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.

Formation of an oxo-radical of peroxovanadate during reduction of diperoxovanadate with vanadyl sulfate or ferrous sulfate

Formation of oxygen radicals during reduction of H2O2 or diperoxovanadate with vanadyl sulfate or ferrous sulfate was indicated by the 1:2:2:1 electron spin resonance (ESR) signals of the DMPO adduct typical of standard radical dotOH radical. Signals derived from diperoxovanadate remained unchanged in the presence of ethanol in contrast to those from H2O2. This gave the clue that they represent a different radical, possibly radical dotOV(O2)2+, formed on breaking a peroxo-bridge of diperoxovanadate complex. The above reaction mixtures evolved dioxygen or, when NADH was present, oxidized it rapidly which was accompanied by consumption of dioxygen. Operation of a cycle of peroxovanadates including this new radical is suggested to explain these redox activities both with vanadyl and ferrous sulfates. It can be triggered by ferrous ions released from cellular stores in the presence of catalytic amounts of peroxovanadates.

ESR studies of X-irradiated strontium mixed calcium tartrate crystals

The electron spin resonance spectra of X-ray irradiated single crystals of strontium doped calcium tartrate tetrahydrate (CST) with molecular formula Ca0.88Sr0.12C4H4O6.4H(2)O grown in gels has been investigated. Only one species of free radical but with two magnetically unequivalent sites was observed at room temperature. The free radical was found to be the result of the splitting of a C-II bond adjacent to both the hydroxyl and carboxyl groups. The a factor was found to be slightly anisotropic. Couplings with two H nuclei, believed to be the proton of the OH group attached directly to the unsaturated asymmetric carbon atom and the proton attached directly to the: other asymmetric carbon atom of the molecule were observed. The principal g-values were found to be 2.0030, 2.0017, 2.0027. The principal elements of the nuclear coupling are 7.45, 6.59, 4.28 and 8.56, 7.22, 18.71 G, respectively. The radical was found to be very stable. (C) 2000 Elsevier Science Ltd. All rights reserved.

Coexistence of para and ferromagnetic phases of Fe3+ in undoped CdZnTe (Zn similar to 4%) crystals

The signatures of the coexistence of para and ferromagnetic phases for the Fe3+ charge state of iron have been identified in the low temperature electron spin resonance (ESR) spectra in undoped CdZnTe (Zn similar to 4%) crystals and independently verified by superconducting quantum interference device (SQUID) and AC susceptibility measurements. In the paramagnetic phase the inverse of AC susceptibility follows the Curie-Weiss law. In the ferromagnetic phase the thermal evolution of magnetization follows the well-known Bloch T-3/2 law. This is further supported by the appearance of hysteresis in the SQUID measurements at 2 K below T-c which is expected to lie in between 2 and 2.5 K. (C) 2010 Elsevier Ltd. All rights reserved.

Phase relations in the system SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K

Phase relations in the systems SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K were established by equilibrating different compositions in flowing oxygen gas at a pressure of 1.01 × 105 Pa. The quenched samples were examined by optical microscopy, X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX), and electron spin resonance (ESR). In the system SrO-Y2O3-CuO-O2, except for the limited substitution of Y3+ for Sr2+ ions in the ternary oxide Sr14Cu24O41, no new quaternary phase was found to be stable. The compositions corresponding to the solid solution Sr14−xYxCu24O41 and the compound SrCuO2+δ lie above the plane containing SrO, Y2O3, and CuO,displaced towards the oxygen apex. However, in the system CaO-Y203-CuO-O2 at 1173 K, all the condensed phases lie on the plane containing CaO, Y203, and CuO, and a new quaternary oxide YCa2Cu306.s is present. The quaternary phase has a composition that lies at the center of the nonstoichiometric field of the analogous phase YBa2Cu307_~ in the BaO-Y203-CuO-O2 system. The compound YCa2Cu306.s has the tetragonal structure and does not become superconducting at low temperature. Surprisingly, phase relations in the three systems CaO-Y203-CuO-O2, SrO-Y203-CuO-O2, and BaO-Y203-CuO-O2 are found to be quite different.

Effect of calcium stoichiometry on the dielectric response of CaCu3Ti4O12 ceramics

CaxCu3Ti4O12 (x=0.90, 0.97, 1.0, 1.1 and 1.15) polycrystalline powders with variation in calcium content were prepared via the oxalate precursor route. The structural, morphological and dielectric properties of the ceramics fabricated using these powders were studied using X-ray diffraction, scanning electron microscope along with energy dispersive X-ray analysis, transmission electron microscopy, electron spin resonance (ESR) spectroscopy and impedance analyzer. The X-ray diffraction patterns obtained for the x = 0.97, 1.0 and 1.1 powdered ceramics could be indexed to a body-centered cubic perovskite related structure associated with the space group Im3. The ESR studies confirmed the absence of oxygen vacancies in the ceramics that were prepared using the oxalate precursor route. The dielectric properties of these suggest that the calcium deficient sample (x = 0.97) has a reduced dielectric loss while retaining the high dielectric constant which is of significant industrial relevance. (C) 2012 Elsevier Ltd. All rights reserved.

Structural modification and enhanced magnetic properties with two phonon modes in Ca-Co codoped BiFeO3 nanoparticles

Bi1-xCaxFe1-xCoxO3 nanoparticles with x=0.0, 0.05, 0.10 and 0.15 were successfully synthesized by cost effective tartaric acid based sol gel route. The alkali earth metal Ca2+ ions and transition metal Co3+ ions codoping at A and B-sites of BiFeO3 results in structural distortion and phase transformation. Rietveld refinement of XRD patterns suggested the coexistence of rhombohedral and orthorhombic phases in codoped BiFeO3 samples. Both XRD and Raman scattering studies showed the compressive lattice distortion in the samples induced by codoping of Ca2+ and Co3+ ions. Two-phonon Raman spectra exhibited the improvement of magnetization in these samples. X-ray photoelectron spectroscopy (XPS) showed the dominancy of Fe3+ and Co3+ oxidation states along with the shifting of the binding energy of Bi 4f orbital which confirms the substitution Ca2+ at Bi-site. The magnetic study showed the enhancement in room temperature ferromagnetic behavior with co-substitution consistent with Rama analysis. The gradual change in line shape of electron spin resonance spectra indicated the local distortion induced by codoping. (C) 2015 Published by Elsevier Ltd and Techna Group S.r.l.

Study of coexisting phases in Bi doped La0.67Sr0.33MnO3

We report the remarkable phase separation behavior in La0.67Sr0.33MnO3 doped with Bi3+ ion at La site. The temperature dependent resistivity and magnetization of La0.67-xBixSr0.33MnO3 (x>0) show the presence of phase separation of ferromagnetic metallic and charge ordered antiferromagnetic insulating phases. Markedly, the field dependant magnetization studies of La0.67-xBixSr0.33MnO3 (x=0.3) show the metamagnetic nature of ferromagnetic metallic state implying the competition of coexisting ferromagnetic metallic and charge ordered antiferromagnetic phases. The electron spin resonance and exchange bias studies of La0.67-xBixSr0.33MnO3 (x=0.4 and 0.5) substantiate the coexistence of ferromagnetic clusters in antiferromagnetic matrix. (C) 2016 Elsevier B.V. All rights reserved.

Long-term natural acidification of upland sites in Cumbria: Evidence from post-glacial lake sediments

Studies by the Freshwater Biological Association over the last 25 years have supplied data relevant to the levels of acidity in local soils and water before the onset of industrial pollution and current interest in acid rain. This article reviews published analysis from cores of lake sediments, in or near the catchment of the River Duddon. Electron spin resonance spectra of humic acids and iodine values confirm evidence from pollen analysis for a history of progressive acidification of the source material of lake sediments since before 5000 radiocarbon years, in upland catchments of the Lake District. Processes involved included: removal of basic ions from soils by rainfall, the effects of which were intensified by removal by man of deciduous forest; acidification of soils and waters by decomposition products of Calluna and further acidification of waters by Sphagnum species which colonized habitats where drainage became impeded by paludification processes.

LiMn2-xGexO4 como material catódico para baterías de ión-litio

32 p.

飞秒激光辐照K9玻璃引起的暗化和折射率变化

对不同辐照条件下近红外飞秒激光在K9玻璃内部诱导产生的暗化现象和永久性折射率改变进行了实验研究。通过辐照前后的显微镜图片、吸收光谱、电子自旋共振谱(ESR)以及激光衍射实验，分析了K9玻璃中暗化现象产生的微观过程，发现暗化是由诱导产生的空穴型色心引起的。暗化程度和折射率改变随激光强度、扫描速度、扫描行间距变化而变化。光致色心的形成与非线性电离有关。对折射率永久性改变进行了简单说明，其机理仍在探索中。

Photoreduction of Ag+ in aluminoborate glasses induced by irradiation of a femtosecond laser

We report on photoreduction of Ag+ in aluminoborate glasses induced by irradiation of a femtosecond laser. Novel fluorescence was observed in the femtosecond laser irradiated glass when excited by a 365 nm ultraviolet lamp. Optical absorption, emission, and electron spin resonance spectra of the glass samples demonstrated that after the laser irradiation, portions of silver ions near the focused part of the laser beam inside the glass were reduced to silver atoms, which resulted in the formation of the characteristic fluorescence. The observed phenomenon may have promising applications in the fabrication of functional optical devices.

飞秒激光脉冲照射诱导含芴结构树脂共聚物结构变化及机理的研究

在室温下用聚焦的飞秒激光照射高折射率、低双折射的透明含芴结构树脂-对苯二甲酸乙二醇酯(PET)共聚物，探索飞秒激光制备高分子光学功能微结构的可能性。通过紫外-可见吸收光谱、红外光谱、电子自旋共振谱、光学显微镜、扫描电镜及透射电镜等分析手段，对该材料在飞秒激光照射后的结构变化及机理进行研究。结果发现：含芴结构树脂共聚物在飞秒激光照射后产生化学键断裂，生成未成对电子，并形成无定形碳；照射区在可见光区域的吸收增强；随激光能量密度的减少在激光会聚点附近诱导结构由慧尾状向单一细丝转变。演示了三维着色内雕。

Synthesis and luminescence of ZnMgS : Mn2+ nanoparticles

Efficient green emission from ZnMgS:Mn2+ nanoparticles prepared by co-doping Mg2+ and Mn2+ ions into ZnS lattices has been observed. The synthesis is carried out in aqueous solution, followed by a post-annealing process, thus showing the features of less complexity, low cost, and easy incorporation of dopants. In comparison with the emission of ZnS:Mn2+ nanoparticles, which is located generally around 590 nm, the photoluminescence of ZnMgS:Mn2+ nanoparticles is blue-shifted by 14 nm in wavelength, leading to the enhanced green emission. The X-ray diffraction, electron spin resonance, and pressure dependent photoluminescence measurements suggest that the change of the crystal field caused by Mg2+ ionic doping and the lower symmetry in the nanoparticles may account for the blue-shift of the photoluminescence. The ZnMgS:Mn2+ nanoparticles with 1% Mn2+ doping exhibit the strongest luminescence, which could potentially meet the requirements for the construction of green light emitting diodes.

氦离子注入4H-SiC晶体的纳米硬度研究；Study on nanohardness of helium-implanted 4H-SiC

4H-SiC晶体经能量为100keV,剂量为3×1016cm-2的氦离子高温(500K)注入后,再在773—1273K温度范围内进行了退火处理,最后使用纳米压痕仪测量了样品注入面的硬度.测试结果表明,在500—1273K温度范围内样品的硬度随退火温度升高呈现先增大后减小再增大的趋势,其中773K退火样品的硬度增大明显.分析认为,退火样品的硬度变化是由退火过程中缺陷复合与氦泡生长导致样品内部的Si—C键密度、键长和键角改变引起的.