Radical annihilation of γ‐ray‐irradiated contact lens blanks made of a 2‐hydroxyethyl methacrylate copolymer at elevated temperatures

The annihilation of the radicals in irradiated 2‐hydroxyethyl methacrylate copolymer was analyzed by the use of electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra were deconvoluted into three radicals: a quartet (Ra), a triplet (Rb), and a broad singlet (Rc). Radical Ra was attributed to coupling with a methyl radical and/or a doublet or triplet with about the same hyperfine coupling due to a methylene radical. Radical Rb was due to a methylene radical produced by main‐chain scission. Radical Rc was attributed to various free radicals without coupling to protons. By comparing the EPR spectra of radicals Ra, Rb, and Rc with the spectrum of a 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) standard with a known spin number, we calculated the spin numbers of the radicals, which decreased with time in the temperature range 25–45°C, regardless of the irradiation dose. The annealing of Ra and Rb and the annealing of Rc at longer times followed second‐order kinetics; these were different from the kinetics for the color formation and defect‐controlled hardening of polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

EPR study of radical annihilation kinetics of γ-ray-irradiated acrylic (PMMA) at elevated temperatures

High-energy irradiations of polymers may cause bond cleavage or crosslinking and change the structures and physical properties of the polymers, which may offer various applications. Despite wide investigation, relationship between the kinetics and mechanism of annihilation after irradiations and the structure and some physical properties of irradiated polymers is still poorly established. We have been exploring such possible relationship and report herein investigation of the kinetics of radical annihilation of γ-ray irradiated acrylic, i.e., poly(methylmethacrylate) or PMMA, at elevated temperatures with EPR spectroscopy. The EPR spectra consist of three components, a quintet Ra, a quartet Rb, and a broad singlet Rc. Ra and Rb follow second-order annihilation kinetics, while the decay of the radical Rc is comprised of at least two parallel kinetic processes, a slow second-order pathway and a fast pathway which can be equally well fitted to first- or second-order kinetics. The kinetics is analogous to that for the radical decays in irradiated 2-hydroxyethyl methacrylate copolymer. On the basis of the large hyperfine coupling constant of 2.3 mT, Ra may be assigned to a radical adjacent to two groups of protons, such as a doublet of quartet with similar coupling constants due to an anti-methylene proton and a methyl group; the Rb signal, possibly a methyl radical; and the broad singlet Rc, a magnetically coupled combination species. Alternative assignments of the radicals have also been suggested. The rate constant increases with increasing dose for each radical at a given temperature, possibly due to increase in radical concentrations at higher doses. The rate constants satisfy the Arrhenius equation, suggesting a single mechanistic pathway for the annihilation process in the temperature range; wherein the activation energy decreases with increasing dose for all radicals, possibly due to higher concentrations of free radicals in close proximity produced at higher doses.     

Carbon radicals generated by solid polymers: Electron spin resonance spectroscopy for detection of species in water

Radicals generated in plastic medical devices (solid phase) by γ-rays or electron-beam irradiation during sterilization are known to cause oxidation of protein drugs, resulting in a loss or reduction in drug efficacy. The generation of radical species in water by the radical species in solid polymers has not been proved. Using electron spin resonance (ESR) spectroscopy, we confirm the generation of new radicals in water by γ-ray irradiated cyclic olefin polymers (COP). ESR measurements are obtained using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) as a spin probe and 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO) as a spin trap, in which the irradiated COP was immersed. The ESR signals indicate the TEMPOL radicals decline over time, suggesting the generation of new radicals. Conversely, the characteristic ESR signals of the adduct formed by the reaction between CYPMPO and the hydroxyl radical are observed. Thus, hydroxyl radicals are generated because of the migration of the radicals from COP to water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48604.     

Grafting of poly(ethylene-block-ethylene oxide) onto a vapor grown carbon fiber surface by γ-ray radiation grafting

To modify the surface of vapor grown carbon fiber (VGCF), poly(ethylene-block-ethylene oxide) (PE-b-PEO, M_n=1400, PEO content=50 wt%) was successfully grafted onto the surface by using γ-ray irradiation of the PE-b-PEO-adsorbed VGCF in solvent-free system. It is found that the percentage of polymer grafting reached 15.0% when the PE-b-PEO-adsorbed VGCF was irradiated by γ-ray over 40 kGy dose at 110 °C, but at the lower irradiation temperature of 75 °C, the grafting reaction scarcely proceeded. This indicates that polymer radicals formed by γ-ray irradiation were successfully trapped by VGCF surface above melting point of PE-b-PEO. On the other hand, when the dispersion of VGCF in THF solution of PE-b-PEO was irradiated, the percentage of PE-b-PEO grafting was less than 4.0%. It was confirmed by a field-emission scanning electron microscope (FE-SEM) that the surface of the VGCF was uniformly covered by grafted PE-b-PEO. In addition, the surface free energy of ungrafted and PE-b-PEO-grafted VGCF was determined.     

Optical Absorption and EPR Studies on Gamma-Ray Irradiated RE<Superscript>3+</Superscript>-Doped Fluorophosphate Glasses

We have studied the effect of γ-ray irradiation on optical absorption, emission and decay characteristics of RE³⁺ (RE?=?Sm, Eu and Dy)-doped fluorophosphate glasses. Electron paramagnetic resonance (EPR) study confirms the POHC and PO₃ EC defects induced in glasses by the γ-irradiation. The presence of induced defect centers significantly affects the optical and emission properties. The optical band gap values of the studied systems increased after the γ-ray irradiation. The phonon energy and electron–phonon coupling strength of Eu³⁺-doped fluorophosphate glass were determined from the phonon sideband analysis. The emission intensity of the RE³⁺ ions increased significantly after the γ-ray irradiation. The intensity parameter, R is the ratio of the intensities of the ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁ transitions of Eu³⁺ ion and Y/B intensity parameter is the ratio of intensities of the ⁴F_9/2 → ⁶H_13∕2/⁴F_9/2 → ⁶H_15/2 transitions of Dy³⁺ ion reveal that the local environment around the RE³⁺ ion changed after the γ-ray irradiation in the present system. The lifetime of excited states of RE³⁺ ions decreased after the γ-ray irradiation due to the formation of defects induced by the γ-ray irradiation. The CIE color coordinates were determined before and after the γ-ray irradiation for the Dy³⁺-doped glass system.     

A reorientation of the PO3-groups and radiation damage effect in ferroelectric phase transition studied by CW-EPR of PO32- radical in glycine·H3PO3 single crystal

EPR of γ-ray generated PO₃^2- radicals indicates that the four radical centers are equivalent in the paraelectric phase and become inequivalent in the ferroelectric phase due to a ±3° rotation. The phase transition temperature is shifted by irradiation from T_c = 224 K to T_c = 180 K. The molecular mechanism of the order-disorder phase transition is discussed     

Synthesis of conductive microspheres by radiation polymerization

A conductive monodisperse microspheres consisting of poly(ethylene glycol)dimethacrylate and methyloxycarbonyl-bicyclo[2.2.1]hepta-2,5-diene was synthesized by radiation induced polymerization. Ionic conductivity and relative dielectric constant were found to be greatly dependent on the content of poly(ethylene glycol)methacrylate in the copolymer. The diameter of the microspheres was 0.48-0.86 μm, in which the irradiation was carried out without stabilizer at a dose rate of 20 kGy/h with ⁶⁰Co γ-ray.     

Functionalization of multi-walled carbon nanotubes by free radical graft polymerization initiated from photoinduced surface groups

An easy method for preparing polymer-grafted multi-walled carbon nanotubes (MWCNTs) with high graft yields was developed by using free radical graft polymerization (FRGP) from photoinduced surface initiating groups on MWCNTs. The surface initiating groups were first formed by UV irradiation of MWCNTs previously modified with 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA-086) (MWCNTs-OH) in the presence of benzophenone in benzene, and the subsequent FRGP of vinyl monomers was carried out consecutively at 80 °C. The surface initiating groups were homolytically cleaved to surface radicals and semipinacol radicals by thermal activation, and the surface radicals initiated FRGP. Polystyrene, poly(butyl acrylate), poly(methyl methacrylate), and poly(2-hydroxyethyl methacrylate) were successfully grafted onto the surface of MWCNTs with graft yields of 46, 26, 37, and 53 wt.%, respectively, after 15 h of FRGP.     

Photochemical reactions of antioxidant sesamol in aqueous solution

Antioxidant intermediate radicals generated by continuous ultraviolet (UV) and pulsed UV laser irradiation of sesamol in aqueous solutions were investigated. Radical species with the intensity ratio of 1∶4∶6∶4∶1 were observed by using continuous wave electron paramagnetic resonance (EPR) with continuous UV irradiation. The radical was also observed after the irradiation. To observe the intermediate radical right after the excitation, Fourier transform EPR (FT EPR) was used. Trace amounts of the same radical were also detected by FT EPR with pulsed UV laser. Based on the hyperfine coupling constant (2.3 G) and g-value (2.0048), together with FT EPR results, this radical was found to be a benzoquinone anion radical. The radical might have been produced via multistep reactions of the excited sesamol in aqueous solution, and it was stable for at least several minutes. In addition to the benzoquinone radical, the formation and dynamics of the sesamolyl radical were investigated by using FT EPR. FT EPR showed the detailed behavior of the radical. Characterization of the intermediate is important to evaluate the antioxidant sesamol. Part of these results was presented at the 90th American Oil Chemists’ Society Annual Meeting & Expo, Orlando, FL, May 1999.     

Post-irradiation thermal degradation of poly(olefin sulphones)

Post-irradiation thermal degradation of six poly(olefin sulphones) has been studied by measuring (1) the increases in volatile product yields upon isothermal annealing at various temperatures after irradiation at 0°C, and (2) the decay of trapped free radicals, produced by γ-irradiation at ?196° and 20°C, with time at various temperatures. Above the ceiling temperature for each poly(olefin sulphone) rapid depolymerization occurred, generally yielding equal amounts of sulphur dioxide and olefin. The rates of radical decay also increased greatly in this temperature region.     

Functionalization of single-walled carbon nanotubes by using alkyl-halides

In this paper we demonstrate the functionalization of single-walled carbon nanotubes prepared by chemical vapor deposition. The chosen functionalization agents were alkyl-halides such as trifluoromethane (TFM) and trichloromethane (TCM); or double bond containing alkyl-halides as tetrachloroethylene (TCE) and hexafluoropropene (HFP) that can easily form radicals. Functionalization of samples was carried out under mild conditions, by ball milling of nanotubes in an atmosphere of functionalization agent, at room temperature. For the sake of comparison, chlorination was also performed by chlorine gas. In this process the cleavage of nanotube C-C bonds results in active sites, which can activate molecules in gas phase or adsorbed on the surface of carbon nanotubes. Halogenated samples were characterized by means of particle induced γ-ray emission, transmission electron microscopy, thermogravimetry, and X-ray photoelectron spectroscopy. We concluded that this method gives functionalized single-walled carbon nanotubes in the range of 0.3-3.5 wt.% of fluorine and 5.5-17.5 wt.% of chlorine.     

Arylidene polymers. VI. Gamma irradiation effects on the electrical conductivity behavior,IR absorption spectra,and DSC measurements of some new synthesized poly(arylidenecycloalkanones)

Gamma irradiation effects on the electrical conductivity behavior of some new synthesized poly(2,5-arylidenecyclopentanone) 1 , poly(2,6-arylidenecyclohexanone) 2 , and their co-polymers 3 , have been investigated. Thermal studies over the temperature range 300-500 K showed that the conductivity behavior follows a two-term Arrhenius-type equation. The first term has a small activation energy and predominates at lower temperature (extrinsic region), and the second term with higher activation energy predominates at higher temperatures (intrinsic region). Change in the activation parameters with the change in the γ-ray dose and the nature of the polymers are discussed. The IR absorption spectra showed a decrease in the intensity of most bands of the γ-irradiated samples. A mechanism based on the formation of trapped free radicals and their recombination has been suggested. DSC measurements indicated that the crystallization and the melting temperature transitions decreased in size considerably with the increase in the γ-ray dose until they nearly disappeared at higher γ-ray dose.     

Control of pore formation in macroporous polymers synthesized by single-step γ-radiation-initiated polymerization and cross-linking

Pore formation during the γ-radiation-initiated synthesis of porous polymer monoliths has been systematically investigated. The major advantages of this approach include absence of typical free radical initiators and ability to obtain monoliths with the same chemical structure in a variety of sizes, shapes and porous characteristics. Monomer concentration, type of porogenic solvent, temperature, irradiation dose, and dose rate are variables mostly affecting the properties of the final polymer monolith. Monoliths prepared from diethyleneglycol dimethacrylate in the presence of 60-80 vol.% of lower alcohol such as methanol and 2-propanol with large channel-like pores in the micrometer range exhibit both good flow-through characteristics and appropriate rigidity. The optimum doses and dose rates were found in the range 20-40 kGy and 10-16 kGy/h, respectively.     

Durability of radiation-sterilized polymers. I. Estimation of oxidative degradation in polymers by chemiluminescence

In relation to sterilization of medical supplies, the degree of degradation by γ-ray and electron beam irradiations of homopolypropylene (HP), copolypropylene (CP, coplymer including 6% of ethylene unit) and polymethylpentene were compared, and chemiluminescence (CL) of irradiated polymers were measured. HP degraded extremely around the sterilization dose (2.5 Mrad) by either γ-ray or electron beam irradiations. In the case of CP and polymethylpentene, stabilities of polymers far differed between γ-ray and electron beam irradiations. The polymethylpentene was more stable than the polypropylenes against irradiation. The counts of CL emitted by recombination of peroxy radical (ROO ·) increased with increasing dose, reflecting degrees of oxidation of polymers. The degradation of polymers was independent of irradiation sources, rather it depended on the degree of oxidation. It was found that CL analysis are favorable for estimation of degradation in irradiated polymers.     

Thermal cross-link behavior of an amorphous poly (para-arylene sulfide sulfone amide)

Cross-link behavior of an amorphous poly (para-arylene sulfide sulfone amide) synthesized via low temperature solution polycondensation was observed for the first time, when the polymer was subject to a series of thermal curing at 260 °C in air condition. The formation of cross-link network was demonstrated by the DSC and TGA results that T_g of the polymer enhanced from 259.17 °C to 268.89 °C, and the 1% weight loss temperature increased remarkably from 243.75 °C to 345.87 °C. EPR analysis further suggested that two kinds of free radicals, CO and C, induced by thermal curing were responsible for this cross-link behavior. According to FT-IR spectrum, the origin of these free radicals was confirmed as amide CO group in the polymer backbone. The cross-linking type was attributed to conventional radical cross-link reaction and the cross-link mechanism was discussed in detail subsequently.     

One-step fabrication of multihollow polystyrene particles from miniemulsion system with nonionic surfactant

This paper presented a new facile approach to fabricate polystyrene (PS) multihollow particles from miniemulsion polymerization. The surfactant used in this miniemulsion system was OP-10, a nonionic surfactant of nonyl phenyl polyoxyethylene with an average of 10 ethylene oxide units per molecule (hydrophilic-lipophilic balance, HLB = 13.9). Due to the partition characteristic of OP-10 in miniemulsion, W/O/W structured monomer droplets could be formed after ultrasonic dispersion. Under irradiation by γ-ray, styrene polymerized through a droplet nucleation mechanism, which was the feature of miniemulsion polymerization. The formation of multihollow structure was affected by the content of OP-10 (W_OP) and pre-added PS (W_PS). It was found that when W_OP was above 2 wt% and W_PS was in the region of 2-10 wt% based on the monomer, multihollow PS particles could be obtained. The molecular weight of the PS latex particles synthesized was determined to be 10⁵ g/mol by GPC.     

γ射线辐射法制备石墨/镍复合材料及其电磁性能

为提高鳞片状石墨在电磁波吸收方面的应用性能,采用γ辐射一步法制备了鳞片状石墨/镍复合材料。实验在常温常压下进行,将鳞片状石墨置于镍盐溶液内,控制溶液的镍盐浓度,再加入氧化性自由基清除剂并将该混合溶液置于钴60辐照室辐照,获得了纳米金属镍包覆在鳞片状石墨表面的复合材料。通过XRD、SEM对复合材料进行了结构和形貌的表征,复合材料为核壳结构、由纯纳米镍与石墨构成,同时提出了γ辐射法合成该复合材料的复合机理,并且研究了复合材料在2～18GHz频段的电磁性能。     

Small angle neutron scattering studies on structural inhomogeneities in polymer gels: irradiation cross-linked gels vs chemically cross-linked gels

A comparison of network structure in a solvent was made for two types of poly(N-isopropylacrylamide) gels cross-linked by chemical reaction with N,N′-methylenebisacrylamide (BIS) (chemical gels) and by γ-ray irradiation (γ-ray gels). The cross-linking density dependence for these gels was examined by small angle neutron scattering (SANS). The SANS results indicated an increase of frozen inhomogeneities with an introduction of cross-links for both chemical and γ-ray gels. However, it was found that the effect of cross-linking is much stronger in the chemical gels than in the γ-ray gels. The differences in the structure were successfully interpreted by a statistical-mechanical theory of gels proposed by Panyukov-Rabin (Phys. Rep. 269 (1996) 1). The degree of polymerization between cross-links, N, was a decreasing function of cross-linking content for both types of gels, while that for the γ-ray gels was a weak function of irradiation dose. Quantitative analyses on BIS concentration and γ-ray dose dependence led to an experimental evidence of the existence of cross-linking saturation threshold.     

Co γ-irradiation-initiated RAFT polymerization of VAc at room temperature

In this work, the reversible addition-fragmentation chain transfer (RAFT) polymerization of vinyl acetate (VAc) was successfully performed at room temperature using ⁶⁰Co γ-irradiation as the initiation source. Under the dose rate of 10 Gy/min irradiation, the polymerization proceeded smoothly and converted approximately 90% of the monomer within 7 h. The molecular weight distribution (M_w/M_n) remained narrow (M_w/M_n < 1.35) up to 90% conversion. Compared to AIBN-initiated RAFT polymerization at 60 °C, ⁶⁰Co γ-irradiation-initiated RAFT polymerization is a technique that can better control the molecular weight, especially at high conversion. The ¹H NMR spectra and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry confirmed that most of the chain ends of poly(VAc) (PVAc) from γ-irradiated RAFT polymerization were living and can be reactivated for chain-extension reactions. The microstructures of PVAc from ⁶⁰Co γ-irradiated RAFT polymerization (almost head-to-tail addition) and AIBN-initiated RAFT polymerization (5% tail-to-tail addition) were different, as revealed by the ¹³C NMR spectra. For the first time, ⁶⁰Co γ-irradiation was used as an initiation source for RAFT polymerization of VAc at room temperature.