Annihilation kinetics of color center in polycarbonate irradiated with gamma ray at elevated temperatures

Annihilation kinetics of color center in polycarbonate (PC), irradiated with gamma ray at elevated temperatures, was investigated. The transmission loss in the PC was monitored in the ultraviolet and visible wavelength range. The transmittance decreased with increasing gamma‐ray dose. The loss was attributed to the presence of annealable and permanent color centers. The absorbance in situ data were detected at the wavelength of 450 nm and found in good agreement with the theoretical model in which the annealable color center followed a first‐order kinetic process. The rate constant satisfies the Arrhenius equation, with the activation energy of the color centers decreasing with increase of the gamma‐ray dose. The results were compared with the early findings reported in the literature. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Structure–property behavior of gamma‐irradiated poly(styrene) and poly(methyl methacrylate) miscible blends

Polymer blends based on various ratios of polystyrene (PS) and polymethyl methacrylate (PMMA) were exposed to different doses of gamma radiation up to 25 Mrad. The structure–property behavior of the polymer blends before and after they had been irradiated was investigated by DSC, TGA, and FTIR spectroscopy. The DSC scans of the glass transition temperature (T_g) of the different polymer blends showed that the T_g was greatly decreased by increasing the ratio of the PMMA component in the polymer blends. Moreover, the T_g of PS/PMMA blends was found to decrease with increasing irradiation dose. The depression in T_g was noticeable in the case of blends rich in PMMA component. The TGA thermograms showed that the thermal stability of the unirradiated polymer blends decreases with increasing the ratios of PMMA component. Also, it was found that the presence of PS polymer in the blends affords protection against gamma radiation degradation and improves their thermal stability. However, exposing the polymer blends to high doses of gamma radiation caused oxidative degradation to PMMA components and decreased the thermal stability. The investigation of the kinetic parameters of the thermal decomposition reaction confirm the results of thermal stability. The FTIR analysis of the gamma‐irradiated polymer blend films gives further support to the TGA data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 509–520, 1999     

Effects of a Hindered Amine Stabilizer (HAS) on radiolytic and thermal stability of poly(methyl methacrylate)

Commercial Poly(methyl methacrylate) (PMMA) containing Tinuvin 622, a Hindered Amine Stabilizer (HAS), in 0.3% (wt/wt) concentration was investigated. The samples were irradiated with gamma radiation (⁶⁰Co) at room temperature in air. The viscosity‐average molecular weight (M_v) was analyzed by viscosity technique. Both control PMMA (without HAS) and PMMA + 622 (with HAS) showed a decrease in molecular weight with the increase in dose, reflecting the random scissions that occurred in the main chain. The G value (scissions/100 eV of energy transferred to the system) was also obtained by viscosity analysis. G value results showed that the addition of Tinuvin 622 into the PMMA matrix significantly decreased the number of scissions/100 eV at dose range of 0–60 kGy. Analysis of infrared spectra showed a decrease in the carbonyl index (CI) in irradiated samples. However the CI decrease was found lower for PMMA + 622 than for control PMMA sample. Thermogravimetric analysis (TGA) revealed that maximum decomposition temperature of additive PMMA is 42°C higher than control PMMA for unirradiated system. On the other hand this difference is not significant in irradiated systems at 60‐kGy irradiation dose. The activation energy of the thermal degradation of PMMA was 165 kJ/mol, this activation energy increased 60 kJ/mol when Tinuvin 622 was added to PMMA matrix. Therefore Tinuvin 622 is a suitable radiostabilizing agent for commercial PMMA in a 0–60 kGy dose interval. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of titanium dioxide pigments on the optical properties of polycarbonate and polypropylene for diode laser wavelengths

In laser transmission welding of polymers, additives and colorants could influence the welding result. In this work, polypropylene and polycarbonate probes colored with titanium dioxide (TiO₂) pigments of various concentrations are investigated. The probes are produced using an extrusion process to obtain a homogeneous distribution of colorants. The TiO₂ pigments change the optical properties of the polymers considerably. The measured reflectance increases with increasing pigment load while the transmittance decreases. From the measured data of transmittance, reflectance, and collimated transmittance, the scattering, the absorption coefficient, and the anisotropy factors are calculated. It is shown that the scattering coefficient at 1530 nm (laser) wavelength is smaller than for 968 nm, while the absorption coefficient is negligible for both wavelengths. Scattering coefficient and anisotropy factor are used to simulate the propagation of the laser radiation in the polymers. The influence of the scattering process on the beam propagation is represented by the change of the power density distribution. It is shown that the maximum intensity of the distribution is reduced more than the transmittance with increasing pigment concentration. The effect is higher for 968 than for 1530 nm wavelength making the larger wavelength more favorable for transmission welding. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40073.     

Radiation Stability of Spark‐Plasma‐Sintered Lead Vanadate Iodoapatite

Spark‐plasma‐sintered lead vanadate iodoapatite Pb_9.85(VO₄)₆I_1.7, a promising nuclear waste form for the immobilization of I‐129, was irradiated with energetic ions, electrons, and gamma rays, to investigate its radiation stability. In situ TEM observation of the 1 MeV Kr²⁺ irradiation shows that lead vanadate iodoapatite generally exhibits higher tolerance against ion irradiation‐induced amorphization than lead vanadate fluorapatite, and the spark plasma sintering can further enhance its radiation stability attributed to the enhanced crystallinity, reduced defect concentration, and denser microstructure. The critical amorphization dose and critical temperature for the SPS‐densified iodoapatite at 700°C are determined to be 0.25 dpa at room temperature and 230°C, respectively. No significant phase transformation or microstructural damage occurred under energetic electron and gamma irradiations. Raman spectra of gamma‐ray‐irradiated iodoapatite indicate improved V–O bond order at 500 kGy dose. Generally, the spark‐plasma‐sintered iodoapatite exhibits excellent radiation stability for nuclear waste form applications. The significantly enhanced radiation stability of the SPS‐densified iodoapatite suggests that SPS holds great promise for fabricating iodoapatite waste form with minimum iodine loss and optimized radiation tolerance for effective management of highly volatile I‐129.     

Thermal behavior of gamma‐irradiated amorphous poly (ethylene terephthalate) films

Poly (ethylene terephthalate) (PET) was irradiated in air by gamma rays at dose rate of 28 kGy/h for doses up to 3500 kGy. The influences of gamma irradiation on the glass transition and degree of crystallinity were investigated by differential scanning calorimetry. For amorphous PET, the observed glass transition temperature T_g and step of heat capacity ΔC_p decreased with absorbed dose. These decreases were attributed to a predominant chain scission process. The glass transition temperature may be useful as an indicator of radiation to the PET. The results also showed that such chain scission increases in mobility lead to a greater crystallizability. POLYM. ENG. SCI. 46:1374–1377, 2006. © 2006 Society of Plastics Engineers     

Effect of melting atmospheres on the optical property of radiation-hard fluorophosphate glass

High-energy radiation in space and nuclear irradiation environment induces colour centres in optical glass, causing solarisation, and a serious condition can render optical systems and optical loads unusable. To develop space radiation-resistant optical glass, CeO₂-stabilised radiation-hard fluorophosphate glass was prepared under three different atmospheres (nitrogen, oxygen, and ambient air). The glass-melting atmospheres' effects on the glass's transmission, defect formation, and structural changes before and after exposure to gamma radiation were investigated by a comprehensive study on their transmittance, absorption, and electron paramagnetic resonance spectra. Introducing a small amount of CeO₂ (～0.34 wt%) into the fluorophosphate base glass converted NBO and BO into ABO in the glass network, red-shifted the UV absorption edge, and decreased the optical density increment by almost half after radiation. As the total dose of gamma radiation increased, the transmittance of the irradiated glass at a wavelength of 385 nm significantly increased due to absorption of POHC2 defects. After exposure to 250 k of rad gamma irradiation, the corresponding optical density increment per centimeter thickness at 385 nm of the radiation-hard fluorophosphate glass that melted in the nitrogen, oxygen, and air atmospheres decreased from 1.839 to 1.388 and 1.215. As it melted in air, the NBO ratio of the fluorophosphate glass reached the lowest level and the Ce⁴⁺ ratio in the glass was 92.49%, which helped suppress the generation of POHC, Fe³⁺, PO₄-EC, and PO₃-EC defects during the gamma irradiation process, improving the glass's radiation resistance.     

Effect of gamma‐irradiation on the mechanical behavior of EPDM rubber‐recycled newsprint microfibers composites

Waste newsprint paper was collected from the local market and subjected to chemical pulping using 2 M NaOH. The fiber, after getting rid of water, was treated again using 2 M HCl solution for the same time period. The obtained newsprint microfibers (NPFs) were characterized by using scanning electron microscopy (SEM), X‐ray diffraction (XRD), and Fourier transform infrared spectra. Then the dried and grounded NPF batch was mixed with ethylene propylene diene monomer (EPDM) rubber using different concentrations ranged from 5 to 50 phr. The prepared composites were irradiated by using gamma rays at different doses from 20 to 100 kGy. The mechanical properties of prepared EPDM/NPFs composites such as tensile strength (Ts), elongation at break (E_b%), tensile modulus (M₁₀₀), toughness (T_t), and crosslink density (Cd) were measured as a function of fiber contents and irradiation dose. The results indicated that the tensile strength (Ts) increases with increasing microfibers contents up to 10 phr and irradiation dose up to 40 kGy, while E_b% decreases as the fibers content and irradiation dose increase. M₁₀₀ and Cd values increase with increasing fibers content up 50 phr fibers and irradiation dose up to 60 kGy. The results also concluded that the toughness values of EPDM/NPFs composites reach its maximum degree when using 10 phr NPFs concentration and 60 kGy irradiation dose. J. VINYL ADDIT. TECHNOL., 25:198–212, 2019. © 2018 Society of Plastics Engineers     

The Influence of Gamma Irradiation Dose on the Formation of Radiation Defects in xCu2Se · (1 – x)As2Se3 Glasses

The defects generated under exposure to gamma radiation at a temperature of 77 K in glasses lying along the xCu₂Se · (1 – x)As₂Se₃ quasi-binary join are studied by the electron paramagnetic resonance (EPR) method. The intensity of EPR signals (I) of radiation-induced defects associated with dangling bonds of atoms in the glass network is examined as a function of the gamma irradiation dose (D = 10⁴–1.5 × 10⁵ Gy). Unlike the As₂Se₃ glass, for which the signal intensity increases almost linearly with an increase in the irradiation dose, the curves I(D) for ternary glasses are characterized by saturation dependent on the copper content in the network. The saturation of the dependences I(D) at a high copper content is explained by the formation of regions with an increased Cu content and the enhancement of the electron–phonon interaction, which prevents the stabilization of dangling bonds in the glass network. The concentration of NO₂ paramagnetic molecules formed by nitrogen and oxygen uncontrollable impurities increases linearly with an increase in the irradiation dose.     

Preparation and properties of poly(methyl methacrylate)/iron carbonate(p) nanocomposites

The mass transport of methanol mixed with ferric chloride hexahydrate (FeCl₃ · 6H₂O) in poly(methyl methacrylate) and poly(methyl methacrylate)/iron carbonate particulate_(p) nanocomposites is prepared by chemical vapor crystallization and the resulting materials, which are subjected to characterization to evaluate thermal and optical properties, have been investigated. Mass transport is an anomalous and endothermic process and satisfies the van't Hoff plot. We have prepared successfully poly(methyl methacrylate)(PMMA)/iron carbonate particulates nanocomposites using CO₂ gas slowly diffused into saturated solvent mixture‐treated poly(methyl methacrylate) for 48 h. After SEM observation, approximately 80 nm iron carbonate particulates were precipitated and evenly distributed in the poly(methyl methacrylate) matrix. In comparison with solvent mixture‐treated PMMA, the cut‐off wavelength of transmittance in nanocomposites shifts to the shorter wavelength side (red shift). The presence of nanoscale iron carbonate particulates increased the glass transition temperature of the nanocomposites as determined by differential scanning calorimeter, and the glass transition temperature increased with increasing content of nanoscale iron carbonate particulates. The FTIR spectra of solvent mixture‐treated poly(methyl methacrylate) and nanocomposites are also studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2329–2338, 2005     

Thermal,structural, and optical properties of γ‐irradiated poly(vinyl alcohol)/poly(ethylene glycol) thin film

Poly(vinyl alcohol)/poly(ethylene glycol) (PVA/PEG) copolymer was prepared using casting technique. The obtained PVA/PEG thin films have been irradiated with gamma rays with doses ranging from 1.5 to 20 Gy. The resultant effect of gamma irradiation on the thermal properties of PVA/PEG has been investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The onset temperature of decomposition T_o and activation energy of thermal decomposition E_a were calculated, results indicating that the PVA/PEG thin film decomposes in one main weight loss stage. Also, the gamma irradiation in dose range 4–12 Gy led to a more compact structure of PVA/PEG copolymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition. The variation of transition temperatures with gamma dose has been determined using DTA. The PVA/PEG thermograms were characterized by the appearance of an endothermic peak due to melting of crystalline phase. In addition, structural property studies using X‐ray diffraction and infrared spectroscopy were performed on both nonirradiated and irradiated samples. Furthermore, the transmission of the PVA/PEG samples and any color changes were studied. The color intensity (E was greatly increased with increasing the gamma dose and was accompanied by a significant increase in the blue and green color components. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of γ-irradiation on chlorendic acid based unsaturated polyesters

The effect of gamma ray irradiation on chlorendic acid based unsaturated polyesters was studied. Four different types of unsaturated polyesters, made by varying the molar ratios of chlorendic acid to isophthalie acid were irradiated with a Co⁶⁰ qource. After irradiation, the chlorine content decreases rapidly as the isophthalate content in the polyester chain increases. As the chlorendle acid content increases, the change in acid value after irradiation decreases. The increase in intrinsic viscosity is quite marked in high isophthalate containing polyesters after gamma ray irradiation and there is a noticeable decrease in intrinsic viscosity after gamma irradiation of high chlorendic acid containing polyesters. The effect of gamma irradiation on the percentage of cis and trans forms of these polyesters was studied with the help of infrared spectra. It appears that as the chlorendic acid content increases, on gamma irradiation conversion from trans unsaturation to cis unsaturation increases rapidly.     

Morphological studies of elongated PMMA by excimer formation

The technique of excimer fluorescence has been employed to study the orientational structure of poly (methyl methacrylate) (PMMA). The PMMA films used contain a small amount of naphthalene‐labeled PMMA, and were uniaxially stretched to various elongation at 80°C. The results show that the fluorescence intensity ratio of excimer to monomer, I_E/I_M , increases with the elongation ratio. The increase of excimer forming sites in the system after drawing is attributed to the orientation of both the chain segments and side groups along the drawing direction. The orientation leads to highly dense packing of the PMMA molecules. The conclusion drawn from excimer fluorescence is in agreement with those from other techniques. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1869–1872, 2000     

Effects of vacuum ultraviolet on the structure and optical properties of poly(tetrafluoroethylene) films

The effects of vacuum ultraviolet (VUV) at wavelengths of 5–200 nm on the microscopic structure and optical properties of poly(tetrafluoroethylene) (PTFE) films were investigated. X‐ray photoelectron spectroscopy analysis showed that the C_1s spectra changed from a single peak at 292.8 eV to multiplex peaks with binding energies of 284.6, 286.6, 288.6, 290.5, and 293.0 eV after VUV irradiation at 680 esh. With an increasing irradiation dose, the C_1s peaks at 290.5 and 293.0 eV disappeared. After the PTFE film specimens irradiated at 1600 esh were sputtered with argon ions for 3 min, the C_1s peaks at 290.5 and 293.0 eV appeared again, and the height of the peaks at 286.6 and 288.6 eV increased. The content of fluorine decreased after VUV irradiation. The content of fluorine in the film surface layer decreased significantly with the increase in the VUV intensity, but it did not change with the irradiation dose. Fourier transform infrared (FTIR) analysis results indicated that some conjugated bonds, such as ? FC?CF? , were formed during VUV irradiation, but no CH absorption bands were observed in the FTIR spectra; this indicated that the increase in the height of the C_1s peak at 284.6 eV arose mainly from the carbon–carbon bonds, that is, from carbonification. The spectral transmittance of the PTFE film decreased gradually with an increasing VUV irradiation dose, and at a given dose, the lower the intensity was of the VUV irradiation, the greater the change was in the spectral transmittance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 115–121, 2003     

Wavelength sensitivity of the photodegradation of poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) was photolyzed with monochromatic light of wavelengths 260, 280, 300, 320, 400, and 500 nm in vacuo by the use of the Okazaki Large Spectrograph. UV spectral changes, the quantum yields of main-chain scission (?cs), and effects of wavelength were investigated. UV spectral changes around 280 nm were observed with irradiation at 260 nm. The ?cs has a maximum value in case of irradiation with 300 nm light. It turned out that photodegradation of PMMA took place by irradiation of 260–320 nm light but did not by irradiation with the light longer wavelength than 340 nm. The average values of ?cs obtained in this work were 0.84 × 10^?4, 1.06 × 10^?4, 4.21 × 10^?4, 1.23 × 10^?4, 0, and 0 for irradiations at 260, 280, 300, 320, 400, and 500 nm, respectively. It was found that the photo-induced side-chain scission initiates the main-chain scission of PMMA by irradiation of 260 and 280 nm light. © 1993 John Wiley & Sons, Inc.     

Effects of inclination angle applied to a polyethylene terephalate substrate before the coating of Al-doped ZnO on film quality and mechanical and optical properties

A flat plate in the deposition stage is designed to be tilted flexibly with an angle such that an inclination angle is formed between the ion beam and the direction normal to a polyethylene terephthalate (PET) substrate. Five kinds of PET/aluminum-doped zinc oxide specimen, with 0°, 15°, 30°, 45°, and 60° inclination angles, respectively, were prepared to examine the effect of inclination angle on the mechanical, electrical, and optical properties and morphology of coating films. Using the peaks of the ZnO (002) and ZnO (103) planes in X-ray diffraction analyses, the relative intensity ratios for these two crystallines are defined and used to evaluate the parameters of composite grain size ((g)_Composite) and residual stress ((σ)_Composite). The experimental results indicate that (σ)_Composite increases but (g)_Composite mostly decreases with increasing inclination angle. A nearly linear relationship is found between (g)_Composite and the d-spacing parameter ((d)_Composite). They both decrease with increasing inclination angle. The intensities of ZnO (002) and ZnO (103) planes significantly influence the mean transmittance, absorption, and reflection in the wavelength range of 801–2500 nm (near-infrared). An increase in the relative peak intensity of ZnO (002) increases the mean transmittance and thus lowers the mean absorption and reflectance. The average transmittance decreases and the average reflection increases in the wavelength range of 300–2500 nm with increasing inclination angle. Increasing the composite grain size decreases the average reflection. The ZnO film thickness is proportional to the mean surface roughness of the film.     

Water transport in crosslinked 2‐hydroxyethyl methacrylate

Water transport in crosslinked 2‐hydroxyethyl methacrylate (HEMA) was investigated. Crosslinked HEMA was irradiated by gamma ray in vacuum for this study. The sorption data of de‐ionized water transport in crosslinked HEMA subjected to various gamma ray dosages are in excellent agreement with Harmon's model which accounts for Case I, Case II, as well as the anomalous transport processes. The diffusion coefficient for Case I transport and velocity for Case II transport satisfy the Arrhenius equation for all dosages. The transport process was exothermic and the equilibrium‐swelling ratio satisfied the van't Hoff plot. The pH value of de‐ionized water after the sorption/de‐sorption treatment of the irradiated crosslinked HEMA specimen was analyzed. The transmittance of irradiated crosslinked HEMA treated by de‐ionized water was also studied. The effect of irradiation on the polymer chains was revealed by the measurement of glass transition temperature and the quantitative determination of water structures in crosslinked HEMA hydrogel. The UV cut‐off wavelength of crosslinked HEMA shifted to longer wavelength side with increasing irradiation dosage, but the trend of transmittance after water treatment was opposite. The effect of specimen thickness on water transport was also studied.     

Effect of PMMA addition on characterization and morphology of PVDF

Polyvinylidene fluoride and polymethylmethacrylate (PVDF/PMMA) films were blended with different concentrations by casting method. Structural, spectroscopic, and morphological characteristics of both the interface and the surface of the films have been investigated. The blends were characterized using X‐ray diffraction (XRD), Fourier transform infrared (FTIR), UV–visible, differential thermal analysis (DTA), and scanning electron microscopy (SEM). All measurements reveal that the blends take place based on the influence of PMMA content on PVDF. FTIR results indicate the possible interactions between carbonyl group of PMMA and CH₂ groups of PVDF which indicates the formation of blends. Optical absorption spectra suggested the presence of an optical gap (E_g) which decreased with increasing PMMA content. UV/VIS spectra were characterized by a sharp edge and a window of wavelength range 290–350 nm for some blends. The optical window can be used as an optical sensor or band pass filter. The degree of crystallinity was found to decrease with increasing PMMA content, which was confirmed by XRD and DTA analysis. SEM micrograph shows spherulites which increase with the addition of PMMA and it becomes sharper and contains a longitudinal shape. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Film formation of poly (methyl methacrylate) latex with pyrene functional poly (divinylbenzene) microspheres prepared by click chemistry

This work reports on the application of steady state fluorescence (SSF) technique for studying film formation from poly(methyl methacrylate) (PMMA) latex and poly(divinylbenzene) (PDVB) microsphere composites. Pyrene (P) functionalized PDVB cross‐linked spherical microspheres with diameters of 2.5 μm were synthesized by using precipitation polymerization technique followed by click coupling reaction. The diameter of the PMMA particles prepared by emulsion polymerization were in the range of 0.5–0.7 μm. PMMA/PDVB composite films were then prepared by physically blending of PMMA latex with PDVB microspheres at various composition (0, 1, 3, 5, 10, 20, 40, and 60 wt%). After drying, films were annealed at elevated temperatures above T_g of PMMA ranging from 100 to 270°C for 10 min time intervals. Evolution of transparency of the composite films was monitored by using photon transmission intensity, I_tr. Monomer (I_P) and excimer (I_E) fluorescence intensities from P were measured after each annealing step. The possibility of using the excimer‐to‐monomer intensity ratio (I_E/I_P) from PDVB microparticles as a measure of PMMA latex coalescence was demonstrated. Diffusion of the PMMA chains across the particle–particle interfaces dilutes the dyes, increasing their separation. The film formation stages of PMMA latexes were modeled by monitoring the I_E/I_P ratios and related activation energies were determined. There was no observable change in activation energies confirming that film formation behavior is not affected by varying the PDVB composition in the studied range. SEM images of PMMA/PDVB composites confirmed that the PMMA particles undergo complete coalescence forming a continuous phase in where PDVB microspheres are dispersed. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis and characterization of new biodegradable fluorescing poly(amide‐anhydrides)

Biodegradable/alternate/poly(amide‐anhydrides), [? C(O)PhNHC(O)(CH₂) _nC(O)O? ] _x, were synthesized by melt polycondensation, where n was 2, 3 or 4. The polymers have been characterized by NMR, DSC, wide‐angle X‐ray diffractometry and fluorometry. All the polymers are amorphous and their T_g ranges from 60 to 80 °C. Poly(p‐(carboxyethylformamido)benzoic anhydride) (PCEFB) as a film or in solution in chloroform can emit strong fluorescence, which was not observed for the other two polyanhydrides (n = 3, 4). The maximum emission wavelength varies with the excitation wavelength, 480 and 520 nm at the excitation wavelength of 470 nm, and 430 nm at 356 nm. In addition, the fluorescence intensities increase linearly with the molecular weight of PCEFB. Such inherent fluorescing properties of PCEFB, together with its biodegradability, make the polymer a potential visible matrix for drug delivery. © 2001 Society of Chemical Industry