Spinel deoxidation equilibria in the Fe Mn Al O system - experiments and computation

The concentration and chemical potential of oxygen in liquid Fe--Mn alloys equilibrated with the spinel solution, (Fe, Mn)Al sub 2+2x O sub 4+3x , and alpha -Al sub 2 O sub 3 have been determined at 1873K as a function of manganese concentration. The composition of the spinel phase has been determined using electron probe microanalysis. The results are compared with data reported in the literature. The deoxidation equilibrium has been computed using data on free energy of solution of oxygen in liquid iron, free energies of formation of hercynite and galaxite, and interaction parameters reported in the literature. The activity--composition relationship in spinel solution was derived from a cation distribution model. The model is in excellent agreement with the experimental data on oxygen concentration and potential and the composition of the spinel phase. 23 ref.--AA

Measurement and modeling of Alloy-Spinel-Corundum equilibrium in the Ni-Mn-Al-0 system at 1873 K

The oxygen content of liquid Ni-Mn alloy equilibrated with spinel solid solution, (Ni,Mn)O. (1 +x)A12O3, and α-Al2O3 has been measured by suction sampling and inert gas fusion analysis. The corresponding oxygen potential of the three-phase system has been determined with a solid state cell incorporating (Y2O3)ThO2 as the solid electrolyte and Cr + Cr2O3 as the reference electrode. The equilibrium composition of the spinel phase formed at the interface of the alloy and alumina crucible was obtained using EPMA. The experimental data are compared with a thermodynamic model based on the free energies of formation of end-member spinels, free energy of solution of oxygen in liquid nickel, interaction parameters, and the activities in liquid Ni-Mn alloy and spinel solid solution. Mixing properties of the spinel solid solution are derived from a cation distribution model. The computational results agree with the experimental data on oxygen concentration, potential, and composition of the spinel phase.

Growth, magnetotransport, and magnetic properties of ferromagnetic (In,Mn)Sb crystals

In1−xMnxSb crystals are grown with different Mn doping concentrations (x = 0.006, 0.01, 0.02, and 0.04) beyond the equilibrium solubility limit by the horizontal Bridgman technique. Structural, magnetic, and magnetotransport properties of the grown crystals are studied in the temperature range 1.4–300 K. Negative magnetoresistance and anomalous Hall effect are observed below 10 K. The anomalous Hall coefficient is found to be negative. The temperature dependence of the magnetization measurement shows a magnetic ordering below 10 K, which could arise from InMnSb alloy formation. Also, the saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic MnSb clusters in the crystals, which has been verified by scanning electron microscopy studies. The carrier concentration increases with Mn doping, and this results in a decrease of resistivity. The carrier concentration and mobility at room temperature for the doped crystals are ∼ 2×1019 cm−3 and ∼ 200 cm2/V s, respectively. The observed anomalous Hall effect suggests the carrier mediated ferromagnetism below 10 K in In1−xMnxSb crystals.

Ba(3)(P(1-x)Mn(x)O(4))(2): Blue/green inorganic materials based on tetrahedral Mn(V)

We describe a blue/green inorganic material, Ba(3)(P(1-x)-Mn(x)O(4))(2) (I) based on tetrahedral MnO(4)(3-):3d(2) chromophore. The solid solutions (I) which are sky-blue and turquoise-blue for x <= 0.25 and dark green for x >= 0-50, are readily synthesized in air from commonly available starting materials, stabilizing the MnO(4)(3-) chromophore in an isostructural phosphate host. We suggest that the covalency/ionicity of P-O/Mn-O bonds in the solid solutions tunes the crystal field strength around Mn(V) such that a blue colour results for materials with small values of x. The material could serve as a nontoxic blue/green inorganic pigment.

Kinetics of carbon monoxide oxidation with Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts

Base metal substituted Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts were synthesized by the solution combustion method and characterized by XRD, XPS, TEM and BET surface area analysis. The catalytic activities of these materials were investigated by performing CO oxidation. The rates and the apparent activation energies of the reaction for CO oxidation were determined for each catalyst. All the substituted catalysts showed high rates and lower activation energies for the oxidation of CO as compared to unsubstituted SnO(2). The rate was found to be much higher over copper substituted SnO(2) as compared to other studied catalysts. 100% CO conversion was obtained below 225 degrees C over this catalyst. A bifunctional reaction mechanism was developed that accounts for CO adsorption on base metal and support ions and O(2) dissociation on the oxide ion vacancy. The kinetic parameters were determined by fitting the model to the experimental data. The high rates of the CO oxidation reactions at low temperatures were rationalized by the high dissociative chemisorption of adsorbed O(2) over these catalysts.

Cation-templated 2-D Mn(II)-oxalate framework with an acyclic tetrameric water cluster

The single-crystal X-ray structure of a cation-templated manganese-oxalate coordination polymer [NH(C2H5)(3)][Mn-2(ox)(3)]center dot(5H(2)O)] (1) is reported. In 1, triethylammonium cation is entrapped between the cavities of 2-D honeycomb layers constructed by oxalate and water. The acyclic tetrameric water clusters and discrete water assemble the parallel 2-D honeycomb oxalate layers via an intricate array of hydrogen bonds into an overall 3-D network. The magnetic susceptibility, with and without the water cluster, are reported with infrared and EPR studies.

Two Novel Heterometallic Chains Featuring Mn-II and Na-I Ions in Trigonal-Prismatic Geometries Alternately Linked to Octahedral Mn-IV Ions: Synthesis, Structures, and Magnetic Behavior

Two new one-dimensional heterometallic complexes, Mn3Na(L)(4)(CH3CO2)(MeOH)(2)]-(ClO4)(2)center dot 3H(2)O (1), Mn3Na(L)(4)(CH3CH2CO2)-(MeOH)(2)](ClO4)(2)center dot 2MeOH center dot H2O (2) LH2 = 2-methyl-2-(2-pyridyl)propane-1,3-diol], have been synthesized and characterized by X-ray crystallography. Both complexes feature Mn-II and Na-I ions in trigonal-prismatic geometries that are linked to octahedral Mn-IV ions by alkoxy bridges. Variable-temperature direct- and alternating-current magnetic susceptibility data indicated a spin ground state of S = 11/2 for both complexes. Density functional theory calculations performed on 1 supported this conclusion.

Stabilization of O-Mn-O clusters (Mn-5) in three dimensionally extended MOF structures: synthesis, structure and properties

Four new three-dimensional Mn2+ ion-containing compounds have been prepared by employing a hydrothermal reaction between Mn(CH3COO)(2)center dot 4H(2)O, sulfodibenzoic acid (H(2)SDBA), imidazole, alkali hydroxide and water at 220 degrees C for 1 day. The compounds have Mn-5 (1-4) clusters connected by SDBA, forming the three-dimensional structure. A time and temperature dependent study on the synthesis mixture revealed the formation of a one-dimensional compound, Mn(SDBA)(H2O)(2), at lower temperatures (T <= 180 degrees C). The stabilization of the fcu related topology in the compounds is noteworthy. Magnetic studies indicate strong anti-ferromagnetic interactions between the Mn2+ ions within the clusters in the temperature range 75-300 K. The rare participation of a sulfonyl group in the bonding is important and can pave way for the design of new structures.

Synthesis, luminescence and EPR studies on CaSiO 3: Pb, Mn-nano phosphors synthesized by the solution combustion method

Nano-ceramic phosphor CaSiO 3 doped with Pb and Mn was synthesized by the low temperature solution combustion method. The materials were characterized by Powder X-Ray Diffraction (XRD), Thermo-gravimetric and Differential Thermal Analysis (TG-DTA), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The Electron Paramagnetic Resonance (EPR) spectrum of the investigated sample exhibits a broad resonance signal centered at g=1.994. The number of spins participating in resonance (N) and its paramagnetic susceptibility (�) have been evaluated. Photoluminescence of doped CaSiO 3 was investigated when excited by UV radiation of 256 nm. The phosphor exhibits an emission peak at 353 nm in the UV range due to Pb 2+. Further, a broad emission peak in the visible range 550-625 nm can be attributed to 4T 1� 6A 1 transition of Mn 2+ ions. The investigation reveals that doping perovskite nano-ceramics with transition metal ions leads to excellent phosphor materials for potential applications. © 2012 Elsevier Ltd and Techna Group S.r.l.

Effect of co-substitution of Mn and Al on thermoelectric properties of chromium disilicide

CrSi2 was earlier reported to be an interesting thermoelectric material for high temperature applications because of its high oxidation resistance and good mechanical properties. In order to enhance its figure of merit, Mn at Cr site and Al at Si site were substituted into CrSi2. Our results indicate that Cr1-x Mn (x) Si2-x Al (x) solid solutions exhibit significantly lower thermal conductivity and a higher figure of merit than CrSi2.

A simple method of synthesis and optical properties of Mn doped ZnO nanocups

A combination of chemical and thermal annealing techniques has been employed to synthesize a rarely reported nanocup structure of Mn doped ZnO with good yield. Nanocup structures are obtained by thermally annealing the powder samples consisting of nanosheets, synthesized chemically at room temperature, isochronally in a furnace at 200-500 degrees C temperature range for 2 h. Strong excitonic absorption in the UV and photoluminescence (PL) emission in UV-visible regions are observed in all the samples at room temperature. The sample obtained at 300 degrees C annealing temperature exhibits strong PL emission in the UV due to near-band-edge emission along with very week defect related emissions in the visible regions. The synthesized samples have been found to be exhibiting stable optical properties for 10 months which proved the unique feature of the presented technique of synthesis of nanocup structures. (C) 2012 Elsevier B.V. All rights reserved.

Magnetization in electron- and Mn- doped SrTiO3

Mn- doped SrTiO3.0, when synthesized free of impurities, is a paramagnetic insulator with interesting dielectric properties. Since delocalized charge carriers are known to promote ferromagnetism in a large number of systems via diverse mechanisms, we have looked for the possibility of any intrinsic, spontaneous magnetization by simultaneous doping of Mn ions and electrons into SrTiO3 via oxygen vacancies, thereby forming SrTi1-xMnxO3-delta, to the extent of making the doped system metallic. We find an absence of any enhancement of the magnetization in the metallic sample when compared with a similarly prepared Mn doped, however, insulating sample. Our results, thus, are not in agreement with a recent observation of a weak ferromagnetism in metallic Mn doped SrTiO3 system.

Effective Mass-Driven Structural Transition in a Mn-Doped ZnS Nanoplatelet

Mn doping in ZnS nanoplatelets has been shown to induce a structural transition from the wurtzite to the zinc blende phase. We trace the origin of this transition to quantum confinement effects, which shift the valence band maximum of the wurtzite and zinc blende polyrnorphs of ZnS at different rates as a function of the nanocrystal size, arising from different effective hole masses in the two structures. This modifies the covalency associated with Mn incorporation and is reflected in the size-dependent binding energy difference for the two structures.

Ultranarrow and Widely Tunable Mn2+-Induced Photoluminescence from Single Mn-Doped Nanocrystals of ZnS-CdS Alloys

Extensively studied Mn-doped semiconductor nanocrystals have invariably exhibited photoluminescence over a narrow energy window of width <= 150 meV in the orange-red region and a surprisingly large spectral width (>= 180 meV), contrary to its presumed atomic-like origin. Carrying out emission measurements on individual single nanocrystals and supported by ab initio calculations, we show that Mn PL emission, in fact, can (i) vary over a much wider range (similar to 370 meV) covering the deep green-deep red region and (ii) exhibit widths substantially lower (similar to 60-75 meV) than reported so far, opening newer application possibilities and requiring a fundamental shift in our perception of the emission from Mn-doped semiconductor nanocrystals.

Evolution of microstructure and texture in friction stir processed Al-Mg-Mn alloy

Friction stir processing was carried out on the Al-Mg-Mn alloy to achieve ultrafine grained microstructure. The evolution of microstructure and micro-texture was studied in different regions of the deformed sample, namely nugget zone, thermo-mechanically affected zone (TMAZ) and base metal. The average grain sizes of the nugget zone, TMAZ and base metal are 1.5 mu m +/- 0.5 mu m, 15 mu m +/- 8 mu m, and 80 mu m +/- 10 mu m, respectively. The TMAZ exhibits excessive deformation banding structure and sub-grain formation. The orientation gradient within the sub-grain is dependent on grain size, orientation, and distance from nugget zone. The microstructure was partitioned based on the grain orientation spread and grain size values to separate the recrystallized fraction from the deformed region in order to understand the micromechanism of grain refinement. The texture of both deformed and recrystallized regions are similar in nature. Microstructure and texture analysis suggest that the restoration processes are different in different regions of the processed sample. The transition region between nugget zone and TMAZ exhibits large elongated grains surrounded by fine equiaxed grains of different orientation which indicate the process of discontinuous dynamic recrystallization. Within the nugget zone, similar texture between deformed and recrystallized grain fraction suggests that the restoration mechanism is a continuous process.