Free volume related fluorescent behavior in electron beam irradiated chalcone doped PVA

Effect of electron irradiation on the free volume related microstructural and optical properties of chalcone doped Poly(vinyl alcohol) composite films have been studied using FTIR, UV-Visible, XRD and Positron Annihilation techniques. The FTIR spectral study shows that the irradiation induces the crosslinking within the composite. Using UV-Visible absorption spectra the optical energy band gap and activation energies were estimated and the variation of these parameters suggests the existence of defects and molecular ordering within the irradiated composite. XRD diffractograms reveal that the crosslinking enhances the crystallinity of the sample. In this cross-linked polymer composite the fluorescence enhancement has been observed in the fluorescence spectral study. The Positron annihilation result suggests that the irradiation affects the free volume properties and crosslinking hinders the chalcone chromophore molecular rotation. Under this restricted condition the chromophore molecules likely to emit enhanced fluorescence and its mobility is directly related to the free volume around it.     

Electron irradiation induced microstructural modifications in BaCl2 doped PVA: A positron annihilation study

Thin films of pure and 10 wt% BaCl₂ doped poly(vinyl alcohol) (PVA) were prepared by solution casting method. These films were subjected to electron irradiation for different doses ranging from 0 to 400 kGy in air at room temperature. The effect of electron irradiation on the optical and free volume related microstructures of these polymer films was studied using positron annihilation lifetime spectroscopy, FTIR and UV-vis techniques. The FTIR spectral studies indicate that the electron irradiation induces chemical modifications within the doped PVA, which results in chain scission as well as cross-linking of the polymer. The positron lifetime study on these irradiated polymers shows that the chain scissions and cross-linking within the polymer matrix affect the free volume content and hence the microstructure. The UV-vis optical absorption studies show that the induced microstructural change by electron irradiation also modifies the optical properties. Using UV-vis spectra, the optical energy band gap was estimated and it decreases with increase in electron dose. A correlation between positron results and optical results is obtained and electron irradiation induced microstructure modifications within the doped polymer are understood. The results highlight the usefulness of positron annihilation technique in the study of the microstructure of irradiated polymers.     

Thermogravimetry and differential scanning calorimetry of γ-irradiated i-polypropylene films

Isotactic polypropylene films, Buplen Type, 40m thick, irradiated by a⁶⁰Co source to doses 0.37–37 Mrad, are investigated by means of optical microscopy, WAXS, thermogravimetry, DSC and DTA. The original film exhibits a paracrystal structure. Irradiation does not change the films' structure. The kinetic parameters of the non-isothermal destruction and the thermodynamic parameters of melting are obtained. The samples irradiated to small doses (up to 3 Mrad) are thermally more stable; the activating energy of the destruction is higher than that of the original film. The temperature of melting slightly increases, while the enthalpy of melting decreases. For the range of doses of 3.7–37 Mrad, the films show low thermal stability and the destruction proceeds with low activating energy. From the results of the data obtained, the following assumptions are made: the-irradiation causes simultaneous crosslinking and chain scission at random sites along the chains. Fragments of partially crosslinked molecules and fractions of low molecular linear segments are formed. The destruction caused by radiation prevails above 3 Mrad.     

Quantitative evaluation of photodegradation and racemization of poly(l-lactic acid) under UV-C irradiation

To obtain details of poly(l-lactic acid) (PLLA) photodegradation behavior, PLLA films were irradiated by UV-C light (λ = 253.7 nm) to directly excite carbonyl groups, resulting in a rapid decrease in the molecular weight accompanying a gradual decrease in the optical purity of monomeric units in the chains. The racemization during the photodegradation was first detected as a result of the chain scission by irradiation. From quantitative analyses of the molecular weight and the monomeric unit composition, it was found that the chain scission ratio and the d-lactate unit ratio increased in parallel during the irradiation, suggesting that approximately one d-lactate unit formed for every chain scission. From a mechanistic consideration, the racemization equilibrium was proposed to occur at both carboxyl and hydroxyl chain ends.     

Effect of vinyl acetate content and electron beam irradiation on the flame retardancy, mechanical and thermal properties of intumescent flame retardant ethylene-vinyl acetate copolymer

Ethylene vinyl acetate copolymer (EVA) flame retarded by ammonium polyphosphate (APP) and pentaerythritol (PER) was cross-linked by electron beam irradiation. The effects of vinyl acetate content and electron beam irradiation on the flame retardancy, mechanical and thermal properties of EVA composites were investigated. The volatilized products of EVA/APP/PER composites were characterized by thermogravimetric analysis/infrared spectrometry. As VA content increased, the volatilized products increased in the second decomposition step, but decreased in the third decomposition step. For all samples, the increase of irradiation dose could improve both the gel content and the Limit Oxygen Index (LOI, the minimum oxygen concentration by volume for maintaining the burning of a material) values of irradiated composites. The mechanical and thermal properties of the irradiated EVA composites were also evidently improved at appropriate irradiation dose as compared with those of unirradiated EVA composites, whereas these properties decrease at higher irradiation dose because of the electron beam irradiation-induced oxidative degradation or chain scission.     

Mass spectrometry investigation of the degradation of polyethylene terephtalate induced by low-energy (<100 eV) electrons

Polyethylene terephtalate (PET) thin films were damaged by low-energy (0–100 eV) electron irradiation to simulate the degradation of this polymer in electronic devices. The products formed were analyzed by mass spectrometry. The emission of anions from the polymer surface is associated with dissociative electron attachment (DEA) and dipolar dissociation (DD) for H⁻, and with DD for O⁻. The monotonic emission rise in O⁻ desorption as a function of incident electron energy is produced by mid-chain C–O–C cleavage, leading to chain scission. The signal of the positive mass fragments showed only a monotonic increase with electron energy. In this case, chemical recombination with hydrogen atoms also leads to chain scission.     

Physico-chemical transformations in swift heavy ion modified poly(ethyleneterephthalate)

Thin films of poly(ethyleneterephthalate) (PET) were exposed to different radiation dose brought about by 80 MeV carbon and 98 MeV silicon ion beam. The UV-vis absorption studies reveal that there is decrease in optical band gap energy to the extent of ∼29.3 and 42.1%. The X-ray diffraction analyses have shown that crystallite size decreased by ∼18.6 and 52.6%, indicating amorphization of PET. The colour of PET films change from colourless to light yellowish followed by light brown as radiation dose is increased. The colour formation has been ascribed to an increase in conjugation in the carbon chain. In the case of PET irradiated with carbon ion, the electrical conductivity increased with frequency beyond a threshold value of 1 kHz. The increase in conductivity of PET films on irradiation is due to formation of defects and carbon clusters as a result of polymer chain scission. The thermal study further confirmed the increase in amorphous nature with increase in radiation dose. The results indicate that radiation dose brings about significant physicochemical transformations in PET.     

Mössbauer and positron life-time study of oxyhemoglobin solution irradiated by electrons

Human oxyhemoglobin concentrated solution exposed to electrons with average energy of 10 MeV in doses of 1.7, 2.5 and 5.0 kGy was studied by Mössbauer spectroscopy and positron life-time technique. Precise measurements of Mössbauer spectra of irradiated oxyhemoglobin samples revealed deoxygenation process and formation of two ferric compounds at 1.7 kGy and ferrous and ferric compounds at 2.5 and 5.0 kGy. Positron life-time parameters showed decrease of the free volume radius and the total free volume in irradiated oxyhemoglobin solutions.     

Modification of microstructure of the surface and the bulk in ion-irradiated membrane studied using positron annihilation spectroscopy

The effect of ion irradiation and etching on the microstructure of polyethyleneterephthalate (PET) membrane has been studied using positron annihilation spectroscopy. PET membrane of 25 μm thickness was irradiated by 100 MeV ³⁵Cl beam (7×10⁷ ions/cm²) and then etched with NaOH for 45 min. The modification in the microstructure at the surface of the membrane was probed by depth-dependent Doppler-broadened S-parameter and positronium 3γ–2γ annihilation ratio using a slow positron beam, while the free volume properties in the bulk of the membrane were studied using the conventional positron lifetime technique. Positron annihilation parameters were found to be very sensitive to the microstructural changes occurring in the polymer at such a low fluence. It was observed that on ion-irradiation, the surface of the membrane is modified in a different way than the bulk. While the ion-irradiation produces large fraction of excess free volumes at the surface of the membrane due to chain scission, the free volumes are reduced in the bulk of the membrane due to cross-linking. FTIR and XRD measurements were also carried out to investigate the changes occurring in the chemical structure and crystallinity of the polymer samples on ion-irradiation and etching.     

Modeling the time and temperature dependence of the oPs formation probability in polystyrene and its derivatives

Positron annihilation lifetime spectroscopy measurements of polystyrene and its derivatives have been performed in the temperature range 20–300 K. The ortho‐positronium lifetime calculated from the lifetime spectrum analysis is related to the mean free‐volume hole size. However, the ortho‐positronium yield in the medium is dependent on the polymer chemistry and also on the irradiation effect induced by the positron source. We proposed a model based on two simple processes that cause, respectively, enhancement and inhibition of positronium formation to fit the experimental data over a broad temperature range. Using this model, intrinsic parameters for the polymers under study, such as the shallowly trapped electron recombination energy and the free‐radical recombination energy, were calculated and discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2063–2073, 2009     

Radiation degradation of poly(methyl methacrylate) in the soft x-ray region

The molecular weight distribution change has been measured for the photoresist poly(methyl methacrylate) [PMMA] after in-vacuo exposure to monochromatic soft x-rays from the Canadian Synchrotron Radiation Facility [CSRF]. The experimental changes in the mo-lecular weight distribations derived from gel permeation chromatography [GPC], were compared to a simple Monte Carlo simulation model that assumes random main chain scission. Using this model a scission radiation chemical yield of G(S) = 1.28± 0.10 at room temperature was found to give the best fit at a photon energy of 621 eV. This value is similar to values reported previously in the literature using electron beam and γ-ray sources, but significantly larger than those reported for fast neutrons, α-particles, or energetically charged particles. It was found that in this soft x-ray energy regime, that degradation of PMMA involves primarily a random scission process of the main chain. The results of a least-squares fit of this soft x-ray G(S) data and all available literature values from other radiation sources, to the linear energy transfer [LET] dE/dx are discussed. © 1993 John Wiley & Sons, Inc.     

A comparison of modifications induced by Li<Superscript>3+</Superscript> and Ag<Superscript>8+</Superscript> ion beams irradiation in poly(lactide-<Emphasis Type="Italic">co</Emphasis>-glycolide) films

Poly(lactide-co-glycolide) (PLGA) films were irradiated by 180 MeV/amu Ag⁸⁺ ions and 50 MeV/amu Li³⁺ ions at different fluences of 5 × 10¹⁰, 5 × 10¹¹ and 1 × 10¹² ions/cm². Modifications of polymer films induced by the swift heavy ions (SHI) irradiation were studied by X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR) and UV–Vis spectroscopy. The dominant effect of the SHI beam irradiation is proposed to be chain scission which leads to breakage of polymer chains, followed by hydrogen abstraction. The results from FTIR spectroscopy showed that the intensity of all peaks of the irradiated samples decreased at high fluence of SHI, suggesting PLGA samples significantly degraded at high SHI fluence. The variation in optical band gap energy and Urbach energy with increasing fluence was calculated from UV–Vis spectroscopy and explained in terms of changes occurring in the polymer matrix. X-ray diffraction patterns also show appreciable changes in PLGA at high fluence. FESEM results revealed that the hydrophilicity of the PLGA surface increased with an increase in ion fluence. In this paper the optical, chemical and structural changes with different fluence rates are discussed.     

Energy dispersive X-ray fluorescence analysis of airborne particulate matter

Positron annihilation lifetime technique was applied to study the electric field dependence of size, intensity and size distribution of free volumes in various liquid crystals negative nematic MBBA(N-(4-methoxybenzylidene)-4-n-butylaniline), positive nematic 5CB (4-cyano-4-n-pentylbiphenyl) and cholesteric mixture of MBBA and cholesteryl oleate. Positron annihilation decay curves were obtained in the direct and alternate electric field range from 0 to 120 V/mm, and annihilation curves were resolved into four lifetime components. The relation between the free volume parameters and the variation of molecular alignment is discussed for nematic and cholesteric liquid crystals.     

Thermally stimulated currents depolarization study of gamma ray irradiated PMMA

We will investigate the effect of γ-irradiation on the polymethyl methacrylate (PMMA) properties. The Fourier transform infrared spectroscopy technique in attenuated total reflexion mode (FTIR-ATR) results allowed us to show that the irradiated PMMA undergoes a scission in its lateral chain combined to an oxidation phenomenon. In fact, a decrease in the carbonyl index, versus the radiation dose, is observed. The differential scanning calorimetry and the thermostimulated depolarization currents revealed that the scission in the lateral chain provides a better flexibility to the PMMA chain and an increase in the free volume of the material. The consequences of these phenomena appear in the decrease of the activation energy of PMMA and the appearance of a local order in the material at a temperature T_c which decreases versus the radiation dose.     

Study on the Mechanism of the Radiation-Induced Chain Oxidation of N,N,N,N-Tetramethyl-4,4′-diaminodiphenylmethane by Tetrabromomethane in Poly(vinyl chloride) Films

Kinetics and mechanism of the radiation-induced chain oxidation of N,N,N,N-tetramethyl-4,4-diaminodiphenylmethane (Am) by tetrabromomethane in poly(vinyl chloride) (PVC) films were studied by ESR and optical spectroscopy. The quantitative analysis of the ESR spectra of PVC films containing Am and CBr₄ irradiated with -rays at 77 K was performed. The nature of radical species involved in the chain process was established. It was shown that the heating of the films after their irradiation at 77 K resulted in the formation of free radicals Am^·, which initiated the chain oxidation of amine with a chain length of 100. The kinetic features of the chain oxidation–reduction reactions occurring in vacuum and in the presence of oxygen were compared.     

Fourier transform infrared investigation of the effects of irradiation on the 19 and 30°C phase transitions in polytetrafluoroethylene

Fourier transform infrared spectroscopy has been used in conjunction with differential scanning calorimetric measurements to investigate the nature of molecular degradation and its effect on the phase transition temperatures in irradiated polytetrafluoroethylene (PTFE). Both the 19 and 30°C transitions are observed to exhibit similar shifts to low temperatures upon irradiation. Infrared absorbance subtraction data from irradiated PTFE indicate a continual decrease in sample crystallinity accompanied by an increase in the number of free and bonded ? COOH groups with increasing dose consistent with molecular degradation by chain scission. By comparing infrared band intensities on a number of irradiated PTFE samples with those from short chain perfluoro n-alkanes, it was determined that the overall reduction in chain length caused by irradiation was primarily responsible for the observed reduction in both phase transition temperatures.     

Creep behavior of epoxy resin during irradiation at cryogenic temperature

Creep tests of an epoxy resin during bending and irradiation have been carried out to investigate the synergistic effects of radiation and stress on mechanical properties of the resin. Simultaneous application of stress and irradiation on the epoxy resin enhanced creep rates in comparison with the application of stress on an irradiated sample. In order to clarify the mechanism of the radiation-induced creep, measurements of solvent swelling of specimens have been performed. The swelling increased with the dose and the increase of the swelling corresponds to the increase of the chain scission. The mechanism of increased deformation of the resin during irradiation is proposed to be caused by increased chain scission following the release of the local strain energy.     

Mechano-ions produced by mechanical fracture of solid polymers

It is said that the free radical caused by C-C-bond scission, homogeneous scission, is produced by mechanical degradation. In addition to free radicals, ionic species are produced due to the mechanical destruction of the polymers. Studies in our group concerning this problem are summarized. When the polymers were ground with tetracyanoethylene (TCNE) powder in a vibration glass ball mill in vacuum in the dark at 77 K, the TCNE anion radical (TCNE$ \bar . $) was detected by electron spin resonance (ESR) method. The TCNE$ \bar . $ is formed by the abstraction of electrons by TCNE from the anion produced by a heterogeneous bond scission of carboncarbon bonds in the polymer main chain. The identification of TCNE$ \bar . $ was carried out by the spectral simulation on the basis of an anisotropic hyperfine tensor including a forbidden transition term. Several polymers were examined; polyethylene, polypropylene, poly(tetrafluoroethylene) and poly(vinylidene fluoride). The ratio of ionic species and free radicals is discussed.     

Compatibilisation of polyethylene/ground tyre rubber blends by γ irradiation

In the present work, γ irradiation is used for the in situ compatibilisation of blends of recycled high density polyethylene (rHDPE) and ground tyre rubber (GTR) powder. The expected compatibilisation mechanism involves the formation of free radicals, leading to chain scission within rubber particles, crosslinking of polyethylene matrix and co-crosslinking between the two blend components at the interface. While uncompatibilised rHDPE/GTR blends show poor mechanical properties, especially for elongation at break and Charpy impact strength, irradiation leads to a significant increase of these mechanical performances. Such behaviour is attributed to the development of an adhesion between GTR particles and the surrounding thermoplastic matrix. This conclusion is supported by in situ scanning electron microscopy observations during microtensile tests, showing strong elongation of GTR particles upon deformation of irradiated blends.     

Thermal and crystallization behaviour of gamma irradiated PLLA

Structure, crystallization behaviour and some thermal properties of poly-l-lactide (PLLA), gamma irradiated up to 300 kGy, have been studied. Through differential scanning calorimetry measurements, radiation-induced changes were evident in the enthalpy of melting and cold crystallization, as well as in the degree of crystallinity. Decay of the glass transition, cold crystallization and melting temperatures with irradiation dose was observed in all cases. The annealing treatment, which can substantially reduce the concentration of free radicals, also had a great impact on thermal/crystallization behaviour of irradiated PLLA. Extensive chain scission, as a dominant effect of gamma irradiation, confirmed by gel permeation chromatography, has as a consequence a growth of new thin crystal lamellae and occurrence of the second low-temperature melting peak. Thermogravimetric analyses have shown that irradiation lowered the thermal stability of PLLA.