Effects of electron irradiation on poly(vinylidene fluoride–trifluoroethylene) copolymers studied by solid‐state nuclear magnetic resonance spectroscopy

The effects of electron irradiation on the molecular chemical structure, conformation, mobility, and phase transition of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) copolymer have been investigated with variable‐temperature, solid‐state ¹⁹F nuclear magnetic resonance (NMR). It has been found that electron irradiation converts all‐trans conformations of both VDF‐rich and TrFE‐containing segments into dynamically mixed trans–gauche conformations accompanied by a simultaneous ferroelectric‐to‐paraelectric (or amorphous) transition. The variable‐temperature ¹⁹F magic‐angle‐spinning spectra results show that the paraelectric phase melts at much lower temperatures in irradiated films than in an unirradiated sample. Moreover, ¹⁹F NMR relaxation data (spin–lattice relaxation times in both the laboratory and rotating frames) reveal that electron irradiation enhances the molecular motion in paraelectric regions, whereas the molecular motion in a high‐temperature amorphous melt (>100 °C) is more constrained in irradiated films. Besides these physical changes, electron irradiation also induces the formation of several CF₃ groups. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1714–1724, 2006     

Influence of molecular mass on the liquid crystal alignment of photosensitive fluorinated polyester films

Photosensitive fluorinated polyesters (polymer-n) of varying molecular mass M _n (number-average molecular mass) were synthesized. The thin films formed from polymer-n samples could induce liquid crystal (LC) alignment after irradiation by linearly polarized ultraviolet light. The LC alignment direction on the irradiated films was investigated in detail by linearly polarized infrared spectroscopy and polarizing optical microscopy. It was found that LC alignment behaviour changed with change in the molecular mass of polymer-n: irradiated films with lower or higher M _n induced homeotropic or homogenous alignment, respectively. There was no clear morphological anisotropy in these aligned films, as observed by atomic force microscopy. The surface energies of the irradiated films were also measured using the indirect contact angle method, where both surface energy and its polar component increased with increasing M _n. The variation in M _n could be considered as a main reason for varying alignment behaviour.     

Director orientation of a ferroelectric liquid crystal on substrates with rubbing treatment: The effect of surface anchoring strength

Abstract

One of the most important problems with ferroelectric liquid crystals is obtaining homogeneous as well as bistable alignment, not only to study their physical characteristics but also for their application to optical devices. In this connection it was predicted that the formation of homogeneous alignment requires strong surface anchoring, whereas bistability requires weak anchoring. We have therefore developed a method to determine the surface anchoring strength, and have tried to clarify whether there is a suitable anchoring range. It was found that A/K ₂₂ (A is the surface anchoring and K ₂₂ is the twist elastic constant of liquid crystal) of 4 × 10^?2 to 2 μm^?1 satisfies the contradictory requirements for homogeneous as well as bistable alignments for the material studied, and the bookshelf structure is successfully formed with this condition.     

Thermomechanical properties of polytetrafluoroethylene in different zones of impact of continuous CO2 laser radiation

The pseudo-network structure of the amorphous block of polytetrafluoroethylene is formed by branching points, the crystallites of low- and high-melting crystalline polymorphs and the cluster segments of macromolecules. The polymer treated by laser irradiation is amorphized, with the degree of amorphization and other changes depending on the radiation fluence. A depression of the molecular flow onset and initial melting temperatures of the crystalline polymorphs, a decrease in the molecular mass, and the disappearance of the crystalline branching points characteristic of the original polymer have been observed in the irradiated polymer. Areas with different degrees of modification of the molecular structure appear in the dynamic mode with moving boundaries during continuous CO₂ laser irradiation. The difference in absorbance of the crystalline and amorphous portions of the polymer at the laser emission wavelength and a relatively high transmittance make laser-induced degradation differ from thermolysis in contact with a hot surface.     

Identification of irradiation treatment of spices by thermoluminescence of contaminating minerals

Five spices, cumin, coriander, clove, cinnamon and black pepper were irradiated by gamma-ray doses of 1.0 and 5.0 kGy and thermoluminescence (TL) method was used for identification of the irradiation treatment. The TL response of the minerals isolated from irradiated samples was much higher as compared to the mineral particles from unirradiated control samples. For the normalisation of results the separated minerals were reirradiated to a normalisation dose of 1.0 kGy and the TL glow curve was recorded a second time. By comparing the glow curves of irradiated and unirradiated samples, finding the ratio of the areas of first and second glow curves (TL₁/TL₂) and comparing the shapes of the glow curves, all the irradiated and unirradiated samples were identified correctly.     

Chemical state of Na and K ions in Na10K5 silicate glass under electron irradiation investigated by XPS with the aid of the line shape analysis

The Na? K (Na10K5) silicate glass, unirradiated and electron irradiated (electron dose from 25 to 8239 Cm^?2) is investigated using XPS. The measurements are performed in the angular‐resolved ADES‐400 spectrometer using AlKα X‐ray radiation and an electron beam of energy 2 keV. Owing to surface charging and ambiguity of identification of the atomic oxidized chemical states, the line shapes of selected XPS transitions are analyzed with the aid of the pattern recognition (PR) method. This method is based on a distance measure and deals with spectra representation as vectors in the n‐dimensional space. The algorithm presented, called the fuzzy k‐nearest neighbor (fkNN) rule, allows for identification of ambiguous vectors with the membership vectors described by classes membership probabilities. Under electron irradiation, the Na and K content in a surface region undergoesincrease and then slow systematic decrease. The line shape analysis indicates difficult classification of XPS spectra recorded for unirradiated and irradiated glass, especially for Na 1s transition. The chemical state of Na is a mixture of elemental and oxidized form and remains unchanged for all electron doses. Larger changes in the chemical form are observed for the K atom. In an unirradiated silicate glass, a mixture of elemental and oxide form is observed with increasing content of oxide under irradiation. The alkali atoms, Na and K, exhibit a migration effect. Comparison of PR and fitting results indicates better reliability and accuracy of the PR method. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of bombardment with helium ions on the molecular-topological structure and elemental composition of the surface of Kynar polyvinylidene fluoride resin

A polyvinylidene fluoride film has been bombarded with accelerated (1–5 MeV) helium ions at a fluence of 10¹⁵ ion/cm². Unlike the completely amorphous structure of the unirradiated polymer, the weight fraction of the crystalline modification in the irradiated polymer is 0.86–0.90, which is indicative of the efficient conversion of the amorphous structures of the polymer pseudo-network into the crystalline ones. Irradiation with 1-MeV ions leads to the greatest changes in the fraction of the crystalline modification and the glass-transition and flow temperatures of the polymer. The detachment of fluorine and the surface carbonization of the irradiated polymer occur under the ion beam.     

Homogeneous liquid crystal orientation on ion beam exposure TiO2 surfaces depending on an anisotropic dipole field

We studied homogeneous liquid crystal (LC) alignment properties on ion-beam (IB) irradiated TiO₂ films deposited by the electron beam evaporation method. Stable homogeneous LC alignment on a TiO₂ surface resulted from IB irradiation energy over 1800 eV. X-ray photoelectron spectroscopy analyses showed that Ti⁴⁺ 2p_3/2 and Ti⁴⁺ 2p_1/2 peaks were increased with increasing IB energy. Assuming that the increased peaks produced anisotropy dipole fields in the direction of the IB exposure process, we confirmed that the increasing IB energy induced strengthened the surface energy for entirely clear and stable LC molecule orientation. The voltage-transmittance characteristics of the twisted-nematic cell on the TiO₂ surface indicate that the TiO₂ film has potential for use as the LC alignment layer.     

Physicochemical analysis of ion beam-induced surface modifications on polyethylene glycol films for liquid crystal alignment

ABSTRACT

We investigated the surface modification induced by the ion-beam (IB) irradiation of a polyethylene glycol (PEG) film and its liquid crystal (LC) alignment characteristics. The X-ray photoelectron spectroscopy analysis revealed the chemical modification; as the IB incidence angle increased, the number of surface C–O bonds decreased, inducing an anisotropic dipole moment on the PEG film surface. In addition, the physical modification was demonstrated via atomic force microscopy analysis using three-dimensional images as a function of the IB incidence angle. The surface roughness was analyzed; the modification with the smoothest surface was observed for an IB incidence angle of 45°. This modification affected the LC alignment state of the PEG film, as demonstrated by the polarized optical microscopy analysis with pre-tilt angle measurements. Furthermore, for the same IB incidence angle, the residual DC measured using the capacitance–voltage curves was extremely low. Hence, a PEG film irradiated with an IB incidence angle of 45° could be a suitable LC alignment layer.     

Molecular-topological and thermal properties of gamma-irradiated alternating carbon monoxide-ethylene copolymer

Gamma-irradiation to a dose of up to 2000 kGy does not lead to substantial changes in the topological structure of a carbon monoxide copolymer with ethylene, thereby suggesting it high radiation resistance. The topological structure of unirradiated and irradiated copolymer samples is polyblock in nature having four crystalline phases as the branching “junctions” in the pseudo-network structure of its amorphous block. Copolymer molecular flow begins after completion of melting of its high-melting fraction and at an onset flow temperature of 484 ± 4 K regardless of the absorbed radiation dose. The irradiated and unirradiated copolymer releases the same gaseous products upon heating, and the irradiation itself does not affect the onset temperature of effective gas evolution.     

Effects of radiation and chain ends on fatigue behaviour of polystyrene

Fatigue lifetimes, under a given alternating stress amplitude, have been determined for a series of linear and branched polystyrenes. The branched polymers were obtained by a crosslinking reaction using γ-irradiation from a Co⁶⁰ source. By control of irradiation time, a series of branched samples of progressively increasing weight average molecular weight ($\text{M}$_w), with little change in number average molecular weight ($\text{M}$_n, were obtained. From comparison of fatigue data for these irradiated and branched samples with fatigue data obtained on a series of linear polystyrenes of increasing molecular weight, it may by concluded that appreciable increases in fatigue endurance can be achieved by increase in $\text{M}$_n and reduction in chain end density. For the irradiated samples, whether irradiated in air or in vacuum, fatigue lifetimes were comparable to or less than lifetimes to fracture for the unirradiated polymer, even though significant increases in $\text{M}$_w had occurred. It is suggested that the improved fatigue performance with increase of $\text{M}$_n is a consequence of increased craze stability resulting from the greater degree of chain entanglement and the smaller proportion of chain end defects.     

RADIATION DEGRADATION OF CHITOSAN IN THE PRESENCE OF H2O2

INTRODUCTIONChitosan, poly-β-(1 -?4)-D-glucosamine, can be obtained from chitin by deacetylation with alkali. It is soluble indilute acidic medium due to the presence of amino groups. The use of chitosan in many areas, such as foodprocessing, biochemistry, Pharmaceuticals, medicine, and agriculture has been developed over the pastdecades[1,2].In recent years, it has been reported that many properties of chitosan depend on the molecular weight[3]. Thechitosan oligomers possess better fun…     

TiO2颗粒在羟基表面的沉积行为及图案化

比较了3种具有羟基表面SiO2层的差异:紫外光照SAMs形成的羟基表面,紫外光照射前、照射后的羟基表面;用光照前后表面的差异,结合化学浴沉积技术在单晶硅基底上制得了TiO2微图案薄膜。系统考察了光源、硅片表面性质的变化、溶液等方面对图案生成的影响。实验表明TiO2沉积在未照区,电子和空穴动力学上的差异造成光照区表面正电荷增多,抑制了TiO2的沉积。该方法不需要光刻胶和自组装膜作为辅助模板,具有简单廉价的特点。     

Hydrogels synthesised through photoinitiator-free photopolymerisation technique for delivering drugs including a tumour-tracing porphyrin

Hydrogels were synthesised using the photoinitiator-free photopolymerisation technique involving interactions between donor/acceptor pairs for delivering drugs of different molecular weights including a porphyrin used as a tumour-tracing agent. N-(5-hydroxy) pentylmaleimide, an acceptor, formed hydrogels with N-vinyl-2-pyrrolidinone, 2-hydroxyethyl methacrylate and N-vinylcaprolactum. Glucosamine, an effective H-donor in enhancing polymerisation as shown by Differential Photocalorimetric results, was found unsuitable for hydrogel preparation. Drugs of different molecular weights releasing at the same rate was discussed. The hydrogels were found to have no toxic effects and were biocompatible with a human keratinocyte cell line.     

Field-free molecular alignment control by phase-shaped femtosecond laser pulse

In this paper, we theoretically show that the field-free molecular alignment can be controlled by shaping the femtosecond laser pulse with a periodic phase step modulation, involving the maximum degree and temporal structure of the molecular alignment. We show that the molecular alignment can be completely suppressed or reconstructed as that by the transform-limited laser pulse, the temporal structure of the alignment transient can be controlled with a desired shape, and the molecular alignment and antialignment for any temporal structure can be switched. Furthermore, we also show that both the degree and direction of the molecular alignment at a fix time delay can be continuously modulated.     

Role of each part of cyanobiphenyl-containing polymers in porous-film preparation by using the breath-figure method

ABSTRACT

The breath-figure method using the condensation of water droplets can easily fabricate regular porous films. Although the method is simple, the phenomenon itself requires the control of many parameters that change throughout the process. Therefore, we require a unified understanding of polymers for the fabrication of ordered porous films. In this study, to clarify the required molecular structures of polymers to form a regular porous structure, we systematically explored poly(methacrylate)s with cyanobiphenyl moieties connected by dodecyl groups in the side chain (P11CB); these could form a hexagonal ordered porous structure on the entire film surface. The comparison of P11CB and P11B, which is a P11CB without cyano groups, showed that the local polar groups in hydrophobic polymers promote the formation of ordered porous films. Furthermore, no holes were formed in films of P0CB which is a P11CB without alkyl spacers due to its hydrophilicity. Long alkyl chains resulted in changed hydrophilic polymers to hydrophobic polymers. The introduction of long alkyl chains as a spacer between the biphenyl moiety and polymer backbone is preferred in the cases of particularly few amounts of biphenyl groups in the polymer. The biphenyl groups showed the ability to improve film formability.     

A 13C NMR study of the effect of γ-irradiation on the chain dynamics of poly(ethylene oxide)

A comparison of solid-state ¹³C nuclear magnetic resonance (NMR) spectra of virgin and vacuum γ-irradiated poly (ethylene oxide) (PEO) evidences marked differences. The unirradiated PEO shows a well-resolved amorphous resonance and a weak, broad envelope of crystalline resonances, while the irradiated PEO presents well-resolved resonances for both the crystalline and amorphous carbons. Upon recrystallization from the melt both PEO samples yield solid-state ¹³C NMR spectra that are closely similar to that of the virgin, unheated sample. Observation of both melt-recrystallized samples at ?60°C yields similar spectra with well-resolved crystalline resonances. Crosslinking is the predominant chemical change occurring during the γ-irradiation of PEO under vacuum and produces a change in the motional character of the crystalline phase. This change is not the result of a reduction in crystallinity as evidenced by differential scanning calorimetry (DSC) observations. The most probable explanation is that the crosslinks are concentrated at the surface of the crystalline lamellae with a resultant change in the low frequency molecular motions of the crystalline chains. This motional change shifts the T_1p^H such that the crystalline carbon nuclei can now be cross-polarized at room temperature and the resonance linewidth is reduced. Following melting and recrystallization the motional characteristics of the irradiated PEO are nearly identical to those of the unirradiated sample, probably as a result of a redistribution of the crosslinks throughout the amorphous phase during recrystallization.     

Pork fat peroxidation by gamma-irradiation

In this paper, pork fat peroxidation by γ-irradiation and the possible effects of oxygen, UV-irradiation and storage after the γ-irradiation have been investigated. It has been found that the level of peroxides in irradiated pork increases linearly with the increasing absorbed dose. The chemical yield of peroxides formed in the irradiated fat is about 4.2 and independent on the sample temperature or absorbed dose rate, but dependent on storage time of sample before γ-irradiation. The irradiated pork exhibits some unusual features as following: 1) the peroxide content in irradiated pork is higher than that in unirradiated one; 2) the peroxide content in irradiated pork increases gradually on storage and is essentially constant in unirradiated one, which is very useful for the detection of irradiated pork; 3) the further peroxidation in irradiated pork is much more susceptible to UV radiation than that in unirradiated pork.     

Nanodomain analysis with cluster‐SIMS: application to the characterization of macromolecular brush architecture

We present the application of cluster‐SIMS for the analysis of the nanoscopic surface of diblock brush terpolymers (DBTs). This novel SIMS technique differs from conventional SIMS. It uses Au₄₀₀⁴⁺ projectiles at 520 keV and an event‐by‐event bombardment/detection regime for the analysis of co‐localized molecular species. The performance of this SIMS method was tested on ‘bottle brush’ block molecules featuring a vertical aligned backbone structure. We were able to assess the extent of secondary ion emissions from the surface and analyze the degree of ordered alignment for DBTs by the fluorocarbon surface coverage. We demonstrate the feasibility of characterizing the homogeneity of macromolecular films at the nanoscale. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigations into the characteristics of irradiated zircaloy cladding material in connection with reactor operation and spent fuel reprocessing

To monitor and improve the performance of nuclear fuel assemblies, the uptake of gases (oxygen, nitrogen and hydrogen) is determined in zircaloy cladding materials. Gas chromatography and/or mass spectrometry combined with hot vacuum fusion were applied. Deviations from the initial concentrations (ca. 5 μg g^?1 H₂, 30 μg g^?1 N₂ and 1200 μg g^?1 O₂) in the “as fabricated” condition, are important in estimating cladding corrosion. The material characteristics of zircaloy are altered substantially by the neutron irradiation and the chemical environment in the reactor coolant, thus the irradiated material must also be studied. For reprocessing safety consideration, the ignition and explosion parameters of unirradiated and irradiated zircaloy dusts were examined. Standard methods, tailored to hot-cell operation, were used to evaluate the minimum ignition temperature of a dust layer on a heated surface at constant temperature, the ignition temperature of a dust cloud, the auto-ignition temperature of a cylindrical dust formation as a function of sample volume, and the explosion pressure and pressure rise in a 20-l spherical chamber. Samples of fines (<100 μm diameter) were characterized by measuring their density and particle-size distribution, and by scanning electron microscopy. For samples of irradiated zircaloy, the ignition temperatures were lower and the explosion pressures and pressure rises higher than for unirradiated zircaloy. These findings can be explained by the different particle-size distribution of irradiated material samples. The increased brittleness of the irradiated material produces more small particles (<20 μm) which favour ignition and explosion.