Thermoluminescence characterization of functionalized grafted polymers and its application for radiation dosimetry at low doses

Functionalized polymers were prepared by radiation-induced graft copolymerization of binary monomer system acrylic acid/acrylamide (AAc/AAm) onto low-density polyethylene (LDPE) and polypropylene (PP) films using direct radiation-grafting technique. Sulfonation was carried out for the prepared grafted copolymers using concentrated sulfuric acid (97%) at 60 ^°C for 15 min. The grafted and sulfonated grafted films found to have good properties such as thermal stability and hydrophilic properties. The sulfonated grafted films found to have a better hydrophilic character than the grafted ones due to ionic character resulted by this conversion. The thermoluminescence (TL) characteristics of a set of grafted and sulfonated films have been studied with regard to their use as off-line dosimeters in radiotherapy. The structural characterization has been performed by means of infrared spectroscopy. Their TL responses have been tested with radiotherapy beams of ⁶⁰Co photons in the dose range 0.1–7 Gy. The dosimetric characterization has yielded a very good reproducibility and is independent of the radiation energy. The TL signal is not influenced by the dose rate and exhibits a very low thermal fading. Moreover, the sensitivity of the samples compares favorably with that of the standard TLD100 dosimeters. Finally, at the same dose, the TL response for LDPE-g-P (AAm/AAc) films is higher than the PP-$g$-P(AAm$/$AAc), and the sulfonated grafted films are more sensitive to radiation than the grafted ones.     

Pre-irradiation-induced graft reaction of maleic anhydride onto polypropylene

The radiation induced graft polymerization is a well-known method to obtain new materials. Until recently, only conventional radiation sources, such as Co-60 and electron beams, were used. Moreover, part of the damage induced in polymers by heavy ions can produce active sites (peroxides and hydroperoxides) that are useful to initiate grafting reactions. Maleic anhydride (MAH) was grafted onto polypropylene (PP) wax with a number-average molecular weight (Mn) of 8000 by gamma pre-irradiation technique. Effects of total dose, monomer concentration, reaction time, and temperature on percentage of grafting are studied in detail. It is shown that the optimum conditions for grafting are temperature of 70 ^°C and total dose of 14.4 kGy. PP-g-MAH is characterized by infrared spectrum. Differential scanning calorimetry shows that the compatibility of PP-g-MAH is better than that of PP.     

Theoretical analysis on geometries and electronic structures of antiaromatic pentalene and its N‐substituted derivatives: monomer,oligomers and polymer

The antiaromatic compounds have received a great deal of attention for several decades because of their unusual electronic structures. The electronic structures and properties of antiaromatic pentalene and its six nitrogen heterocyclic derivatives were systematically studied by the density functional theory at the Becke, three‐parameter, Lee–Yang–Parr level with 6‐31G* basis set. The results indicated that all the monomers have stable singlet states and remarkable bond‐length alternations. From the dimer to polymer in those molecules, pentalene(P), cyclopenta[b]pyrrole(CPP), cyclopenta[d]imidazole(CPI), pyrrolo[2,3‐b]pyrrole(PP1) and pyrrolo[3,2‐d]imidazole(PI) are stable diradical structures; pyrrolo[3,2‐b]pyrrole (PP2) and imidazo[4,5‐d]imidazole(II) are stable singlet ground states. The electronic properties including bond length, bond‐length alternation, electron density at bond critical points, Wiberg bond index and nucleus‐independent chemical shift were analyzed. It was found that in diradical molecules the bond‐length alternations are diminished, the charge tends to equilibrate, the π‐electron delocalization and conjugation are strengthened. The electronic properties of singlet ground state molecules have nearly no variations from monomers to polymers. The band structure analysis shows that diradical structure molecules have small band gaps (<1.0 eV), wide bandwidth and small effective masses of holes and electrons which suggest that diradical structure molecules are very good candidates for conductive materials. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of the effects of soft X-ray irradiation on polymers

The physical and chemical effects of the soft X-ray irradiation of polymers have been systematically evaluated for photon energies just above the C 1s binding energy. This exposure causes radiation damage in the form of the loss of mass and changes to the chemical structure of the polymers. These effects are evident in the Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of the exposed polymers, posing a fundamental limit to the sensitivity of NEXAFS spectroscopy for chemical microanalysis. Quantitative understanding of the chemistry and kinetics of radiation damage in polymers is necessary for the successful and validated application of NEXAFS microscopy. This paper outlines a method for quantifying this radiation damage as a function of X-ray dose, and applies these methods to characterize the loss of mass and loss of carbonyl group functionality from a diverse series of polymers. A series of simple correlations are proposed to rationalize the observed radiation damage propensities on the basis of the polymer chemical structure. In addition, NEXAFS spectra of irradiated and virgin polymers are used to provide a first-order identification of the radiation chemistry.     

Radiation effects on poly(vinylidene fluoride)

Melt-crystallized poly(vinylidene fluoride)s (PVF₂) with different crystallization histories were irradiated with γ-rays within the range of irradiation doses 0–83 Mrad. The effects on the crystalline structure and mechanical properties have been measured, compared, and discussed. The degree of crystallinity of the samples was found to increase with radiation dose. The differential scanning calorimeter scans of the quenched samples indicate that there are two melting peaks, and that the area of the lower temperature peak increases while the area of higher temperature peak decreases with increasing dose. Yield stress and breaking stress for all samples are not significantly affected by irradiation but elongation at break is.     

Proton dose-dependent modification in track etching response in some polymers

In the present work, the effect of four different doses of 62 MeV protons, on the fission fragment track etching characteristics of two polymers, viz. polycarbonate (Makrofol-N (MFN)) and polyimide (PI) are studied by nuclear track technique. The bulk etch-rate of PI increased by around 30% at the highest proton dose, whereas the activation energy of etching remained almost constant for the same. A considerable increase in the bulk etch-rate of MFN was observed (75%) at the highest proton dose. The activation energy of etching of the fission fragment tracks in MFN was also found to be an inverse function of dose.     

Thermoluminescence glow-curve characteristics of LiF phosphors at high doses of gamma radiation

High doses of ionising radiation are becoming increasingly common for radiation-processing applications of various medical, agricultural and polymer products using gamma and electron beams. The objective of this work was to study thermoluminescence (TL) glow-curve characteristics of commonly used commercial LiF TL phosphors at high doses of radiation with a view to use them in dosimetry of radiation-processing applications. The TL properties of TLD 100 and 700 phosphors, procured from the Thermo-Scientific (previously Harshaw) company, have been studied in the dose range of 1–60 kGy. The shift in glow peaks was observed in this dose range. Integral TL responses of TLD 100 and TLD 700 were found to decrease as a linear function of dose in the range of 5–50 kGy. The paper describes initial results related to the glow-curve characteristics of these phosphors.     

High energy electron irradiation effects on polystyrene films

The effect of an 8 MeV electron-beam on the structural, optical and dielectric properties of polystyrene films has been investigated respectively by means of Fourier transform infrared (FTIR) spectroscopy, ultraviolet–visible (UV–VIS) spectroscopy and electrical impedance (LCR) analysis over a radiation dose in the range of 50–250 kGy using a Microtron accelerator. The FTIR spectral analysis shows no change in the overall structure of the irradiated polystyrene films, except a minor change in the intensity of a few peaks in the FTIR spectrum, indicating that polystyrene is resistant to electron-beam irradiation over the range of radiation doses investigated. The optical band gap analysis using the UV–VIS absorption spectra of the polystyrene shows a small decrease in the optical band gap (E _g) and the activation energy with an increase in electron doses. Further, the dielectric measurements over a frequency range of 100 Hz to 1 MHz for the electron-beam-irradiated polystyrene films show that both the dielectric constant and the dielectric loss increase with an increase in electron radiation dose, which may be ascribed to the formation of defect sites in the band gap of polystyrene as a consequence of molecular chain scission in the polymer films upon irradiation.     

Examination of optical properties and estimation of mechanical energies of irradiated polypropylene and teflon

The optical absorption and mechanical yielding energy has been studied under exposure of γ-radiation. Two crystalline polymers, polypropylene (PP) and Teflon, were irradiated with a ⁶⁰Co source, with doses ranging up to 6 kGy. The observed optical energy gap (E _opt) and energy gap tail (Δ E) for irradiated thin sheets of PP were determined from the measured absorption spectra. The average values of (E _opt) and (Δ E) were 5.85 and 0.5 eV, respectively. There is no detectable change in the optical energy gap under the applied γ-ray doses. On the other hand, the effect of γ-radiation on mechanical properties of irradiated Teflon was much pronounced. It was found that Young’s modulus and yield stress increase with radiation dose, whereas the yield strain decreases. The calculated yield energy increases with radiation dose from 0.27 to 0.35 Mpa per unit volume. The enhancement in the mechanical properties of irradiated Teflon was attributed mainly to crosslinking process and other structural changes occuring during irradiation with γ-rays.     

Relationship between Peroxide Initiators and Properties of Styrene Grafted Polypropylene via Reactive Extrusion

To understand the relationship between the initiators and the properties of grafted polypropylene (PP), and provide guidance for designing polymers with different performance through selecting appropriate initiators, a series of styrene (St) grafted PP was prepared by modifying commercial linear PP via reactive extrusion using two different peroxide initiators, dicumyl peroxide (DCP) and benzoyl peroxide (BPO). Fourier transform infrared spectra indicated that the use of DCP led to a higher St grafting degree compared to the system using BPO. The melt flow index and rheological characteristics suggested the existence of short chain branching (SCB) structures in the St grafted PP using DCP, and long chain branching (LCB) structures in the St grafted PP using BPO. Differential scanning calorimetry and polarized optical microscopy results showed that the degradation of the PP chains and the introduction of SCB structures hindered the crystallization process of the St grafted PP using DCP, and the existence of the LCB structures accelerated the crystallization process of the St grafted PP using BPO. We suggest this research can contribute to the understanding of methods to prepare grafted PP with special properties via reactive extrusion by using proper initiators.     

“New” Ginzburg-Pekar waves in the microwave range in ice

The recently discovered effect of microwave radiation spatial dispersion in freshwater ice is studied experimentally. This effect, first studied by Ginzburg and Pekar, shows up most vividly in the emergence of new waves that have the same polarization as the primary wave but different wavevectors. In the case of monochromatic radiation, four waves with different wavevectors may coexist in the medium. Interference of these waves may explain anomalies in the electromagnetic properties of the glacial structures observed earlier. New experimental results on the polarization properties of the signal transmitted through ice corroborate the spatial dispersion in the microwave range.     

Study of Morphology and Mechanical Properties of In Situ PP/PS Alloy

The in situ polypropylene (PP)/polystyrene (PS) alloy was prepared in the presence of dicumyl peroxide (DCP). Purified styrene (St) and pre‐polymerized styrene (PSt), forming a dispersed PS phase in the PP matrix would react with PP matrix to form PP‐g‐PS graft co‐polymers acting as a compatibilizer in these alloys, leading to the formation of in situ PP/PS alloys with in situ compatibilizer during reactive blending in a mixer. The morphology development of the alloy was examined by scanning electron microscopy (SEM) and was described using the characteristic length L and the average characteristic length L_m. The shape of the dispersed PS phase was regular and the distribution of PS particles was uniform. Tensile properties of the alloy were improved with mixing time and fluctuated in a certain composition range.     

Ab-initio calculation of optical properties of AA-stacked bilayer graphene with tunable layer separation

Density functional theory based calculations revealed that optical properties of AA-stacked bilayer graphene are anisotropic and highly sensitive to the interlayer separation. In the long wave length limit of electromagnetic radiation, the frequency dependent response of complex dielectric function becomes vanishingly small beyond the optical frequency of 25.0 eV. Besides, static dielectric constant shows a saturation behaviour for parallel polarization of electric field vector when interlayer spacing is greater than 2.75 Å. As a consequence, an appropriate modification of effective fine structure constant is observed as a function of layer separation. Moreover, the bilayer systems are highly transparent in the optical frequency range of 7.0–10.0 eV. The electron energy loss function exhibits two different in-plane collective (plasmon) excitations and a single out of plane plasmon excitation. The spectral nature of different frequency dependent optical properties is observed to be very similar to that of the monolayer pristine graphene apart from their exact numerical values.     

Xyloglucan degradation using different radiation sources: a comparative study

Tamarind seed xyloglucan was subjected to different radiation sources-ultrasound, gamma-radiation, and microwave heating, and the effects of these energies upon its molecular and structural properties were characterised by gel permeation chromatography, viscometry, sugar analysis, FT-IR and NMR spectroscopic techniques. In dependence on the degradation methods and experimental conditions used, the decrease of the relative molecular mass (RMM) was accompanied with alteration of the primary structure. Depolymerisation by ultrasound at a frequency of 20 kHz yielded after 120 min products with RMM of about 131 x 10(3) without significant alteration of the primary structure of the polysaccharide. Intense degradation of XG started by microwave heating at pH 1.5 yielding polymers with RMM in the range of higher oligosaccharides, however, with changed sugar composition due to cleavage of the glycosyl side chains. At gamma-irradiation doses >40 kGy, next to chain cleavage, very high-molecular mass components exhibiting UV(254)-absorption were formed, and the RMM decreased to about 50 x 10(3) at the highest applied dose (100 kGy). The results of the comparative study suggest that ultrasonication was the most convenient procedure to decrease the RMM of xyloglucan to 130 x 10(3) and preserve the primary structure of the polysaccharide.     

Tensile drawing of high and low molecular weight polyethylene terephthalate

The tensile drawing of polyethylene terephthalate fibers spun from polymer of high and low molecular weight over a range of windup speeds has been studied. An analysis of the mechanical properties, orientation, and shrinkage behavior for different draw ratios leads to two conclusions. First, the network structure is the same for both polymers and the same as that described for a medium molecular weight polymer in an earlier paper. Secondly, an increase in molecular weight has an effect similar to an increase in the windup speed on the spun fiber molecular structure, which affects the ultimate mechanical properties obtainable by the chosen processing routes.     

Effects of Viscosity Ratio on Morphological,Rheological and Mechanical Properties of PP/PBT Melt Spun Alloy Fibers

Phase morphology formation plays an important role in the mechanical properties of polymer alloy fibers. The development of the blend morphology depends not only on the intrinsic properties of the component polymers but also on extrinsic factors such as viscosity ratio, λ, in the melt spinning process. The effects of blend component viscosity ratio on the morphological, rheological, and mechanical properties of polypropylene/poly(butylene terephthalate) (PP/PBT) melt spun alloy fibers were investigated. Accordingly, two kinds of PP as matrix phase and two kinds of PBT as dispersed phase, with various melt viscosity, were physically mixed and then blended during the extrusion step of melt spinning. SEM micrographs and rheological and mechanical properties evaluations showed that the morphology of PP/PBT alloy fibers strongly depend on the viscosity ratio, λ. Finer diameter PBT fibrils were observed for Viscosity ratios less than 1 (λ < 1) compared to samples with λ > 1. The best mechanical properties in alloy fiber samples were obtained for the viscosity ratio closest to unity (sample with λ = 0.9). The lowest differences among measured complex viscosities at various shear rates (0.1, 10, and 100 s^?1) were also observed in samples with λ = 0.9. The results showed that the mechanical properties of alloy fiber samples are affected not only by morphological properties observed at different viscosity ratios but also by the properties of the individual polymer components.     

Buckling Behavior of Carbon Nanotubes Functionalized with Carbene under Physical Adsorption of Polymer Chains: a Molecular Dynamics Study

The buckling analysis of functionalized carbon nanotubes (CNTs) is of great importance for the better understanding of mechanical behavior of nanocomposites. The buckling behavior of carbene-functionalized CNTs (cfCNTs) under physical adsorption of polymer chains (cfCNTs/polymers) is studied in this paper by the classical molecular dynamics (MD) simulations. In this regard, to investigate the interactions between non-covalent polymer chains and cfCNTs, two different non-covalent functional groups, i.e. polycarbonate (PC) and polypropylene (PP), are selected. The findings are compared with those of pure CNTs under the physical adsorption of polymer chains (pCNTs/polymers). The obtained results show that at a given weight percentage of non-covalent functional groups, the gyration radius of cfCNTs/polymers is higher than that of pCNTs/polymers. Furthermore, an increase in the critical buckling force of cfCNTs/polymers is dependent on the type of non-covalent polymer chains. For cfCNTs/PC and cfCNTs/PP, the critical buckling force is respectively lower and higher than that of pCNTs/polymers for the similar weight percentage of non-covalent functional groups. In addition, it is found that the critical buckling strain of cfCNTs/polymers is smaller than that of pCNTs/polymers for the same weight percentage of non-covalent polymer chains.     

Radiation graft copolymerization of butyl methacrylate and acrylamide onto low density polyethylene and polypropylene films,and its application in wastewater treatment

Butyl methacrylate and acrylamide (BMA/AAm) comonomers were grafted onto low-density polyethylene (LDPE) and polypropylene (PP) films using the mutual gamma radiation grafting technique. The influences of grafting conditions such as solvent, monomer concentration, monomer composition, and irradiation dose on the grafting yield were determined. It was found that using dimethyl formamide as a solvent enhanced the copolymerization process. The grafting yield increases as the comonomer concentration increases up to 60%. Also it was found that the degree of grafting of BMA/AAm onto both LDPE and PP films increases as the AAm content increases till an optimum value at 50:50 wt%. The grafting yield of the comonomers was found to increase with increase in the radiation dose. It was observed that the degree of grafting of polyethylene films is higher than that of polypropylene (PP) films at the same conditions. Some selected properties of the graft copolymers, such as water uptake and thermal properties, were determined using thermogravimetric analysis. The morphology and structure of the grafted films were investigated using scanning electron microscopy, infra-red, and X-ray diffraction. Improvement in such properties of the prepared copolymers was observed which offers possible uses in some practical applications such as the removal of some heavy metals from wastewater. It was found that the maximum metal uptake by the copolymer followed the order Cu²⁺>Co²⁺>Ni²⁺ ions.     

Morphology,conductivity, and mechanical properties of polypyrrole-containing composites

An electrical-conducting polypropylene/polypyrrole (PP/PPy) composite was prepared by the chemically oxidative modification reaction of pyrrole on the surface of PP particles in suspension. Another type of PP/PPy composite was prepared by mixing the coated PP particles with noncoated PP particles at room temperature. The composites were processed by compression molding or by injection molding. The injection-molded composites exhibited better mechanical properties compared to compression-molded samples, while these composites showed better antistatic behavior and electrical conductivity. The differences in the behavior of the two types of composites were caused by the different structure of the PPy phase, which was studied by hot-stage optical microscopy and X-ray photoelectron spectroscopy (XPS).     

Effect of nano-SiO2 films on the electron radiation induced conductivity of polyimide

The radiation induced conductivity (RIC) behaviors in nano-SiO2 deposited polyimide (PI) were investigated using the in situ measurement technique. The results indicate that, by comparison with the case of virgin polyimide, the RIC in nano-SiO2/polyimide shows low steady state values. Moreover, the steady state RIC is a power function of the dose rate with a power index of 0.659, lower than that of 0.76 in the virgin polyimide. The interfacial barrier and trapping effects are the main reasons for the change. Meanwhile, both of the interfacial effects also result in a unipolar carrier transportation mechanism in nano-SiO2 deposited PI from the dipolar one in the virgin PI. The mechanisms of the RIC behaviors are discussed in the paper.