Sonochemical preparation of high surface area MgAl2O4 spinel

High surface area MgAl(2)O(4) has been synthesised by a sonochemical method. Two kinds of precursors were used, alkoxides and nitrates/acetates and in both cases nanostructured MgAl(2)O(4) was obtained. The effect of the addition of a surfactant during the sonication, cetyl trimethyl ammonium bromide, was also investigated. In the case of alkoxides precursors the as-made product is a mixture of hydroxides of aluminium and magnesium, while with nitrates/acetates a gel is obtained after sonication, containing the metal hydroxides and ammonium nitrate. Heating at 500 degrees C transforms the as-made products into MgAl(2)O(4) spinel phase. The surface area is up to 267m(2)/g after treatment at 500 degrees C and 138m(2)/g at 800 degrees C.     

Synthesis and characterization of nanocrystalline MgAl2O4 spinel by polymerized complex method

Ultrafine MgAl₂O₄ powder has been synthesized by a polymerized complex method. Heating of a precursor solution containing citric acid (CA), ethylene glycol (EG) and Mg and Al salts with a molar ratio of Mg/Al/CA/EG=1/2/8/32 at 180°C produced a transparent polymeric gel, which have been characterized by FT-IR spectroscopy and TG/DTA. The organic fraction was removed by controlled thermal treatments (350–1200°C) whereby the bimetallic oxide was formed. XRD analysis showed the presence of MgAl₂O₄ at 600°C. TEM observation showed that the spherical nanosized powders with good uniformity was obtained. Furthermore, these powders showed excellent sinterability, relative density up to 99.8% was achieved when sintered at 1550°C for 3 h in air without any sintering additive.     

Effect of Y3+ substitution on the structural,dielectric, and electrical properties of nanosized ZnAl 2 O 4 spinel

In the present work, we have studied the structural, dielectric, and electrical properties of a series of nanosized $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ ( $x = 0.00$ , 0.01, 0.02, 0.03, 0.04, 0.05, 0.07, and 0.10) system prepared by chemical coprecipitation method. Powder X-ray diffraction (XRD) was carried out to study the influence of $\mathrm{Y}^{3+}$ substitution on the crystal structure of these samples. High Resolution Transmission Electron Microscopy (HRTEM) images reveal the nanocrystalline nature of the samples. The Fourier Transform Infrared (FTIR) spectra confirmed the preference of $\mathrm{Y}^{3+}$ ions at the octahedral B site. The variation of dielectric constant and loss tangent (1 kHz to 1 MHz) at room temperature for all the samples show the normal behavior of spinel compounds. AC conductivity study reveals that the conduction is due to small polaron hopping. The electrical modulus analysis shows that nanocrystalline $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ system exhibits non-Debye-type relaxation. The DC electrical resistivity measured in the temperature range 303–373 K was found to increase with temperature and yttrium content.     

Nonlinear absorption properties of Co2+:MgAl2O4 crystal

The differential absorption spectra of Co²⁺: MgAl₂O₄ (MALO) crystal were studied with a picosecond pump-probe technique under excitation of the ⁴A₂→⁴T₁(⁴P) and ⁴A₂→⁴T₁(⁴F) transitions of the tetrahedral Co²⁺ ion. The difference spectra of stimulated emission (SE) and excited state absorption (ESA) were derived from the measured differential absorption spectra. The ⁴T₁(⁴P)→⁴A₂ SE band around 660 nm was observed. The ESA bands were assigned to the ⁴T₂→⁴T₁(⁴P) transition and to transitions from the thermally populated ²E(²G) excited state to doublet levels arising from the ²F free-ion level of the tetrahedrally coordinated Co²⁺ ion. Absorption saturation measurements were performed at 1.34 μm and 1.54 μm. Passive Q-switching of 1.34-μm Nd³⁺:YAlO₃ and 1.54-μm Er³⁺:glass lasers was realized using the Co²⁺:MALO crystal as saturable absorber. The Q-switched laser pulses of 38 ns (110 ns) in duration and up to 2.7 mJ (10 mJ) in energy at 1.54 μm (1.34 μm) were obtained. Received: 3 March 1999 / Revised version: 30 June 1999 / Published online: 30 November 1999     

Ni0.8Zn0.2Fe2O4和CO2Y添加Ni0.8Zn0.2Fe2O4磁性质对比研究

采用固相反应法制备了Ni0.8Zn0.2Fe2O4和2wt％ Co2Y添加Ni0.8Zn0.2Fe2O4铁氧体多晶样品,并对样品的磁性质进行了研究.实验发现,添加Co2Y后,铁氧体的磁损耗明显下降,相同条件下Q值增大到原来的3倍左右.对添加Co2Y引起铁氧体磁损耗下降的原因进行了讨论,认为主要是钴离子掺杂引起的铁氧体磁滞损耗明显降低所导致的.     

Investigations of physical aspects of spinel ABi2O4 (A=Zn,Cd) oxides via ab-initio calculations

This present study aims to unravel physical properties of spinel oxides in cubic phase represented by general empirical formula of ABi₂O₄ (A=Zn, Cd) using full potential lineralized augmented plane plus local orbital (LAPW+lo) method. The structural aspect of spinel oxides in cubic phase has been investigated by Perdew-Burke-Ernzerhof generalized gradient approximation (PBEsol-GGA). The thermodynamic stability of ABi₂O₄ is established by computing the cohesive energies. On the other hand, born stability standard which is based on Chapin's tensor analysis method revealed that the mechanical stability of the oxide compounds under considerations gives a stable cubic phase. For a better prediction of electronic and thermoelectric properties of these compounds, the modified Tran-Bhala Becke and Johnson (TB-mBJ) potential is used which revels very precise band gap. Other than these investigations, thermoelectric characteristics i.e., Wiedman-Tranz constant, Seebeck coefficient and power factor are calculated and it provides essential data for fabrication of thermoelectric devices.     

Magnetic properties of ultra-fine particles of Mn0.5Fe0.5Fe2O4 spinel system

A systematic study of the magnetic properties of ultra-fine particles of Mn_0.5Fe_0.5Fe₂O₄ spinel system has been undertaken. The effect of temperature on the magnetic properties of particles and the ferrofluid has been studied. Analysis of the data yields information on the anisotropy constant, particle size distribution and superparamagnetic behaviour. The results are explained on the basis of existing theories.     

Cr3+∶MgAl2O4晶体的基态能级分裂及Jahn-Teller效应*

构造了3d3/3d7离子在三角对称晶场中考虑自旋-轨道相互作用,自旋-自旋相互作用和自旋-其它轨道相互作用的120阶微扰哈密顿矩阵.利用完全对角化该矩阵的方法计算了Cr3+∶MgAl2O4晶体的基态能级、零场分裂参量,理论计算值与实验值相符合.定量研究了自旋二重态对基态能级的贡献,证明该贡献是不可忽略的.定量研究了自旋-轨道相互作用、自旋-自旋相互作用和自旋-其它轨道相互作用对Cr3+∶MgAl2O4晶体的光谱精细结构和零场分裂参量的影响,发现自旋-轨道和自旋-自旋相互作用对基态能级和零场分裂参量的影响的程度和方式是不同的,自旋-其它轨道相互作用的影响也是不可忽略的.通过理论计算值和实验值的比较,证实了在Cr3+∶MgAl2O4晶体中Jahn-Teller效应的存在,解释了该晶体的光谱精细结构的成因.     

Effects of Mn substitution of Co and Fe in spinel CoFe2O4 thin films

Effects of Mn substitution for Co and Fe on the structural and magnetic properties of inverse-spinel CoFe₂O₄ have been investigated. Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ thin films were prepared by a sol–gel method. The observed increase of the lattice constant of Mn_xCo_1−xFe₂O₄ indicates that Mn²⁺ ions substitute the octahedral Co²⁺ sites. Conversion electron Mössbauer spectroscopy data indicate that a fraction of octahedral Co²⁺ ions exchange sites with tetrahedral Fe³⁺ ions through Mn doping. Vibrating-sample magnetometry data exhibit a large increase of saturation magnetization for both Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ films compared to that of the CoFe₂O₄ film. Such enhancement of magnetization can be explained in terms of a breaking of ferrimagnetic order induced by the Co²⁺ migration.     

Distribution and valence of the cations in the spinel system Fe3O4-Fe2VO4

The Mössbauer spectra of the solid solution Fe[Fe_xV_2–x]O₄ within 1.0×2.0 consist of two sets of sextets corresponding to A- and B-sites. From the superimposed sextets of the B-site pattern result typical values of isomer shift and internal magnetic field strength due to different environments of the B-site iron. It is shown that V ions both enhance the conduction electron density at the neighbouring Fe ions and diminish the strength of the magnetic interactions.     

Effects of excessive Zn2+ ions on intrinsic magnetic and structural properties of Ni0.2Zn0.6Cu0.2Fe2O4 powder prepared by chemical coprecipitation method

Zn(OH)₂ is a kind of amphoteric compound. Therefore, for chemical coprecipitation method, the precipitation of Zn²⁺ ions may be incomplete if using NaOH as precipitator. In this study, single-phase powder specimens with a nominal composition Ni_0.2Zn_0.6Cu_0.2Fe₂O₄ were prepared with chemical coprecipitation method, and the effects of excessive Zn²⁺ content (x, x = 3%, 5%, 7%, 9%) in working solution on intrinsic magnetic and structural properties were studied by vibrating sample magnetometer and X-ray diffractometer, respectively. It was found that the magnetization when H_m = 398 kA/m (5000 Oe) reached a maximum when x = 5%, and then decreased with the increase of x, which was attributed to the effect of different amount of Zn²⁺ in A sites on the A–B and B–B exchange interaction. Moreover, it was found that the lattice parameter was affected by the Zn²⁺ and Fe³⁺ ions due to their different ion radius to a certain extent.     

On the shape of iron K absorption edges for monoferrites with a Me(Mg, Mn, Ni, Zn)Fe2O4 spinel structure

Calculations of the K-edge x-ray absorption near-edge structure (XANES) in a pure metal and in monoferrites of stoichiometric compositions MgFe₂O₄, MnFe₂O₄, NiFe₂O₄, and ZnFe₂O₄ are carried out using a FEFF8 program. It was confirmed that the Fe K-edge energy shift found experimentally occurs upon the transition from pure iron to monoferrites. It is demonstrated that this shift is identically directed for ferrites with a structure of normal (MnFe₂O₄, ZnFe₂O₄) and inverted (MgFe₂O₄, NiFe₂O₄) spinels, but numerical values of theoretical Fe K-edge shifts agree well with experimental data only for normal spinels.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.     

绿色长余辉材料MgAl_2O_4∶Mn~(2+)的合成及其发光特性

采用高温固相法在1350℃下合成了Mn2+掺杂的MgAl2O4发光材料,利用X射线衍射对所合成样品的结构进行了表征。用209nm的紫外灯照射样品后,观察到来自Mn2+的4T1-6A1跃迁的绿色长余辉发光。发光的激发光谱表明:Mn2+-3d组态内存在一系列强的激发峰,分别在279,361,386,427,451nm,同时还有209nm处的Mn-O电荷迁移带,激发该吸收带会产生很强的绿色余辉。测量了余辉的衰减曲线及热释光谱,分析了Mn2+掺杂浓度对样品余辉性质的影响,给出了余辉产生的可能模型。     

Cluster calculations of the electronic structure of Fe4C

The electronic structure and magnetic properties of Fe₄C are investigated with the first-principles discrete variational method (DV) in spin-polarized case. It is used for the local spin density approximation of the density functional theory. Clusters of 21 and 27 atoms were adopted to represent the two non-equivalent iron sites in this compound. The calculated magnetic moments for the corner and face centered iron sites are 2.63\mu_B and 1.77\mu_B, respectively, which are in very good agreement with the experimental results. A collapse of the magnetic moment for both inequivalent iron sites was verified above 12% of contraction of the lattice spacing. The C atom acts as an acceptor for electrons in this host. This revised version was published online in August 2006 with corrections to the Cover Date.