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     

Electron spin resonance studies on graft copolymerization of gaseous styrene onto preirradiated polypropylene. II. Preirradiation under vacuum

Graft copolymerization of gaseous styrene was carried out at 40°C onto polypropylene preirradiated under vacuum. In order to investigate the origin of graft initiation activity, ESR spectra of irradiated polymers were measured and discussed. Although there are about three times as many radicals trapped in the sample irradiated at ?78°C as in the sample irradiated at room temperature, both the samples showed nearly same degree of grafting. This is due to the ineffectiveness of radicals trapped in the amorphous region for grafting. The samples irradiated under vacuum showed more grafting than those irradiated in an oxygen atmosphere. This is compatible with the conclusion in the previous paper that in grafting of polypropylene irradiated in an oxygen atmosphere the carbon radicals produced by hydrogen abstraction by trapped peroxy radicals are the effective active centers.     

Melting and chemical behaviors of isothermally crystallized gamma-irradiated syndiotactic polystyrene

Melting and chemical behaviors of isothermally crystallized gamma-irradiated sPS have been investigated using differential scanning calorimetry, FTIR, and X-ray diffraction techniques. Amorphous sPS samples were subjected to gamma radiation in vacuum and in oxygen at different doses from 200 to 1000 kGy. Irradiated samples were heated to 310 °C, cooled to 220-260 °C range, held for 10 min, and re-melted. Three melting endothermic peaks observed for irradiated and non-irradiated samples isothermally crystallized at 220 °C were decomposed into individual Gaussian distributions, and enthalpies of the total melting endotherm and individual peaks were determined. Both α and β crystalline forms coexist in the crystallized irradiated sPS, regardless of the radiation treatment environment. Dose and irradiation environment have a great effect on the melting behaviors and chemical structures of the isothermally crystallized gamma-irradiated sPS. Crystallinity increases with increasing dose of irradiation in both vacuum and oxygen, with level of increase is greater in oxygen. The three melting peak temperatures decrease with increasing dose regardless of irradiation environments. Ketone and aldehyde oxidized products are formed in the isothermally crystallized gamma-irradiated sPS in oxygen through a combination of hydrogen abstraction or chain scission process and hydroxyl free radicals formation.     

真空烧结氧化铝的实验研究

以150nm Al2O3粉为原材料,用真空烧结的方法来烧结Al2O3陶瓷。实验发现:在真空条件下烧结时,氧化铝与石墨间会发生还原反应,使真空烧结得到的样品质量明显小于常压烧结样品的质量;而且,真空烧结样品的颜色由白色变成了灰色。其原因是在真空条件下烧结时,烧结气氛为还原性气氛,在样品表面产生氧空位。氧空位捕获电子,产生带有一个电子氧空位的F+色心。     

Electron spin resonance studies on graft copolymerization of gaseous styrene onto preirradiated polypropylene. III. Preirradiation under vacuum followed by exposure to oxygen at −78°C

Grafting of styrene vapor was carried out onto polypropylene γ-irradiated under vacuum followed by exposure to oxygen at ?78°C. A comparison with the results on polypropylene irradiated in an oxygen atmosphere leads to an interesting result. Two samples were irradiated at room temperature under vacuum and in an oxygen atmosphere, respectively, the former being followed by exposure to oxygen. Although irradiation was carried out at room temperature for either sample and nearly the same amounts of the peroxy radicals are trapped, the former showed more grafting than the latter. The origin of this difference was investigated by means of electron spin resonance. Significant differences were observed in ESR spectra as well as in isothermal decays of the trapped peroxy radicals. In the former sample, the trapped peroxy radicals had a higher mobility, and consequently a significant hydrogen abstraction by the peroxy radicals was observed during storage at 40°C. This result supports the conclusion of the previous paper that the radicals effective in the grafting reaction of polypropylene preirradiated in an oxygen atmosphere are the carbon radicals which are produced by hydrogen abstraction by the peroxy radicals.     

Interaction of Gamma Rays with Calcium Aluminoborate Glasses Containing Holmium or Erbium

The optical absorption spectra of nominally pure and rare-earth-ion-doped (Ho³⁺ or Er³⁺) calcium aluminoborate (cabal) glasses were measured from 190 to 900 nm before and after γ-ray irradiation. The induced absorption spectra, calculated as the difference between the spectra of the irradiated and the unirradiated glasses, exhibit the characteristic absorption bands caused by the respective rare-earth ions. The intensity of the induced bands depends on the rare-earth oxide content. The response of the cabal glass to γ-ray irradiation is related to the formation of color centers associated with the intrinsic defects in the lattice structure of the cabal glass. The rates of formation and annihilation of the color centers are believed to approach saturation or equilibrium with prolonged irradiation.     

Application of radiation curing in the preparation of polycarbosilane-derived SiC fibers

Polycarbosilane fibers were irradiated by gamma-rays under vacuum and by electron beam in He gas flow or under vacuum at room temperature. Free radicals on Si and C atoms were produced. Most radicals reacted with each other, causing cross-links between polycarbosilane molecules. Some radicals, which did not contribute to cross-linking, were fairly stable under vacuum or in inert gas at room temperature but oxidized on exposure to air. The number of stable radicals under vacuum could be decreased by annealing. The remaining radical concentration was about 1% after annealing at 513 K. By a combination of radiation curing and annealing, SiC fibers with smaller quantities of oxygen were prepared. The mechanical properties of the SiC fibers showed a high tensile strength of 2.5 GPa after heat treatment at 1773 K. On the other hand, polycarbosilane fibers could be cured by radiation oxidation at room temperature, that is, gamma-ray or electron irradiation in oxygen, and the oxygen content could be well controlled by irradiation dose and dose rate. The SiC fibers obtained by the radiation oxidation had an oxygen gradient from the surface to the center which was dependent on the radiation oxidation conditions.     

Effect of simulated low earth orbit radiation on polyimides (UV degradation study)

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge-transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-centered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was twofold higher than for vacuum irradiation and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C? O binding energy peak relative to the C? C peak was believed to be associated with an aromatic ring-opening reaction. © 1995 John Wiley & Sons, Inc.     

EPR kinetics in irradiated syndiotactic polystyrene at elevated temperatures

Free radicals are formed upon irradiation of polymers. The annealing of γ-ray irradiated syndiotactic polystyrene (sPS) with doses 10, 23 and 36 kGy was studied with electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra are possibly attributed to three types of radicals, (a) the benzyl radical Ra, (b) resonance structure of the phenyl radical Rb, and (c) carbon-superoxide-centered radical Rc with three-, four-, and single-line features, respectively. Radical Ra can be easily formed by the removal of the proton from the tertiary carbon; radical Rb is created from delocalization of the spin of the radical Ra onto the benzene ring; and radical Rc may be generated from the interaction of a carbon-centered radical with dioxygen from the air which forms a carbon-superoxide center. By comparing EPR spectra of the radicals with a DPPH standard, the spin numbers of the radicals can be calculated. The spin number of all radicals decreases exponentially with time in the temperature range of 60-90 °C regardless of dose of the irradiation. The annealing of Ra, Rb, and Rc follows first-order kinetics. The activation energies of the annihilation are determined to be 15.8-19.0, 16.0-19.5, and 23.2-26.6 kJ/mol for radicals Ra, Rb, and Rc, respectively. The kinetic study presented herein can serve as a criterion for γ-ray irradiation process in various applications, such as sterilization of polymer materials and devices.     

XPS and ESR studies of the photodegradation of polyamidoimide and polyimide in O2, O2 + N2, air,N2, and vacuum atmospheres

The photostability of polyamidoimide (PAI) and polyimide (PI) films has been studied. UV irradiation caused a great change in the composition and structure of the film surface. With irradiation in atmospheres such as air, oxygen, and an oxygen—nitrogen mixture, the Cls spectrum had a distinct structure at high binding energy, and the O/C and N/C ratios were considerably increased. On the other hand, in nitrogen and under vacuum, the O/C and N/C ratios remained almost unchanged during an earlier stage of irradiation, but in the latter stage for the nitrogen atmosphere these ratios decreased to a broad minimum and then increased with an increase of irradiation time. UV irradiation also produced free radicals in the polymer films; PAI gave a much stronger ESR signal intensity than PI. The signal intensity vs. irradiation time curve was strongly influenced by irradiation atmospheres. In atmospheres containing oxygen the curve exhibited a broad maximum during an initial stage of irradiation, while under vacuum and in nitrogen the signal intensity increased greatly in the latter stage. The formation of free radicals during an earlier stage of irradiation in atmospheres containing oxygen was promoted by the oxygen incorporated at the film surface, while the radical production under vacuum was considered to be due to rupturing of bonds in the bulk material. The decay of free radicals in the dark after irradiation occurred at a faster speed in oxygen atmospheres than under vacuum.     

Radiation‐induced crosslinking of ultra high molecular weight polyethylene fibers by means of electron beams

Crosslinking of ultra high molecular weight polyethylene fibers (UHMW‐PE fibers) is investigated by means of electron beam irradiation. The structure and mechanical properties of the fibers in different irradiation atmospheres are discussed. The results show that the gel fraction and crosslinking density increase with the increase of absorbed dose. The swelling ratio and average molecular weight of crosslinked net decrease with the increase of absorbed dose. The relation between s + s^?1 of the UHMW‐PE fibers and reciprocal irradiation dose 1/R is obtained. The tensile strength and failure elongation decrease with the increase of absorbed dose, and the tensile modulus increases with the increase of absorbed dose. The samples are irradiated in air, vacuum, and acetylene atmospheres, separately. The radiation effects, such as crosslinking fraction and mechanical properties of UHMW‐PE fibers, are the most significant in acetylene atmosphere in comparison with in air and in vacuum. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1761–1764, 2005     

Production of fine powder from silk by radiation

Silk fine powder was prepared directly from silk fibers irradiated with an accelerated electron beam (EB). Irradiated silk fibers were well pulverized only by physical crushing using a ball mill without any chemical pretreatment. Silk fibroin fibers were irradiated at ambient temperature in the dose range of 250–1 000 kGy. Although unirradiated silk fibers were not pulverized at all, irradiated fibers were easily pulverized and showed a high conversion efficiency from fiber to powder at high irradiation doses. The presence of oxygen in the irradiation atmosphere enhanced pulverization of the silk fibers. The electron microscopic observation showed that the minimum particle size of silk powder obtained from fibers irradiated at 1 000 kGy in oxygen was less than 10 μm. It was found that fibroin powder obtained in this work dissolved remarkably in water, thought unirradiated fibroin fibers were insoluble even in hot water. The soluble fraction was about 60% of fibroin powder for 1 000 kGy irradiation in oxygen.     

Effects of ionizing radiations on fats. II. Accumulation of peroxides and other chemical changes

The accumulation of peroxides, carbonyl com-pounds and reducing substances during irradia-tion and post-irradiation storage of pure fatty acid methyl esters has been studied. Irradiation and storage of irradiated methyl myristate under vacuum results in formation of small quantities of these compounds. Irradiation under oxygen gives peroxides and carbonyl com-pounds in yields indicating that every ionization results in the formation of one molecule of each group, and antioxidants have no effect on the formation of these compounds during irradiation. Irradiation of methyl linoleate under vacuum results in destruction of pre-formed hydroperox-ides. During irradiation in oxygen, approximately one-eighth of the peroxides formed arises from the direct reaction of irradiation-induced free radi-cals with oxygen, while the rest is formed through a chain mechanism with an average chain length of 7. Peroxides continue to accumulate in irradiated methyl linoleate stored under oxygen at a rate increasing with initial irradiation dose. Antioxidants have some effect in retarding the formation of peroxides during irradiation of methyl linoleate and during post-irradiation stor-age, but the effect is small compared to their antioxygenic activity toward simple autoxidation. The effect varies with the nature of the antioxi-dant and with irradiation dose. Propyl gallate is much less effective than butylated hydroxy-anisole and appears to be easily destroyed during irradiation. For paper I of this series, see Ind. Eng. Chem.49. 1713 (1957). Presented at the AOCS Meeting in Minneapolis, 1963.     

Interaction of γ-rays with Some Alkali-Alkaline-Earth Borate Glasses Containing Chromium

The change in the visible spectra of some irradiated ternary borate glasses containing chromium has been studied by increasing the γ-ray doses with changing alkali content or increasing chromium concentration. In the glass without chromium, the γ-rays induce two absorption bands which are attributed to the formation of positive hole centers, whereas in the glass containing chromium at least three absorption bands are observed. The results showed that the visible absorption bands before and after γ-ray irradiation exhibited changes with the radiation dose and/or the chemical composition of the glass. The response of the glasses to γ irradiation is related to the creation of defect color centers, the approach of a saturation condition, and the possible photochemical effect on the transition metal.     

TGA analysis of γ‐irradiated linear low‐density polyethylene

Linear low‐density polyethylene (LLDPE), based on butene‐1 or hexene‐1, was irradiated with γ‐rays under vacuum or in the presence of air. The study focused on the influence of the dose rate and the γ‐dose on the thermal properties of LLDPE. Differential scanning calorimetry, thermogravimetric analysis (TGA), and TGA/FTIR techniques were used to address the thermal behavior as a result of γ‐irradiation. During this irradiation, competition between crosslinking and scission reactions, subsequent to oxidation reactions, occurred in the polymeric material, which strongly depends on the experimental conditions. A decrease of the crystallinity for γ‐irradiated samples was observed in particular for samples irradiated under vacuum. This observation may be explained by increased hindrance of segment mobility due to crosslinking reactions that prevent crystal growth. TGA investigations revealed an enhancement of the thermal stability for samples irradiated under vacuum but not for those irradiated in air. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2790–2795, 2006     

The antioxidant effect of natural substances on lipids during irradiation of chicken legs

Entire fresh chicken legs were subjected to three pretreatments (packaged in air; packaged under vacuum; or marinated in natural plant extracts and packaged in air) followed by irradiation (0, 3, or 5 kGy). The control and irradiated chicken legs were stored at 4°C and analyzed for FA composition and sensory quality at predetermined intervals. Irradiation dose had a significant (P<-0.01) effect on FA derived from phospholipid but less than on FA derived from a neutral lipid. In general, levels of unsaturated FA decreased as the radiation dose increased; however, for marinated chicken legs irradiated with 5 kGy, levels of linoleic acid (C_18∶2) and arachidonic acid (C_20∶4) derived from the phospholipid fraction were significanlty (P≤0.05) higher than those irradiated in air or under vacuum. The concentration of FA also decreased significantly (P≤0.05) as storage time increased. For chicken legs packaged in air or marinated and then packaged in air, significant (P≤0.01) inverse correlations existed between high-carbon-number PUFA and lower-carbon-number (≤17) saturated FA; this relationship was not apparent in samples irradiated under vacuum. A processing combination of marinating and vacuum packaging might better control lipid oxidation and degradation in irradiated chicken. Panelists found no significant difference (P>0.05) in the flavor and oder intensity of cooked irradiated chicken legs and their nonirradiated equivalents.     

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     

The service of silicon-carbide electric heaters in different atmospheres

Conclusions The atmosphere in which the heating element works has a big influence on the life. A protective atmosphere (nitrogen, argon) creates the most favorable conditions for the life of the heater. Failure of the rod in these atmospheres occurs as a result of the reaction between the silicon carbide and impurities in the atmosphere — oxygen and water vapors, and also oxygen evolved from the material of the furnace. Furthermore, the silicon of the heater reacts with the SiC, which also tends to destroy the heater.In an oxidizing atmosphere (oxygen, carbon dioxide gas, and air) the service life is longer, the less active the oxidant. The most favorable is an air atmosphere and the least favorable oxygen.During the operation of the heater in vacuum at high temperatures, volatilization and dissociation of the silicon carbide occur, and also migration and volatilization of the silicon existing in the heater, and that formed as a result of dissociation.The shortest heater life was found in vacuum.     

Formation of 2,4-dinitrophenylhydrazones in high-density polyethylene film irradiated with ultraviolet light

Polyethylene films were irradiated in air by ultraviolet light. 2,4-Dinitrophenylhydrazine was reacted on the irradiated films. The changes in amounts of carbonyl groups and 2,4-dinitrophenynlhydrazones formed in the films were inferred by comparing their absorptions in the infrared and ultraviolet spectra, respectively. It seems that the contents of carbonyl groups formed in the amorphous regions in the high-density polyethylene films by the irradiation were larger than the contents of carbonyl groups formed in the amorphous regions in the low-density polyethylene films. The decreases in contact angles of water on the high-density polyethylene films by the irradiation were larger than the decreases in the contact angles on the low-density polyethylene films. The amounts of 2,4-dinitrophenylhydrazones formed in the irradiated high-density polyethylene films were less than the amounts of 2,4-dinitrophenylhydrazones formed in the irradiated low-density polyethylene films.     

Wood photography using light irradiation and heat treatment

To apply the coloring method using light irradiation and thermal treatment to print photographs on wood, the effect of the transmittance of negative films was investigated. ΔE* decreased with light irradiation when specimens covered with films with transmittances exceeding 20% were irradiated for 100 h. It was thought that this phenomenon was due to the decrease in Δb*. The color of light‐irradiated wood changed remarkably with thermal treatment; however, the change in the color of exposed specimens covered with films with transmittances exceeding roughly 20% became constant. Clear photographs could be printed on wood using negative films with transmittances less than approximately 20%. Furthermore, the difference between the maximum and minimum values of ΔE* after thermal treatment was about 22. Humans can distinguish four to seven colors that can be created by this method. © 2004 Wiley Periodicals, Inc. Col Res Appl, 29, 312–316, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.20027