The effect of ions irradiation on the thermal properties of poly(ether ether ketone)

The effect of irradiating amorphous poly (ether ether ketone), PEEK, with ions, 11 MeV proton (H⁺), and 25.6 MeV helium (He²⁺), has been investigated focusing on the changes in thermal properties. The extent of chain scission and crosslinking was evaluated using the Charlesby‐Pinner equation. Crosslinking increased the glass transition temperature (T_g) in line with the DiBenedetto equation from which the crosslinking constant for each ion was calculated. The effect of irradiation on the thermal degradation kinetics was studied in an argon atmosphere at a constant heating rate by mean of the Chang and the second Kissinger methods. Irradiation significantly reduced the thermal stability of the polymer and its service lifetime. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2212–2221, 2008     

Surface studies of ultra‐high molecular weight polyethylene irradiated with high‐energy pulsed electron beams in air

Ultra‐high molecular weight polyethylene (UHMWPE) was irradiated in air with high‐energy (9 MeV), pulsed electron beams to doses ranging from 2.5 to 100 Mrad and subsequently heat treated at 120°C for a time period of 120 min. Surface characterization of the target side of irradiated UHMWPE samples was carried out both before and after the heat treatment by means of attenuated total reflection Fourier‐transform infrared (FTIR/ATR) spectroscopy and microhardness measurement. The obtained results provided further evidence supporting our earlier observation (Tretinnikov, O. N.; Ogata, S.; Ikada, Y. Polymer 1998, 39, 6115) that thermal decomposition of hydroperoxides formed upon irradiation of UHMWPE with high‐energy, pulsed electron beams in air leads to surface crosslinking, and the subsequent surface hardening of the irradiated polymer. Importantly, we found that this phenomenon has the highest contribution to the surface hardness enhancement of the polymer when the radiation dose is in the range of 10–30 Mrad. In addition, we found that this irradiation and subsequent heat treatment of UHMWPE in air does not lead to formation of carbonyl‐containing products unless the radiation dose exceeds 20 Mrad. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1503–1512, 1999     

The sulfonation of crosslinked poly(ether ether ketone)—Diffusion‐controlled kinetics

The effect of crosslinks introduced by ion irradiation with 11.7 MeV proton and 30 MeV helium ions on the reactivity of poly(ether‐ether‐ketone) (PEEK) to sulfonation have been investigated following the kinetics of the reaction at room temperature. Concentrated sulfuric acid was used as a swelling and sulfonating agent and the reaction was followed by changes in the FTIR spectrum. The rate of reaction decreased with the degree of crosslinking and the progress with time was consistent with diffusion control of the sulfuric acid into the crosslinked matrix. The results were consistent with the efficiency of the ions in crosslinking PEEK and in particular with the differences in their linear energy transfer (LET). © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 775–783, 2009     

Degradation of polymer coating systems studied by positron annihilation spectroscopy. II. Correlation with free radical formation

The photo‐degradation of polymer coating systems due to irradiation by UV and Xenon light sources is studied using positron annihilation spectroscopy and electron spin resonance (ESR). Doppler broadened spectra of positron annihilation, as a function of slow positron implantation energy and ESR spectra, are measured in two types of polyurethane which were exposed, ex situ, to UV irradiation for up to 800 h. The UV irradiation systematically decreases the S parameter as a function of exposure duration and increases the ESR signals. Thus, significant S parameter decrease is correlated with the ESR signal increase resulting from photo‐degradation of polymers due to UV irradiation. Parallel in situ positron annihilation and ESR experiments are performed as a function of Xenon light exposure for up to 100 min. These results show that the photo‐degradation of the polyurethane coatings involves initial free‐radical formation, which is correlated with the subnanometer defects detected by positron annihilation spectroscopy. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1289–1305, 1999     

Effect of the polymer matrix on the formation of silver nanoparticles in polymer–silver salt complex membranes

When polymer–silver salt complex membranes were exposed to UV irradiation, the separation performances of both the permeance and selectivity for propylene–propane decreased, which was primarily attributed to the reduction of the silver ions in the membranes to silver nanoparticles. Here, the effect of the polymer matrix on the formation of silver nanoparticles in the polymer–silver salt complex membranes was investigated. This effect was assessed for the complexes of two kinds of silver salts (AgBF₄ and AgCF₃SO₃) with several polymeric ligands containing three different carbonyl groups, including poly(vinyl pyrrolidone) (PVP) with an amide group, poly(vinyl methyl ketone) (PVMK) with a ketone group, and poly(methyl methacrylate) (PMMA) with an ester group. UV–vis spectra and transmission electron microscopy (TEM) images clearly indicated that the reduction rate of the silver ions has the following order in the various polymer matrices: PVP > PVMK > PMMA, whereas the size and the distribution of the nanoparticles exhibited the reverse order. The tendency to form silver nanoparticles was explained in terms of the differences between the comparative strengths of the interactions of the silver ions with the different carbonyl oxygens in the matrices, as well as that of the silver ions with counteranions, which was characterized by X‐ray photoelectron spectroscopy (XPS) and FT‐Raman spectroscopy. It was concluded that when the concentration of free silver ions was low due to weak polymer–silver ion and strong silver ion–anion interactions, as found with PMMA, the reduction rate of silver ions to silver nanoparticles was slow. Therefore, the PMMA–silver complex membranes were less sensitive to decreases in separation performance upon UV irradiation than compared to the PVP membranes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1168–1178, 2006     

Radiation damage in dielectric and semiconductor single crystals (direct observation)

The surfaces of boron-doped synthetic and natural diamonds have been investigated by using the scanning tunnelling microscope (STM) and the scanning electronic microscope (SEM) before and after irradiating the samples with ⁴⁰Ar (25 MeV), ⁸⁴Kr (210 MeV) and ¹²⁵Xe (124 MeV) ions. The structures observed after irradiation showed craters with diameters ranging from 3 nm up to 20 nm, which could be interpreted as single ion tracks and multiple hits of ions at the nearest positions of the surface. In the case of argon ion irradiation, the surface was found to be completely amorphous, but after xenon irradiation one could see parts of surface without amorphism. This can be explained by the influence of high inelastic energy losses. The energy and temperature criteria of crater formation as a result of heavy ion irradiation are introduced.     

Trace Analysis by Heavy Ion Induced X-Ray Emission

 Various K-, L- and M-shell X-ray production cross sections are measured for heavy ion impact on elements in the range Z ₂ = 13 to 83. The ion species range from Z ₁ = 10 to 36, and ion energies from 1 to 16 MeV are used. Enhanced cross sections are observed when the projectile K- or L- binding energy is similar to the energy of the target K-, L- or M-shell. This effect is used to improve the analysis sensitivity for selected elements. As an example trace analysis of Fe in glass with V, Mn, Co and Ni ions is investigated. Results are compared with proton induced X-ray emission analysis on the same samples. In these samples Fe-K_α X-ray production is similar for irradiation with 3 MeV protons and 14 MeV Ni ions. However the signal to background ratio is four times higher for the irradiation with Ni ions as compared to irradiation with protons. Advantages and drawbacks of heavy ion induced X-ray emission for quantitative analysis compared to proton induced X-ray emission analysis are discussed.     

Observation of latent tracks formed by heavy ion irradiation in poly(methyl methacrylate)

The irradiation effect in poly(methyl methacrylate) changed from main‐chain scission to crosslinking, depending on the stopping powers of the Au and Xe ions irradiated with high stopping powers. The latent ion tracks, including an end of the ion range in the polymer, were observed clearly by field emission and atomic force microscopies. Additionally, it was also observed that a crosslinked structure (formed by nuclear stopping) existed across an end of the ion range calculated by a Transport of Ion in Matters code, and it was different from that formed by electronic stopping. The nuclear stopping of the heavy ions can play an important role around the end of the ion range in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 757–762, 2001     

Effect of irradiation in InGaAs photo devices

Results are presented of an extended study on the degradation of electrical and optical performance and the induced lattice defects of In_0.53Ga_0.47As p-i-n photodiodes, subjected to a 20 MeV alpha-ray irradiation. The difference in radiation damage with 1 MeV fast neutrons and 1 MeV electrons is discussed taking into account the energy transfer. The radiation source dependence of performance degradation is attributed to the difference of mass and the probability of nuclear collision for the formation of lattice defects.     

On the propagation rate constants of cationic polymerizations

The concepts employed to explain polymerizations by ionizing radiations are used for a critical examination of the concepts involved in interpreting the kinetics of chemically initiated cationic polymerizations. It is explained how the interactions of the propagating carbenium ions with the solvent, monomer, and anion can result in the formation of up to six distinct unpaired species and several kinds of ion pairs; therefore, the consumption of the monomer can be governed simultaneously by many rate constants. Only one of these can have any general theoretical use, and suggestions are made for how it can be measured. For the first time, it is shown that the ion‐pairing process must involve a ligand displacement and so resembles the amination of the Ag⁺ ion, for example, in an aqueous solution by NH₃, rather than an association of inert ions of unchanging identity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2537–2544, 2002     

Physio-chemical influence of high electron-phonon coupling induced by 120 MeV Ag9+ SHI irradiation on exfoliated MoS2 - PVA nanocomposite films for achieving remarkable electrical conductivity for potential application in organic electronics

Swift heavy ion (SHI) irradiation technology is known to enhance the optical, electronic, mechanical, and electrical properties in polymer nanocomposites by the virtue of electron-phonon coupling. In the present work, Molybdenum disulphide (MoS₂), a two-dimensional metal dichalcogenide, has been exfoliated via liquid-phase exfoliation using N-methyl-2- pyrrolidone (NMP) as the solvent that yielded nanosheets of around 2–4 layers as depicted by HR-TEM images. MoS₂ - PVA free-standing films were prepared by wet chemical technique i.e. solution casting method and irradiated by focussed high-energy Ag⁹⁺ ion beam at fluence range of 1E10 - 3E11 ions/cm². As a consequence, the structural modification was observed by X-Ray diffraction studies that showed the shift of (002) plane of MoS₂ while Raman studies indicated the decrease of degree of disorderness at fluence 1E10 ions/cm². SHI irradiation has found to induce a two-order increase in the electrical conductivity yielding a 9.7 E-3 S/cm against that of the pristine films at 2.6E-5 S/cm. The enhanced conductivity is attributed to the induced dispersion and annealing of MoS₂ nanosheets in the PVA matrix due to the interaction of 120 MeV Ag⁹⁺ ion beam irradiation as explained by Thermal spike model.     

Characterization of heavy ion tracks in polymers by transmission electron microscopy

Ultrathin sections of two polymers—poly(ethylene terephthalate) and polyimide—were irradiated with heavy ions of 11.1 MeV per nucleon. The size and morphology of the latent tracks were examined with transmission electron microscopy. Polymers readily decomposed under the imaging electron beam. Samples were therefore stained with either osmium tetroxide or ruthenium tetroxide before and/or after ion irradiation. This treatment significantly reduced the radiolytic sensitivity. In addition, however, with dynamic video electron imaging, quasi‐instantaneous damage processes were observed within seconds of observation, modifying in particular both tracks in the bulk and to a lesser extent those on the two confining surfaces. The staining agent was embedded into amorphous regions of the matrix as metallic nanoparticles. Prestained tracks appeared as bright cylindrical regions with diameters of ～6–10 nm. In ultrathin samples, the central track region showed a significant loss of material and even an open hole. Following poststaining, tracks exhibited a dark contrast because of preferential diffusion of the staining agent into the tracks. Poststained tracks were larger than prestained tracks. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2892–2901, 2003     

Ultraviolet photocatalytic degradation of cholesterol on TiO2: secondary ion mass spectrometry

Cholesterol (C₂₇H₄₆O stated as M) is used as a model of bio‐organic contamination, because this compound is in almost every living organism, and its photocatalytic degradation on titanium oxide (TiO₂) surface with UV exposure is investigated. Secondary ion mass spectrometry as a surface‐sensitive technique is suited to study this degradation process with focus on intermediates. A fragment of M–OH represents the intact molecule of cholesterol and provides its relative concentration on the surface. The intensity of M–OH decreases after 24‐h UV irradiation, and the level of degradation is 89% with the pseudo‐first kinetic constant of 0.0207 min^?1 within 2 h. A fragment of MO–H represents an intermediate as one of the cholesterol oxidation products. The irradiation from a bottom in comparison with a top reveals the differences in the mechanism of the intermediate formation through the intensity and the kinetics with values of factor of 1/3 and 30 min, respectively. The roles of electrons and holes, primarily generated in TiO₂ by UV, and also of superoxide anion radical and hydroxyl radical, as the secondary reactive species, are discussed to illustrate the bottom/top mechanisms. Copyright © 2016 John Wiley & Sons, Ltd.     

Photo-stimulated luminescence of KCl:Eu under X-ray and ion irradiation

We compared the photo-stimulated luminescence (PSL) process of storage phosphor KCl:Eu under the irradiation of X-ray, 2.0 MeV H⁺ ions and 2.0 MeV He⁺ ions. The purpose of the irradiation of H⁺ and He⁺ ions was to mimic the irradiation effects of neutrons. In each case, it was revealed that F-centers were involved in the PSL process. We observed an entirely different fluence-dependent PSL behavior between the X-ray and the ion irradiation, whereas the behavior of the F-center absorption was quite similar. This difference was due to the different yields of the trapping sites for the electrons liberated from the F-centers, and the difference in the yield was ascribed to the difference in the excitation density. This result clearly indicated a marked difference in the PSL process under X-ray and neutron irradiations and indicated that the analysis of the PSL process under ion irradiation is highly important for the application of PSL phosphors to neutron radiography.     

Uranyl ion complexation of 2,2′-dihydroxyazobenzene enhanced on a backbone of poly(ethylenimine)

The formation constant (K_f) for the uranyl complex of 2,2′-dihydroxyazobenzene (DHAB) was measured with DHAB attached to poly(ethylenimine) (DHAB-PEI) at pH 7.7 to 9.4. The value of K_f was estimated from the equilibrium constant for extraction of uranyl ion from the uranyl complex of DHAB-PEI (UO₂DHAB-PEI) with carbonate ion, which in turn was measured from the absorbance change observed on addition of bicarbonate ion to the solution of UO₂DHAB-PEI. At pH 8.0, the uranyl-binding ability of DHAB was enhanced by about 10⁴ times on attachment of DHAB to PEI. The major origin of the increased ability of uranyl ion complexation is the basic local microenvironment of PEI, which encourages ionization of the phenol groups of DHAB. Various other possible origins are discussed also. The log K_f for DHAB-PEI at pH 8.0 indicates that DHAB moieties of DHAB-PEI are mostly occupied, whereas DHAB unattached to PEI is mostly unoccupied by uranyl ion under conditions of seawater when only the pH and concentrations of bicarbonate and uranyl ions of seawater are considered. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3936–3942, 1999     

Changes in structural and conducting characteristics of zinc nanotubes by bombardment with Xe<Superscript>+22</Superscript> heavy ions

Results of targeted modification of the structure and properties of ordered arrays of zinc nanotubes (Zn NTs) by accelerated Xe⁺²² heavy ions with a fluence of 1 × 10⁹ to 5 × 10¹¹ cm^–2 in the energy range of 1.0–1.75 MeV/nucleon are reported. Dynamics of changes in the crystallite shape and orientation of Zn NTs before and after irradiation has been studied by X-ray diffraction. It has been shown that irradiation with accelerated ions has a significant effect on the texture coefficients of Zn NTs. In addition, at a fluence of 1 × 10¹¹ m^–2 or higher, the formation of loose areas in the structure of Zn NTs as a result of partial degradation of the crystal structure and, consequently, a decline in conductivity are observed.     

Acyclic diene metathesis (ADMET) depolymerization: Ethenolysis of 1,4-polybutadiene using a ruthenium complex

α,ω-Vinyl-terminated butadiene oligomers can be generated through the cross-metathesis of ethylene and high molecular weight 1,4-polybutadiene catalyzed by the complex RuCl₂(CHPh)(PCy₃)₂. The effect of varied ethylene pressure is studied in order to obtain the highest conversion to the monomer 1,5-hexadiene. A dramatic increase in yield of this monomeric diene is realized relative to previous published attempts utilizing a well-defined group VI metal alkylidene in the same chemistry. Traces of side products are observed, and alternate mechanisms for their formation were proposed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1857–1861, 1999     

Reversible gelation of poly(dimethylsiloxane) with ionic and hydrogen‐bonding substituents

Poly(dimethylsiloxane) copolymers containing a small fraction of carboxylic acid or Zn‐carboxylate groups were prepared and compared regarding reversible gelation by hydrogen‐bonding and ion‐pair interaction. The polymers were synthesized by condensation of a t‐butylcarboxylate functionalized dichlorosilane with an α,ω‐dihydroxy‐poly(dimethylsiloxane), followed by thermal cleavage of the ester bond. Neutralization of the resulting carboxylic acid substituents was achieved by addition of Zn (acac)₂. Reversible crosslinking was investigated by step stress and oscillating shear experiments. The carboxylic acid containing poly(dimethylsiloxane) became rubberlike upon increasing the temperature and liquified again when it was brought back to room temperature. This observation has been explained tentatively by segregation of the carboxylic acid groups into polar domains at high temperatures [i.e., a behavior like it is observed for systems with a lower critical solution temperature (LCST)]. At ambient temperature, the carboxylic acid groups undergo hydrogen bonding to the Si–O–Si backbone. Clustering of the carboxylic acid groups occurs only as these hydrogen bonds break upon raising temperature. Moisture was found to have a strong influence on the reversal of the crosslinking. Addition of zinc acetylacetonate resulted in the formation of an elastic network already at ambient conditions consistent with the concept of ionomers which undergo reversible gelation by formation of ion‐pair multiplets and clusters in the hydrophobic polymer matrix in particularly at low temperatures. At high temperature, both the carboxylic acid and the carboxylate sample exhibited a rather similar viscoelastic behavior consistent with a common structure where transient crosslinks are formed by clusters of the carboxylic acid and the carboxylate groups. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 485–495, 1999     

Gas transport properties of asymmetric polyimide membranes prepared by ion‐beam irradiation

Ion beam irradiation has been widely used to modify the structure and properties of membrane surface layers. In this study, the gas permeability and selectivity of an asymmetric polyimide membrane modified by He ion irradiation were investigated using a high vacuum apparatus equipped with a Baratron absolute pressure gauge at 76 cmHg and 35 °C. Specifically, we estimated the effects of the gas diffusion and solubility on the gas permeation properties of the asymmetric membranes with the carbonized skin layer prepared by ion irradiation. The asymmetric polyimide membranes were prepared by a dry–wet phase inversion process, and the surface skin layer on the membrane was irradiated by He ions at fluences of 1 × 10¹⁵ to 5 × 10¹⁵ ions/cm² at 50 keV. The increase in the gas permeability of the He⁺‐irradiated asymmetric polyimide membrane is entirely due to an increase in the gas diffusion, and the gas selectivity increases of the membranes were responsible for the high gas diffusion selectivities. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 262–269, 2007.     

Epoxy‐amine reticulates observed by infrared spectrometry. II. Modifications of structure and of hydration abilities after irradiation in a dry atmosphere

This article is part of a series of articles devoted to the study of the responsibilities of both humidity and irradiation in the aging process of amine‐cured epoxy resins. The basic technique used in this study is infrared spectrometry. In a previous article we have observed, with this technique, hydration of two kinds of epoxy resins, which are widely used in the nuclear industry. In this article the same technique is used to observe the same resins, which have been previously submitted to ionizing radiations. It allows us to determine the effects these radiations have on these resins at molecular level and how they consequently modify their hydration mechanisms. It could thus be established that irradiation by electrons almost does not induce modifications on resins cured with aromatic diamines, which results in their hydration capacity being only slightly changed. Irradiation by γ rays induces stronger modifications, which reflect themselves in a greater capacity of absorption of water and different ways of fixing H₂O molecules. Epoxy resins cured with alkyl diamines are more sensitive to irradiation and, after it, absorb a greater amount of H₂O molecules. After irradiation, steric conditions, which hinder H₂O molecules to bind on other H₂O molecules, apparently become less severe. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 329–340, 2000