ENDOR studies of hydrogen bonding of the AsO44- centre in x-ray irradiated KH2AsO4

We here report what we believe to be an important method for studying hydrogen bonding in systems containing a paramagnetic centre. The technique of electron-nuclear double resonance ( ENDOR) has been applied to study the hydrogen-bond network around the AsO44-. centre in X-ray irradiated KH2AsO4. ENDOR transitions from several sets of hydrogen nuclei surrounding the centre were observed at 4.2 degrees K and the spectra for two sets of neighbouring nuclei are identified. The angular dependences for these spectra are fitted with a spin-Hamiltonian to obtain the isotropic and anisotropic magnetic hyperfine constants. The results are discussed in terms of the available spectroscopic and crystallographic data on KH2AsO4 and the order-disorder model of ferroelectrictricity in this class of crystals.

Graphene scavenges free radicals to synergistically enhance structural properties in a gamma-irradiated polyethylene composite through enhanced interfacial interactions

A unique strategy for scavenging free radicals in situ on exposure to gamma irradiation in polyethylene (PE) nanocomposites is presented. Blends of ultra-high molecular weight PE and linear low-density PE (PEB) and their nanocomposites with graphene (GPEB) were prepared by melt mixing to develop materials for biomedical implants. The effect of gamma irradiation on the microstructure and mechanical properties was systematically investigated. The neat blend and the nanocomposite were subjected to gamma-ray irradiation in order to improve the interfacial adhesion between PE and graphene sheets. Structural and thermal characterization revealed that irradiation induced crosslinking and increased the crystallinity of the polymer blend. The presence of graphene further enhanced the crystallinity via crosslinks between the polymer matrix and the filler on irradiation. Graphene was found to scavenge free radicals as confirmed by electron paramagnetic resonance spectroscopy. Irradiation of graphene-containing polymer composites resulted in the largest increase in modulus and hardness compared to either irradiation or addition of graphene to PEB alone. This study provides new insight into the role of graphene in polymer matrices during irradiation and suggests that irradiated graphene-polymer composites could emerge as promising materials for use as articulating surfaces in biomedical implants.

Assembly of sol-gel-grown $Li _{(x)} CoO_{2}$ nanocrystals through electromagnetic irradiation

We report the fabrication of assembled nanostructures from the pre-synthesized nanocrystals building blocks through optical means of exciton formation and dissociation. We demonstrate that Li (x) CoO2 nanocrystals assemble to an acicular architecture, upon prolonged exposure to ultraviolet-visible radiation emitted from a 125 W mercury vapor lamp, through intermediate excitation of excitons. The results obtained in the present study clearly show how nanocrystals of various materials with band gaps appropriate for excitations of excitons at given optical wavelengths can be assembled to unusual nanoarchitectures through illumination with incoherent light sources. The disappearance of exciton bands due to Li (x) CoO2 phase in the optical spectrum of the irradiated film comprising acicular structure is consistent with the proposed mechanism of exciton dissociation in the observed light-induced assembly process. The assembly process occurs through attractive Coulomb interactions between charged dots created upon exciton dissociation. Our work presents a new type of nanocrystal assembly process that is driven by light and exciton directed.

Dynamics of the ammonium ion in the ferroelectric transition in sodium ammonium selenate, NaNH4SeO4·2H2O-an E.S.R. study

E.S.R. investigations of γ-irradiated ferroelectric Sodium ammonium selenate, NaNH4SeO4•2H2O and its deuteriated analogue in powder and single crystal forms have led to a deeper understanding of the nature of the ferroelectric transition of 180 K. A number of paramagnetic species formed due to γ-irradiation have been identified on the basis of their g-factors and hyperfine features from 77Se. The radical SeO4 has been used as a microprobe in studying the phase transition.

Switching Process in Ferroelectric Triglycine Selenate

Triglycine selenate (TGSe) is isomorphous with Triglycine sulphate and is ferroelectric below 22°C. It is interesting to study the switching process in TGSe in the ferro-state with a view to comparing the results with TSG. The switching process was studied by applying electrical square pulses to produce fields up to 5 kV/cm on the sample, and measuring the parameters characterizing the transient current flowing in the sample, according to the Merz method. The temperature range in which the process was studied was 15°C to -20°C. The results were analysed by applying the Pulvari-Kuebler theory and the parameters α the activation field and µ the mobility of the domains were evaluated. It is found that µ varies with temperature in TGSe in a manner similar to TGS. µ is lesser for TGSe than for TGS for the same shift of temperature from Tc. The switching behaviour of γ-irradiated TGSe is qualitatively similar to that of unirradiated crystal eventhougth the process gets slowed down as a result of irradiation.

Polarization switching in radiation damaged ferroelectric crystals

The polarization switching processes in radiation damaged ferroelectrics were studied by the Merz method. In irradiated triglycine sulphate and sodium nitrite, the switching time depends exponentially on the applied electric field. Irradiation increases the importance of nucleation and sideways motion of the domain walls in polarization switching.

Study of switching characteristics and thermal noise in ferroelectric crystals both in the pure and radiation damaged state

The phase transition in gamma-irradiated triglycine sulphate (TGS) has been investigated by using a method based on the measurement of thermal noise. The results of a study of the polarization switching characteristics of gamma irradiated TGS and sodium nitrite (NaNO2) have also been presented. The effect of irradiation on the phase transition and the switching processes has been discussed.

ESR Study of a Cr5+ Centre in Ferroelectric Ammonium Sulphate

X-band electron spin resonance (ESR) studies of (CrO4)2- doped, X-irradiated single crystals of ferroelectric ammonium sulphate ((NH4)2SO4, TC = 223 K) at 300 and 208 K are reported. The paramagnetic centre responsible for the ESR spectrum is identified to be Cr5+. Superhyperfine interaction of the unpaired electron with two equivalent protons is observed. The spin-Hamiltonian parameters which are nearly axial at 300 K, with g < g indicating a dx2-y2 orbital ground state, acquired rhombic character below TC indicating a distortion of the sulphate tetrahedron. An increase in the value of the proton superhyperfine constant in the ferroelectric phase is indicative of stronger hydrogen bonding.

Spinodal Decomposition in Tellurite-Based Glasses Induced by Excimer Laser Irradiation

Tellurite-based glasses in the TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30, and V2Te2O9 were fabricated by the conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via the X-ray powder diffraction technique and differential thermal analysis, respectively. The as-quenched samples were irradiated by an excimer laser (248 nm). The effect of laser power, duration of irradiation, and the frequency of the laser pulses on the surface features of the above glasses were studied. The optical microscopic studies carried out on the above systems revealed the presence of quasi-periodic and periodic structures on their surfaces. The local compositional variations of these structures were confirmed by back-scattered electron imaging using scanning electron microscope accompanied by energy-dispersive X-ray analysis. These results were convincing enough to state that the glasses in the present investigations had undergone spinodal decomposition on laser irradiation. The incidence of the interconnected texture of two different phases was observed owing to the quenching effect produced by the heating and cooling cycle of the successive laser pulses. Ring- and line-shaped patterns were also observed, respectively, when the pulse frequency of the laser and the duration of irradiation were increased.

Enhanced catharanthine and vindoline production in suspension cultures of Catharanthus roseus by ultraviolet-B light

Suspension cultures of Catharanthus roseus were used to evaluate ultraviolet-B (UV-B) treatment as an abiotic elicitor of secondary metabolites. A dispersed cell suspension culture from C. roseus leaves in late exponential phase and stationary phase were irradiated with UV-B for 5 min. The stationary phase cultures were more responsive to UV-B irradiation than late exponential phase cultures. Catharanthine and vindoline increased 3-fold and 12-fold, respectively, on treatment with a 5-min UV-B irradiation.

Ion irradiation enhances the mechanical performance of metallic glasses

We demonstrate that irradiation may enhance the plasticity in metallic glasses by increasing the free-volume content via micropillar compression experiments on an ion-irradiated bulk metallic glass (BMG). Results show that irradiation decreases the flow stress and enhances the shear band formation by lowering the magnitude of stress serrations in plastic flow regime. These results highlight that amorphous alloys can mitigate the deleterious affects of severe ion irradiation as compared to their crystalline counterparts. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr0.53Ti0.47O3 (PZT), (Pb0.90La0.10)TiO3 (PLT10) and (Pb0.80La0.20)TiO3 (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance-voltage (C- V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C-V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 degrees C for 10 min. The phase transition temperature [T-c] of PLT20 increased from 115 degrees C to 120 degrees C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 degrees C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation. (C) 2007 Elsevier B.V. All rights reserved.

On photooxidation of Ge in obliquely deposited Ge and Ge25X75(X = S, Se, Te) thin films

It has been established by photoemission studies that Ge in obliquely deposited pure Ge and Ge-chalcogenide thin films undergoes predominant photooxidation when irradiated with band gap photons. The role of Ge appears to be that of providing a highly porous low density microstructure and photooxidation seems to be a direct consequence of such large scale porosity in these films. The formation of low vapour pressure oxide fractions of Ge and Te and volatile high vapour pressure oxide fractions of S and Se is responsible for anomalous photoinduced transformations in these films.

Effect of √-irradiation on the structure and dynamics of domains in triglycine selenate

A comparative study of the switching properties of pure and √-irradiated TGSe crystals has been carried out to see the effect of irradiation on the structure and dynamics of domains. The switching behaviour of √-irradiated TGSe has been found to be qualitatively similar to that of unirradiated crystal and this has been interpreted in terms of structural inhibition caused by the formation of radiolysis products as well as the difference between the domain structures of the unirradiated and irradiated samples. Confirmation of this has been obtained by studying the domain patterns using the etch method.

Polarization reversal studies in ferroelectric taap

Telluric Acid Ammonium Phosphate (Te(OH)62(NH4)H2PO4(NH4)2HPO4) reffered to as TAAP is a recently discovered class m ferroelectric.1 It undergoes FE-PE transition at 48°C. Switching studies in this crystal has been carried out in the temperature range -14°C to 39°C by applying fields up to 4 kV/cm. Measurements were carried out on (101) plates cut from the crystals grown from solution. X-ray irradiation was carried out at room temperature by means of an x-ray tube operating at 25 kV and 15 mA with copper target. Air drying silver paste was used as electrodes. Samples were checked for hysteresis loop using a modified Sawyer-Tower circuit. The Ps value obtained from the loop is 2.1 μC/cm2 which is comparable to the earlier reported value. It was however noticed that the loop was slightly shifted to right with respect to the origin indicating the presence of a small internal bias which was 100 V/cm in the virgin crystal. This bias could not be removed even after repeated crystallization. On irradiation the internal biasing field increased which was indicated by a further shift of the hysteresis loop. The bias seems to saturate at about 750 V/cm for which the crystal had to be irradiated for about 3 hours.