Crystal field parameters and energy level structure of the MnO4 tetroxo anion in Li3PO4, Ca2PO4Cl and Sr5(PO4)3Cl crystals

A comparative study concerning the electronic structure of the Mn⁵⁺ ion in the Li₃PO₄, Ca₂PO₄Cl, Sr₅(PO₄)₃Cl host lattices has been carried out in the framework of the exchange charge model. The crystal field parameters have been evaluated using the structural data as the only input information. The 10 K absorption spectra of the investigated compounds have been measured in order to verify the correspondence between experimental and calculated energy levels. A systematic trend of the crystal field splitting of the most intense transitions has been evidenced and discussed by considering the symmetry properties of the coordination polyhedra around Mn⁵⁺.     

Effect of K doping on the physical properties of La0.65Ca0.35−xKxMnO3 (0?x?0.2) perovskite manganites

The effects of K doping in the A-site on the structural, magnetic and magnetocaloric properties in La_0.65Ca_0.35−xK_xMnO₃ (0?x?0.2) powder samples have been investigated. Our samples have been synthesized using the solid-state reaction method at high temperature. The parent compound La_0.65Ca_0.35MnO₃ is an orthorhombic (Pbnm space group) ferromagnet with a Curie temperature T_C of 248 K. X-ray diffraction analysis using the Rietveld refinement show that all our synthesized samples are single phase and crystallize in the orthorhombic structure with Pbnm space group for x?0.1 and in the rhombohedral system with R3¯c space group for x=0.2 while La_0.65Ca_0.2K_0.15MnO₃ sample exhibits both phases with different proportions. Magnetization measurements versus temperature in a magnetic applied field of 50 mT indicate that all our investigated samples display a paramagnetic-ferromagnetic transition with decreasing temperature. Potassium doping leads to an enhancement in the strength of the ferromagnetic double-exchange interaction between Mn ions, and makes the system ferromagnetic at room temperature. Arrott plots show that all our samples exhibit a second-order magnetic-phase transition. The value of the critical exponent, associated with the spontaneous magnetization, decreases from 0.37 for x=0.05 to 0.3 for x=0.2. A large magnetocaloric effect (MCE) has been observed in all samples, the value of the maximum entropy change, |ΔS_m|_max, increases from 1.8 J/kg K for x=0.05 to 3.18 J/kg K for x=0.2 under a magnetic field change of 2 T. For x=0.15, the temperature dependence of |ΔS_m| presents two maxima which may arise from structural inhomogeneity.     

Elastic behaviour of strontium-doped lanthanum calcium manganites in the vicinity of TC

Colossal magnetoresistance (CMR) manganites with compositional formula, La_0.67Ca_0.33−xSr_xMnO₃ (where x=0, 0.09, 0.11, 0.13, 0.33) were prepared by citrate gel route mainly to understand the elastic behaviour in the vicinity of their magnetic transition temperature T_C. The structural characterizations of all the materials clearly indicate that samples upto x=0.13 doping, are having orthorhombic structure with Pbnm space group and sample with x=0.33 is having rhombohedral structure with space group. The magnetic transition temperatures (T_C) are determined by AC susceptibility measurements and are found to increase continuously with increasing strontium concentration. Finally, a systematic investigation of the ultrasonic longitudinal velocities of all the samples was carried out. Further, all the samples are found to exhibit anomalous behaviour in the vicinity of their magnetic transition temperatures and the observed behaviour is explained using Landau's theory.     

Some basic principles in dynamic theory of viscoelastic materials with voids

According to the basic idea of classical yin-yang complementarity and modern dual-complementarity, in a simple and unified way proposed by Luo, some basic principles in the dynamic theory of viscoelastic materials with voids can be estab- lished systematically. In this paper, an important integral relation in terms of con- volutions is given, which can be considered as the generalized principle of virtual work in mechanics. Based on this relation, it is possible not only to obtain the principle of virtual work and the reciprocal theorem, but also to derive systemati- cally the complementary functionals for the eight-field, six-field, four-field simpli- fied Gurtin-type variational principles and the potential energy-functional for the two-field one in the dynamic theory of viscoelastic materials with voids by the generalized Legendre transformations given in this paper. Furthermore, with this approach, the intrinsic relationship among various principles can be explained clearly.     

掺杂Ag纳米粒子对偶氮聚合物光致异构效应的影响

报道了通过宏观测量偶氮聚合物光致异构效应,及其引起的光学各向异性变化,讨论了一种影响偶氮聚合物顺反异构效应的有效途径。在偶氮高分子聚合物中,添加了不同浓度的Ag纳米粒子,采用了波长为442nm的He-Cd偏振激光为激发光源,当Ag纳米粒子掺杂质量浓度为0.12μg/ml的时候,激发了薄膜样品中Ag纳米粒子的等离子体共振效应,增强了粒子周围纳米尺度的电磁场强度,相当程度上提高了偶氮聚合物光致异构的转换效率;另外,研究了不同的取代基同纳米Ag粒子的相互作用对光致异构效应的影响,探讨了一种能够有效地控制光致异构效应的方法。     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

Characterisation of oxygen defects in calciumdifluoride

We study the aggregation of oxygen dipoles well dispersed in a CaF₂ crystal upon annealing at temperatures ranging from 370 to 420 K. The concentration of oxygen dipoles is monitored by measuring the intensity of the ionic thermocurrent peak as well as by absorption and luminescence spectroscopies. Results from three methods agree within experimental error and yield an activation energy of (1.2±0.1) eV for the diffusion of isolated oxygen centres in the crystal.     

First-principles study of electronic structure and ferromagnetism in Ti-doped ZnO

We perform first-principles spin polarized calculations of the electronic structure of Ti-doped in ZnO. Ferromagnetism in Ti-doped ZnO is identified, which is in agreement with recent experimental and calculated results. A net magnetic moment of 0.715μ_B is found per Ti. At a Ti concentration of 12.5%, total energy calculations show that the ferromagnetic state is 68 meV lower than the antiferromagnetic state. The electronic states near Fermi energy are dominated by strong hybridization between O 2p and Ti 3d, which is just the origin of impurity band in Ti-doped ZnO and also implies that the Ti-O bond is quite covalent instead of purely ionic. Since there is no magnetic element in this compound, Ti-doped ZnO appears to be an unambiguous dilute magnetic semiconductor.     

Effect of preparation and metal content on the introduction of Fe in BEA zeolite, studied by DR UV-vis, EPR and Mössbauer spectroscopy

Fe-containing SiBEA zeolites were prepared by a two-step postsynthesis method: creation of vacant T-sites by dealumination of tetraethylammonium BEA zeolite with nitric acid and then impregnation of the resulting SiBEA zeolite with an aqueous solution of Fe(NO₃)₃. X-ray diffraction shows that iron is incorporated in SiBEA at lattice sites. The presence of Fe in its oxidation state +3 and at isolated tetrahedral sites for low metal content, was demonstrated by diffuse reflectance UV-vis, EPR and Mössbauer spectroscopy. For high iron content, diffuse reflectance UV-vis and Mössbauer spectra revealed the additional presence of extra-lattice FeO_x oligomers and superparamagnetic Fe-oxyhydroxide. Mössbauer spectroscopy identified superparamagnetic Fe-oxyhydroxide as the main phase when basic conditions are used for the preparation.     

Optical and photocatalytic properties of nanocrystalline TiO2 synthesised by solid-state chemical reaction

Nanoparticulate TiO₂ is of interest for a variety of technological applications, including optically transparent UV-filters and photocatalysts for the destruction of chemical waste. The successful use of nanoparticulate TiO₂ in such applications requires an understanding of how the synthesis conditions effect the optical and photocatalytic properties. In this study, we have investigated the effect of heat treatment temperature on the properties of nanoparticulate TiO₂ powders that were synthesised by solid-state chemical reaction of anhydrous TiOSO₄ with Na₂CO₃. It was found that the photocatalytic activity increased with the heat treatment temperature up to a maximum at 600 °C and thereafter declined. In contrast, the optical transparency decreased monotonically with the heat treatment temperature. These results indicate that solid-state chemical reaction can be used to prepare powders of nanoparticulate TiO₂ with properties that are optimised for use as either optically transparent UV-filters or photocatalysts.