Amylose graft polymers made by 60Co gamma-irradiation

Model products were needed to elucidate structure–property relationships in a starch graft polymer research program. Simultaneous irradiation of amylose and acrylamide in oxygen-free, dilute aqueous solutions gave graft polymers with maximum add-on of about 16%. The graft polymers were separated from homopolymer and subfractionated by incremental additions of nonsolvent (methyl or ethyl alcohol) to irradiated aqueous reaction media. The graft polymers were fairly homogeneous in graft content. Effects were determined of ratios of monomer to substrate, dose rate, and total dose on yield, graft content, intrinsic viscosity, and homopolymer characteristics. Under some conditions, crosslinks probably formed between graft side chains. Large differences in solution properties of a synthetic mixture of separately irradiated amylose and acrylamide and an irradiated solution of amylose and acrylamide indicated that grafting had occurred. Further evidence for true grafting was based on the action of a selective precipitant, n-butyl alcohol, on graft polymer solutions.     

Relation between dielectric property and desulphurization of coal by microwaves

Dielectric properties of various coals and aqueous NaOH solutions were determined to study thermochemical coal desulphurization by microwave irradiation. Aqueous NaOH solutions were used as media for irradiation. The coal samples were placed in a rectangular cavity and irradiated with 2450 MHz microwaves, resulting in 70–80% desulphurization efficiency.     

Long‐chain branching of polypropylene by electron‐beam irradiation in the molten state

The electron‐beam irradiation of polymers generates modification effects in the macromolecular structure and material properties. Therefore, irradiation processing is mostly realized in the polymer solid state. In this way, the modification of linear polypropylene may result in long‐chain branching of polypropylene macromolecules. The objective of this article is to investigate the effect of a polymer in the molten state during electron‐beam irradiation on the macromolecular structure and material properties of polypropylene. For this procedure, a special irradiation vessel (BG3) has been developed in which a rapid transfer of polymer films from the solid state to the molten state and a defined temperature during electron‐beam irradiation are realizable. The irradiated samples have been analyzed by high‐temperature size exclusion chromatography coupled with a multi‐angle laser light scattering detector and differential scanning calorimetry (DSC) measurements. With an increasing irradiation dose, a high reduction of the molar mass and an increasing amount of long‐chain branching are found. Compared with irradiation in the solid state, the modification in the molten state leads to a higher degree of branching. The rheological experiments in elongation flow clearly exhibit the existence of long‐chain branching. Furthermore, DSC measurements show that the glass‐transition temperature and peak temperatures of melting and crystallization decrease. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 260–265, 2006     

Effect of gamma‐irradiation on the electret properties of poly(L‐lactide)

Electret stability of poly(L ‐lactide) (PLA) films, gamma‐irradiated up to 100 kGy has been investigated by measuring the surface potential during the storage period. PLA samples—40‐μm thick films—were prepared by the casting method and then irradiated in a ⁶⁰Co radiation facility at a dose rate of 0.25 kGy/h. The structural changes during the irradiation were estimated by viscometric, differential scanning calorimetry and scanning electron microscope measurements. Random chain scission and appearance of end radicals are the most probable results of the irradiation process. After irradiation, the samples were charged in a corona discharge system and surface potential was measured by the method of the vibrating electrode with compensation. The values of the surface potential of the irradiated samples were higher in comparison with the non‐irradiated samples. This effect could be related to the degradation of the macromolecules and changes in the crystal state of PLA during the irradiation. Both of the mentioned factors lead to structural defects that increase the number of discrete trapping levels. The effect of low pressure on the surface potential drop was also investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structural, optical, thermo-mechanical and transport properties of ion irradiated polymer membranes

Summary The modifications in PET induced by swift heavy ion irradiation are analyzed. PET membrane of 15 μm was irradiated by Cl⁹⁺ ions of 100 MeV at TIFR Mumbai. The changes due to exposure to high-energy ions were investigated by Fourier Transform Infrared (FTIR) and Ultraviolet/ Visible absorption (UV/VIS) spectroscopies, X-Ray diffraction technique, dynamic mechanical analysis and by the gas permeation. A significant loss of crystallinity is observed by the XRD data. Particle size or grain size calculated using Scherrer formula indicates measurable change in particle size of irradiated samples. The polymer chain scissions and structure degradations are expected to occur for irradiated samples. Optical properties of the films were changed due to irradiation that could be clearly seen in the absorption and FTIR spectra. Gas permeation through these membranes before and after irradiation using hydrogen and carbon dioxide gases shows that permeability for both gases increased after irradiation but permeability for hydrogen is higher than carbon dioxide due to its small molecular size.     

Degradation on polyacrylamides. Part I. Linear polyacrylamide

The stability of linear polyacrylamides (PAAM) under thermal and irradiation conditions were investigated. The study showed that PAAm is stable under fluorescent lights and does not release any detectable acrylamide (AAM) in hot aqueous solution at 95 °C. Hydrolysis of side-chain amide groups to acid groups was observed during the thermal aqueous degradation. Under UV irradiation, small levels of released AAm were observed; however they are generally below 50 parts per million repeat monomer units in the polymer. A drop in viscosity is also observed. This indicates that the acrylamide released is due to chain scission, not a unzipping of the polymer chain. Methods of purifying a linear PAAM are also discussed.     

Reactivity of poly(vinyl chloride) containing N-methyl-N-carboxymethyl dithiocarbamate toward metal ions in heterogeneous system and effect of γ-irradiation on the reactivity

The reaction of poly(vinyl chloride) containing N-methyl-N-carboxymethyl dithiocarbamate (PSDC) with metal ions in a heterogeneous system and the effects of γ-irradiation on the reactivity were studied. Slurried PSDC has an affinity for a number of metal ions in aqueous solutions. On the basis of analyses for nitrogen and sulfur and on infrared spectra, a possible chelating structure for PSDC was deduced. The gaseous products evolved during the gamma radiolysis of PSDC under vacuum were measured. Although the dithiocarbamate group bonded to the main chain gave some protection against the dehydrochlorination of poly(vinyl chloride) component, a small amount of the carboxymethyl group was decomposed. It was found that with γ-irradiation doses up to 30 Mrad, only about 1 mole-% out of 17.6 mole-% of N-methyl-N-carboxymethyl dithiocarbamate in the polymer was decomposed. It was shown that the reactivity of the irradiated PSDC in water toward metal ions was almost the same as that before irradiation.     

Photo- and radiation-induced degradation of synthetic polymers: Polymer structure and stability

The effect of polymer density, processing conditions (quenching of annealing), degree of crystallinity, size of crystallite and mobility of polymer chains on the photo-and radiation-induced degradation and the polymer stability have been studied by UV, FTIR spectroscopic, viscosity and mechanical property measurements. Four kinds of annealed or quenched polyethylene (PE) films varying densities were used to the studies. Polystyrene (PSt) films were used to investigate the effect of chain mobility on polymer degradation. The following results were obtained.

• 1. In linear low density (LLD) PE, greater amounts of crosslinking (irradiated in vacuum) and chain scission (irradiated in air) were noticed than in mediun density (MD) PE and high density (HD) PE samples.
• 2. Polyene formation is favored in the case of the irradiation in vacuum for LLDPE.
• 3. Polymer stability evaluated by mechanical property such as elongation at break (%) is superior in LLDPE to MDPE and HDPE for annealed and quenched samples.
• 4. Segmental motion of polymer chain also affects the polymer stability

     

Identification of the active species in the suppression of postirradiation conductivity in polystyrene films for dosimeter application

The resistivity of insulating materials for electrostatic, ion chamber dosimeters must be very high and must remain so after exposure to ionizing radiation. Low dielectric polarization and good fabrication characteristics make hydrocarbon polymers most suitable, but both the conductivity during irradiation and its decay afterward vary greatly even for the same type of polymer, probably depending on impurities. Amorphous, styrene-based polymers and copolymers polymerized in aqueous emulsion and initiated with K₂S₂O₈ were found to have much more rapid decay of conductivity after irradiation than pure polystyrene or other nonpolar polymers. The synthesis method incorporates sulfate groups on the polymer chain ends and leaves emulsifier residues distributed throughout the polymer as was demonstrated by various analytical procedures. To identify the trapping species a synthesis program was carried out varying selected ingredients in the polymerization recipe. It was found that the postirradiation conductivity was not dependent on the chemical nature of the emulsifier residues. On the other hand, the decay time of conductivity after irradiation did depend on the polar groups incorporated in the polymer chain. It was concluded that effective charge carrier traps were constituted of a polar second phase highly dispersed through the polymer by association with polar groups incorporated on the polymer chain.     

Effect of large dosage irradiation in air on polyethylene

The large dosage irradiation effect on polyethylene in air was examined by the method of double irradition. Polyethylene was first irradiated with γ-rays to a dosage of a few hundred Mrad in air at 298°K. The formed radicals were destroyed, and the polymer, changed chemically and morphologically, was irradiated again in vacuo at 77°K with a dose of 12.7 Mrad. The thermal decay of radicals produced in polyethylene by the second irrdiation was investigated. The results were compared with the sample not exposed to the first irradiation. The results were also compared with previous data of polyethylene irradiated in vacuo to a great extent and then treated in the same manner as that in the present experiment. The results show that scission of the polymer chain by oxidation makes the radical decay faster. Simultaneously, crosslinks formed in polyethylene irradiated in air to a great extent slow down the radical decay. Almost the same number of double bonds was formed in polyethylene irradiated in air as in polyethylene irradiated in vacuo. These double bonds react with alkyl radicals to form allyl radicals.     

Characterization of electron beam irradiated polypropylene: Influence of irradiation temperature on molecular and rheological properties

The aim of the investigations was to analyze the influence of the temperature during the irradiation process of polypropylene on the molar mass, the formation of long chain branching and the final branching topology. A linear isotactic polypropylene homopolymer was modified by electron beam irradiation at different temperatures, with two irradiation doses to insert long chain branching. The samples were analyzed by size exclusion chromatography coupled with a multiangle laser light scattering detector, by differential scanning calorimetry, and by shear and elongational rheology. The shear and elongational flow behavior is discussed in terms of the influence of molecular parameters and used to analyze the topology of the irradiated samples. With increasing temperature, a slight reduction of the molar mass, an increase of long chain branching and an increase of crystallization temperature were found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2770–2780, 2006     

The influence of low- and high-linear energy transfers on some physical properties of poly(methyl-methacrylate) samples

Clear poly(methyl-methacrylate)—PMMA—dosimeter is widely used in food irradiations. Positron annihilation lifetime spectroscopy (PALS) is one of the unique tools used for studying free-volumes and open-volume type defects in solid media. The Vicker's microhardness measurements offer a simple and nondestructive tool for investigating the mechanical behavior of polymer materials. PALS as well as microhardness measurements were carried out for PMMA samples, irradiated with low- and high-linear energy transfers (LET). The low-LET irradiations were provided at lethal doses of gamma radiations for vegetative bacteria. Such irradiations showed a chain scission in the PMMA samples. High-LET irradiations showed behavior different from the low-LET ones. The observed behavior depends on the alpha particle fluence. The microhardness testing was carried out for virgin and irradiated PMMA samples at high-LET. A negative correlation was found between PALS measurements and microhardness results. The optical characteristics and structural studies for the virgin and irradiated PMMA samples were in agreement with the PALS and microhardness measurements. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydrogel of Radiation‐Induced Cross‐Linked Hydroxypropylcellulose

Hydroxypropylcellulose (HPC) hydrogel being a material of natural origin, combines the properties of a polymer, which make up the network, with biodegradability. In this report the effects of high energy radiation on the ether of cellulose‐HPC are presented. The polymer irradiated in its solid state or in dilute aqueous solution underwent mainly degradation, induced by the cleavage of glycosidic bonds in its main chain. Irradiation of HPC in aqueous solutions at moderate concentrations resulted in the formation of hydrogels. Chemical cross‐links bond the chains of polymer, turning it to an insoluble macroscopic gel. We have found that in addition to concentration, dosage and dose rate can affect the results of irradiation. Electron beam irradiation gave higher gel fraction, up to 90%, than gamma irradiation, which has a maximum gel fraction of 65%. Swelling of the cross‐linked hydrogels was related to the density of cross‐links and was the highest at low irradiation doses. HPC hydrogels displayed thermally reversible character in their swelling. The volume of gel underwent continuous deswelling with an increase of the solution temperature, with the deswelling rate increasing rapidly over 40°C. At elevated temperatures the hydrogel collapsed, lost its transparency and changed color to translucent white. This transition was fully reversible when the gel was placed in the medium of low temperature. The hydrogel demonstrated superior mechanical properties. Despite of the stable three‐dimensional cross‐linked network, the gels underwent biodegradation under controlled conditions when enzyme was used.     

Photodegradation of polymer materials containing flame-cut agents

Photodegradation of incombustible materials [polystyrene (PSt) and polypropyrene (PP) containing 2 wt% of decabromodiphenyl oxide (DBDE) or tetrabromobisphenol-A (TBA) as a flame-cut agent] were studied using Okazaki Large Spectrograph (OLS). Samples were irradiated in air at 23°C with monochromatic light of wavelengths at 260, 280, 300, 320, 340, and 360 nm, UV-visible spectra and FTIR spectra were measured to identify the chemical structural changes of the polymers. Number of chain scissions, which is a measure of the polymer degradation, was estimated from the results of GPC measurements. It was found that the photostability of PP and PSt was reduced by the addition of DBDE or TBA. Photodegradation of these polymers took place by the irradiation of the light of wavelengths lower than 320 and 360 nm for the polymers containing TBA and DBDE, respectively. The most effective irradiation wavelengths for main chain scission are found to be 260–280 and 300 nm for PP or PSt–TBA samples and PP or PSt–DBDE samples, respectively. © 1993 John Wiley & Sons, Inc.     

Effects of gamma irradiation,gas environments,and postirradiation aging on ultrahigh molecular weight polyethylene

The effects of low-dose (1 to 5 Mrad) gamma irradiation in different gas environments on thermal and tensile properties, and mass of melt-crystallized ultrahigh molecular weight polyethylene (UHMW-PE) have been investigated. The gamma irradiation was conducted under four different environments, air, nitrogen, acetylene, and vacuum. Thermal parameters were investigated using differential scanning calorimetry. The results showed that both irradiation dose and environments affected the thermal and tensile properties. Gamma irradiation significantly increased the melting temperature of UHMW-PE in all cases. However, the oxidation temperatures of irradiated polyethylene was lowered in all cases except those associated with acetylene environment. The crystallinity of the polymer was increased upon irradiation. Tensile yield strength and modulus of irradiated UHMW-PE increased for all cases except those treated at 1.25 and 2.5 Mrad, and in nitrogen environment that showed a decrease in the modulus. Gamma irradiation caused a weight gain of UHMW-PE in all conditions. To further the study, the postirradiation aging effect on the irradiated polymer was examined during a period of 1 year, and the results showed that the thermal and tensile properties of UHMW-PE were, indeed, affected. The data suggests that irradiation in acetylene affects mainly the crosslinking of the polymer. © 1995 John Wiley & Sons, Inc.     

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 irradiation on mechanical and structural properties of ethylene vinyl acetate copolymers hollow fibers

Effect of irradiation on mechanical and structural properties of ethylene vinyl acetate copolymers (EVA) hollow fibers was studied by the tests such as determination of gel content, density, tensile, FTIR, SEM, and DMA. These effects were discussed based on dose and irradiation environment. The results of gel content depicted that irradiated EVA in ambient conditions had tendency to chain scission while the crosslinking overcame in irradiated samples under nitrogen. Density insignificantly enhanced with irradiation dose. In tensile test, irradiation induced increase in tensile strength and decrease in elongation at break (especially in samples irradiated in nitrogen). Also, changing in layer orientation could be observed by SEM images. In addition, irradiation caused altering peak intensity in FTIR spectrum. DMA results demonstrated that irradiation broaden the elastic zone. Totally, irradiation enhances features especially in irradiated EVA18 in nitrogen. Since, according to stabilization of induced deformation and improvement of mechanical properties (that created by radiation), the irradiated samples can be used in different applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of a photoresponsive cell culture surface: Regional enhancement of living‐cell adhesion induced by local light irradiation

Using a functional polymer containing nitrospirobenzopyran residues and poly(ethylene glycol), we developed a photoresponsive cell culture surface (PRCS), at which the cell adhesion can be enhanced locally by UV light irradiation (350–400 nm, 35 mW/cm², 5 min) even on the region where living cells exist. Cell adhesion was evaluated by observing BALB/3T3 fibroblasts, which had been seeded on PRCS and then irradiated with UV light regionally, after 12 h incubation and subsequent washing to remove scarcely adhering cells. As a result, it was confirmed that the number of remaining cells in irradiated region was at most 2.5 times greater than that in nonirradiated regions, suggesting the implementation of a novel scheme to manipulate living cells individually by light irradiation in a parallel and simultaneous manner. Influence of the composition of the polymer material consisting the substrate surface was also investigated systematically. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 495–499, 2006     

Characterization of UV-irradiated Lexan polycarbonate films

Lexan polycarbonate films were irradiated by UV radiation at wavelength $ \lambda $  = 250 nm under different time exposures of 1, 2, 4, 6 and 7 h. Structural, optical and mechanical modifications were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), UV–Visible spectroscopy, impedance analysis, tensile testing and rheometry methods. The crystallite size and percentage of crystallinity were found to decrease upon irradiation as was studied by XRD. It indicated that polymer was moving towards more disordered state after irradiation corroborating DSC results. FTIR Study showed the carbonate linkage is the radiation-sensitive linkage and benzene ring does not undergo any change after irradiation. SEM results showed the formation of pores after irradiation. The atomic force microscopy measurements revealed that the average roughness of the film increased after being irradiated. The glass transition temperature was observed to decrease after irradiation as revealed by DSC measurement. UV–Visible spectra showed decrease in optical band gap after irradiation due to chain scission in the Lexan polycarbonate. Plot of AC conductivity versus log (f) displayed a sharp increase in conductivity at higher frequencies and dielectric constant/loss was observed to change with the irradiation time. The mechanical properties and average molecular weight of Lexan polycarbonate decreased after irradiation, while the average number of chain scissions per original polymer molecule increased with increase in time of exposure.     

Luminescence from γ- and β-irradiated HDPE and LLDPE

The luminescence of polyethylene (high density polyethylene (HDPE) and linear low density polyethylene (LLDPE)) induced by ionising irradiation has been studied. The effects of filling materials, irradiation dose and dose rate on the luminescence have been investigated. For freshly irradiated samples, both unfilled and filled, the luminescence was concluded to consist predominantly of thermoluminescence (TL). Upon subsequent ageing, the contribution of TL was found to decrease due to its decay with time after irradiation. Light emission was found to increase in the later stages of ageing, for irradiated and also for un-irradiated samples. This light was interpreted as chemiluminescence (CL), emitted as a result of polymer oxidation. The maximum of the CL was higher for irradiated than for unirradiated polyethylene, indicating that the ionising radiation gave rise to an increased amount of oxidation products. Thus, CL has been shown to be a feasible technique in studies of radiation-induced oxidation. © of SCI.