)‐irradiated PVDF films and a conventional two‐step grafting method (CTSGM) in which styrene monomer is grafted onto EB‐irradiated PVDF films and subsequently sulfonated. Differential scanning calorimetry, universal mechanical testing and scanning transmission electron microscopy were used to evaluate the thermal, mechanical and structural changes developed in the membranes during the preparation procedures. Physicochemical properties such as water uptake, hydration number and ionic conductivity were studied as functions of ion‐exchange capacity and the results obtained were correlated with the structural changes accompanying each preparation method. Membranes obtained using the SSGM were found to have superior properties compared to their counterparts prepared using the CTSGM suggesting the former method is more effective than the latter for imparting desired functionality and stability properties to the membranes. Copyright © 2010 Society of Chemical Industry     

Mechanical and barrier properties of carbon nanotube reinforced PCL‐based composite films: Effect of gamma radiation

Carbon nanotube (CNT) reinforced (0.05–0.5% by wt) polycaprolactone (PCL)‐based composites were prepared by compression molding. Addition of 0.2% CNT caused a 131% improvement of tensile strength (TS) of PCL films. The tensile modulus (TM) and elongation at break (Eb) of PCL were also significantly improved with the addition of CNT. The water vapor permeability of PCL was 1.51 g·mm/m²·day but 0.2% CNT containing PCL films showed 1.08 g·mm/m²·day. Similarly, the oxygen transmission rate (OTR) of PCL films was found to decrease with the addition of CNT. But, carbon dioxide transmission rate (CO₂TR) of PCL film was improved due to incorporation of CNT. Effect of gamma radiation on PCL films and CNT reinforced PCL‐based composites were also studied. The TS of the irradiated (10 kGy) PCL films gained to 75% higher than control sample. The TS of the 0.2% CNT reinforced composite film was reached to 41 MPa at 15 kGy dose. The barrier properties of non‐irradiated and irradiated (10 kGy) PCL films and composites (0.2% CNT reinforced) were also measured. Both PCL films and composites showed lower values of WVP upon irradiation and indicated better water vapor barrier. The OTR and CO₂TR of the irradiated (10 kGy) PCL films and composites were decreased compared to their counterparts. Surface and interface morphologies of the composites were studied by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the electron beam irradiation on the properties of epoxidized natural rubber (ENR 50) compatibilized linear low‐density polyethylene/soya powder blends

Linear low‐density polyethylene/soya powder blends were prepared by using an internal mixer at 150°C. The soya powder content ranged from 5 to 40 wt %. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) was added as a compatibilizer. The blends were irradiated by electron beam (EB) at a constant dose of 30 kGy. The changes in gel fraction, tensile properties, morphological and thermal properties of the samples were investigated. The gel content increased after EB irradiation. However, the increment of gel content was hindered by increasing soya powder content. The tensile strength and Young's modulus of the blends were increased by EB whereas the elongation at break decreased. The tensile fracture surface also support the reduction of elongation at break by EB irradiation. Further analysis on the irradiated blends using Fourier transform infrared spectra indicated an increase of oxygenated product after undergoing EB irradiation. The differential scanning calorimetry result indicated that the melting temperature of the blends decreased after EB irradiation whereas the crystallinity increased. EB irradiation also enhanced the thermal stability of the blends as indicated by thermogravimetric analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Comprehensive study of polymer fiber surface modifications Part 1: high‐fluence UV‐excimer‐laser‐induced structures

Recently, there has been great interest in physico‐chemical surface treatments for modifying polymer surfaces. Ultraviolet (UV)‐excimer‐laser irradiation of polymers is of particular interest. In this study, polyamide was irradiated by a 193 nm excimer laser with a fluence above its ablation threshold (high‐fluence). Morphological changes of the resulting samples were characterized by scanning electron microscopy (SEM) and tapping mode atomic force microscopy (TM‐AFM). Chemical modifications by laser treatment were studied by X‐ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and chemical force microscopy (CFM). Topographical results indicated that ‘ripple‐like’ structures of micrometer size were formed after laser irradiation. XPS and Tof‐SIMS results showed that bond scission occurred on the polymer surface under the action of high‐fluence. Changes in surface chemical properties of the laser‐irradiated polyamide were supported by CFM experiments. Copyright © 2004 Society of Chemical Industry     

Effects of an oxygen‐ion beam (O+7, 100 MeV) and γ irradiation on polypyrrole films

Nanostructured polypyrrole films doped with para‐toluene sulfonic acid were prepared by an electrochemical process, and a comparative study of the effects of swift heavy ions and γ‐ray irradiation on the structural and optical properties of the polypyrrole was carried out. Oxygen‐ion (energy = 100 MeV, charge state = +7) fluence varied from 1 × 10¹⁰ to 3 × 10¹² ions/cm², and the γ dose varied from 6.8 to 67 Gy. The polymer films were characterized by X‐ray diffraction, ultraviolet–visible spectroscopy, and scanning electron microscopy. The X‐ray diffraction pattern showed that after irradiation, the crystallinity improved with increasing fluence because of an increase in the crystalline regions dispersed in an amorphous phase. The ultraviolet–visible spectra showed a shift in the absorbance edge toward higher wavelengths, which indicated a significant decrease in the band gap of the polypyrrole film after irradiation. The scanning electron microscopy study showed a systematic change in the surface of the polymer. A similar pattern was observed with the γ irradiation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Long‐range‐ordered,hexagonally packed nanoporous membranes from degradable‐block‐containing diblock copolymer film templates

Polystyrene (PS)‐b‐polylactide (PLA) diblock copolymers with different molecular weights and fractions were synthesized through a combination of living anionic polymerization and controlled ring‐opening polymerization. Then, the PS–PLA films were guided to phase‐separate by self‐assembly into different morphologies through casting solvent selection, solvent evaporation, and thermal and solvent‐field regulation. Finally, perpendicularly oriented PS–PLA films were used as precursors for PS membranes with an ordered periodic nanoporous structure; this was achieved by the selective etching of the segregated PLA domains dispersed in a continuous matrix of PS. Testing techniques, including IR, ¹H‐NMR, gel permeation chromatography, scanning electron microscopy (SEM), and atomic force microscopy (AFM), were used to determine the chemical structure of the PS–PLA copolymer and its film morphology. AFM images of the self‐assembled PS‐PLA films indicate that vertical tapers of the PLA domains were generated among PS continuum when either toluene or tetrahydrofuran was used as the annealing solvent. The SEM images certified that the chemical etching of the PLA component from the self‐assembled PS–PLA films led to a long‐range‐ordered array of hexagonally packed nanoporous membranes with a diameter about 500 nm and a center‐to‐center distance of 1700 nm. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39638.     

Influence of γ‐irradiation on poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) was γ‐irradiated (5–20 kGy) by a ¹³⁷Cs source at room temperature in air. The changes in the molecular structure attributed to γ‐irradiation were studied by mechanical testing (flexure and hardness), size‐exclusion chromatography, differential scanning calorimetry, thermal gravimetric analysis, and both Fourier transform infrared and solution ¹³C‐NMR spectroscopy. Scanning electron microscopy was used to investigate the influence of the dose of γ rays on the fracture behavior of PMMA. The experimental results confirm that the PMMA degradation process involves chain scission. It was also observed that PMMA presents a brittle fracture mechanism and modifications in the color, becoming yellowish. The mechanical property curves show a similar pattern when the γ‐radiation dose increases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 886–895, 2002     

The effect of gamma and electron beam irradiation on the thermal and mechanical properties of injection‐moulded high crystallinity poly(propylene)

In the present study, the effect of gamma and electron beam (EB) irradiation on the thermal and mechanical properties of high crystalline polypropylene (HPP) was studied. To study the structural modifications of HPP polymer which could occur following these treatments at different doses (20, 40, 60, 80, 100, and 120 kGy) were applied to all samples. Nonirradiated HPP were used as control samples, differential scanning calorimetry analysis, thermogravimetric analysis, and Mechanical tests were carried out to evaluate the effect of both irradiation treatments (EB and gamma irradiation) on HPP samples. Irradiated samples of HPP decreases melting temperature (T_m) of matrix in EB more than in gamma rays up to 5°C. The changes of mechanical properties exhibit different radiation stability towards ⁶⁰Co‐gamma radiation and EB radiation. This difference reflects much higher penetration of the gamma radiation through the polymeric material as a function of sample thickness. The degradation on polymer properties caused by gamma irradiation was more than that caused by EB irradiation. Next, we compared the effects of gamma and EB irradiation to determine which of these two processes better maintained the integrity of the irradiated product. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers.     

Surface analysis and printability studies on electron beam-irradiated thermoplastic elastomeric films from LDPE and EVA blends

The electron beam-initiated surface modification of films prepared from various blends of low-density polyethylene (LDPE), ethylene vinyl acetate (EVA), and ditrimethylol propane tetraacrylate (DTMPTA) was carried out over a range of radiation doses (20-500 kGy) and concentrations of DTMPTA. The films were characterized by Fourier transform infrared-attenuated total reflectance (FT-ATR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), contact angle measurements, and peel adhesion. The printability of the films was also measured. FT-ATR and XPS revealed that the surface polarity of the films made from a 50 : 50 blend of LDPE and EVA increased up to a radiation dose of 100 kGy, compared with the unirradiated sample. The polarity decreased after 100 kGy radiation. Surface pitting and roughness were observed in the SEM photomicrographs of the same films, irradiated at higher radiation doses. Higher values of the surface energy were obtained at 100 kGy for the samples without DTMPTA and for the samples containing 3 wt% DTMPTA. Excellent printability was observed for all the films irradiated above an irradiation dose of 20 kGy. The data on the printability and peel adhesion of the irradiated films could be explained by surface energy, XPS, and SEM results.     

Study on mechanical properties of perlite‐filled gamma‐irradiated polypropylene

This study covers the preparation and characterization of perlite‐filled polypropylene (PP). The compositions of 15, 30, and 50 % by weight perlite–PP composites were prepared by melt‐mixing. The PP used in this study was either applied in the virgin form or γ‐irradiated in air at the doses of 10, 25, 50, and 100 kGy to determine the effect of oxidative degradation in composite properties. Furthermore, the active sites containing oxygen produced by γ‐irradiation in PP may provide a possible enhancement by the interfacial interaction between perlite and PP. An initial sharp drop in torque readings during the melt‐mixing of perlite–PP composite preparation indicated an extensive chain scission and degradation by γ‐irradiation. The thermal properties of the composites were characterized by DSC. The ultimate tensile strength and elongation and also impact strength decreased in all composites with γ‐irradiation. Yet, these changes appeared not to be faster than was the change in unfilled PP upon irradiation. Scanning electron microscopy revealed an interfacial adhesion between perlite and irradiated PP while virgin PP did not show any evidence of adhesion. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2670–2678, 2001     

Effect of ambient‐temperature and high‐temperature electron‐beam radiation on the structural,thermal, mechanical,and dynamic mechanical properties of injection‐molded polyamide‐6,6

Electron‐beam irradiation of injection‐molded specimens of polyiminohexamethyleneiminoadipoyl (better known as polyamide‐6,6) was carried out in air at ambient temperature (303 K) and a high temperature (393 K). Most of the irradiated specimens were tensile dumbbells, although a few were cylinders for compressive stress relaxation testing. A few representative samples were dipped in triallyl cyanurate (TAC) solution before ambient‐temperature irradiation. The gel content of the specimens increased with radiation dose and the temperature of irradiation. Moreover, the TAC‐treated specimens showed an increase in gel content over the neat specimens irradiated at the same dose levels. Wide‐angle X‐ray scattering and differential scanning calorimetry studies revealed that the crystallinity decreased with increasing radiation dose. Irradiation at the high temperature and treatment with TAC further decreased the crystallinity compared to irradiation at ambient temperature. As determined from compressive stress relaxation and mechanical and dynamic mechanical properties, the optimized radiation dose for ambient‐temperature radiation was 200 kGy. The gels had a stiffening effect, and the rate of relaxation decreased significantly. The water‐uptake characteristics of the tensile specimens were investigated; this revealed a decrease in the water absorption tendency with increasing gel content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1633–1644, 2006     

Thermal analysis of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) irradiated under vacuum

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was irradiated by ⁶⁰Co γ‐rays (doses of 50, 100 and 200 kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one‐step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight‐loss step change. The onset degradation temperature (T_o) and the temperature of maximum weight‐loss rate (T_p) of control and irradiated PHBV were in line with the heating rate (°C min^?1). T_o and T_P of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that ⁶⁰Co γ‐radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T_m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness. Copyright © 2004 Society of Chemical Industry     

Enhanced Interfacial Adhesion of Bioflour‐Filled Poly(propylene) Biocomposites by Electron‐Beam Irradiation

Summary: The effect of electron‐beam (EB) irradiation on interfacial adhesion in bioflour (rice‐husk flour, RHF)‐filled poly(propylene) (PP) biocomposites in which either only the RHF had been EB irradiated or the whole biocomposite had been EB irradiated was examined at different EB‐irradiation doses. The tensile strengths of PP–RHF biocomposites with EB‐irradiated RHF and EB‐irradiated PP and PP–RHF biocomposites were slightly higher than those of the nonirradiated samples. The improved interfacial adhesion of PP–RHF biocomposites with EB radiated RHF and the EB‐irradiated PP–RHF biocomposites compared with the nonirradiated samples was confirmed by the morphological characteristics. In addition, the thermal stability of EB‐treated biocomposites was slightly higher than those of nonirradiated samples at the irradiation doses of 2 and 5 Mrad. However, at the high irradiation dose (30 Mrad), the tensile strengths of the biocomposites were slightly decreased by main‐chain scission (degradation) of PP and RHF. Attenuated total reflectance FT‐IR and X‐ray‐photoelectron‐spectroscopy findings confirmed this result by showing that that EB irradiation changed the functional groups of RHF, PP, and the biocomposites and improved the surface characteristics of the biocomposites. The thermal characteristics of the EB‐irradiated PP and biocomposites were investigated using differential scanning calorimetry. From the results, we concluded that use of low‐dose EB radiation increases the interfacial adhesion between matrix polymer and biofiller.

     

Effect of γ‐irradiation on glycolysis of PET waste and preparation of ecofriendly coatings using bio‐based and recycled materials

Recycling of postconsumer poly (ethylene terephthalate) (PET) is a worldwide concern due to large increasing volume of these materials produced by society. In the present study, we report the effect of gamma irradiation on degradation of PET and its subsequent effect on glycolysis by using excess ethylene glycol (EG). The results as analyzed by molecular weight determination showed that extent of depolymerization of PET were dose dependent. The doses of 30, 50, 70, and 100 kGy resulted in decrease in the molecular weight by about 15%, 25%, 30%, and 40% respectively. The irradiated waste PET samples were further subjected to glycolysis using EG by conventional and microwave method which resulted in increased yield of monomeric product, bis (2‐hydroxyethylterephthalate) (BHET). The recycled material, BHET, was then used in combination with bio‐based monomers to prepare a new eco‐friendly polyester polyol which was analyzed for hydroxyl, saponification, acid value and further characterized by FTIR, ¹HNMR, and GPC techniques for molecular weight determination. Polyurethane coatings were prepared from the polyester polyol and various commercial polyisocyanate curing agents. The coated films were evaluated for their performance properties. Thermal properties of coatings were investigated by differential scanning calorimetry and thermogravimetric analysis. POLYM. ENG. SCI., 55:2653–2660, 2015. © 2015 Society of Plastics Engineers