Magnetic properties of nanostructured ferrimagnetic zinc ferrite

Nanostructured ZnFe2O4 ferrites with different grain sizes were prepared by high energy ball milling for various milling times. Both the average grain size and the root mean square strain were estimated from the x-ray diffraction line broadening. The lattice parameter initially decreases slightly with milling and it increases with further milling. The magnetization is found to increase as the grain size decreases and its large value is attributed to the cation inversion associated with grain size reduction. The Fe-57 Mossbauer spectra were recorded at 300 K and 77 K for the samples with grain sizes of 22 and 11 nm. There is no evidence for the presence of the Fe2+ charge state. At 77 K the Mossbauer spectra consist of a magnetically ordered component along with a doublet due to the superparamagnetic behaviour of small crystalline grains with the superparamagnetic component decreasing with grain size reduction. At 4.2 K the sample with 11 nm grain size displays a magnetically blocked state as revealed by the Mossbauer spectrum. The Mossbauer spectrum of this sample recorded at 10 K in an external magnetic field of 6 T applied parallel to the direction of gamma rays clearly shows ferrimagnetic ordering of the sample. Also, the sample exhibits spin canting with a large canting angle, maybe due to a spin-glass-like surface layer or grain boundary anisotropies in the material.

Solubility and physical stability improvement of natiral xanthine derivatives

Use of natural xanthine derivates in medicine is complicated with their physical properties. Theobromine is poorly soluble while theophylline is highly sensitive to hydration. The aim of this study was to improve bioavailability of xanthines by co-crystallization, theophylline was also cocrystallized with carboxylic acids (capric, citric, glutaric, malenic, malonic, oxalic, stearic, succinic) and HPMC. Co-crystallization was performed by slow evaporation and ball milling. Physical stability was checked by wet granulation and water sorption methods, solubility was measured by intrinsic tablet dissolution. Theobromine formed co-crystal with other xanthines and theophylline interacted with all acids except stearic and HPMC, the latter showed alternative interactions based on hydrogen bonding. Hydration resistance was good in theophylline:succinic acid co-crystal and excellent in complexes containing capric, stearic acids and HPMC. Theophylline:HPMC showed improved solubility. The reported approach can promote use of xanthines and can be recommended for other compounds with similar problems.

Grain size effect on the phase transformation temperature of nanostructured CuFe2O4

We report a large decrease in tetragonal to cubic phase transformation temperature when grain size of bulk CuFe2O4 is reduced by mechanical ball milling. The change in phase transformation temperature was inferred from in situ high temperature conductivity and x-ray diffraction measurements. The decrease in conductivity with grain size suggests that ball milling has not induced any oxygen vacancy while the role of cation distribution in the observed decrease in phase transformation temperature is ruled out from in-field Fe-57 Mossbauer and extended x-ray absorption fine structure measurements. The reduction in the phase transformation temperature is attributed to the stability of structures with higher crystal symmetry at lower grain sizes due to negative pressure effect. (C) 2011 American Institute of Physics. doi: 10.1063/1.3493244]

Preparation and characterization of nanocrystalline powders of bismuth vanadate

The influence of mechanical activation on the formation of Bi2VO5.5 bismuth vanadate (BiV) phase, was investigated by ball-milling a stoichiometric mixture of bismuth oxide and vanadium pentoxide. The structural evolution of the desired BN phase, via an intermediate BiVO4,phase, was investigated using X-ray powder diffraction; (XRD), differential thermal analysis (DTA) and transmission electron microscopy (TEM). Milling for 54h. yielded monophasic gamma-BiV powders with an average crystallite size of 30 nm. The electron paramagnetic resonance (EPR) peaks associated with the V4+ ions are stronger and broader in nanocrystalline (n) BN than in the conventionally prepared microcrystalline (m) BN, suggesting theta significant portion of V5+ has been transformed to V4+ during milling. The optical bandgap of n-BiV was found to be higher than that of m-BiV. High density (97% of the theoretical density), fine-grained (average grain-size of 2 tun) ceramics with uniform grain-size distribution could be fabricated using n-BiV powders. These fine-grained ceramics exhibit improved dielectric, pyre and ferroelectric properties. (C) 1999 Elsevier Science S.A. All rights reserved.

The influence of Fe3+ ions at tetrahedral sites on the magnetic properties of nanocrystalline ZnFe2O4

A systematic study on the variation of Mössbauer hyperfine parameters with grain size in nanocrystalline zinc ferrite is lacking. In the present study, nanocrystalline ZnFe2O4 ferrites with different grain sizes were prepared by ball-milling technique and characterised by X-ray, EDAX, magnetisation and Mössbauer studies. The grain size decreases with increasing milling time and lattice parameter is found to be slightly higher than the bulk value. Magnetisation at room temperature (RT) and at 77 K could not be saturated with a magnetic field of 7 kOe and the observed magnetisation at these temperatures can be explained on the basis of deviation of cation distribution from normal spinel structure. The Mössbauer spectra were recorded at different temperatures between RT and 16 K. The values of quadrupole splitting at RT are higher for the milled samples indicating the disordering of ZnFe2O4 on milling. The strength of the magnetic hyperfine interactions increases with grain size reduction and this can be explained on the basis of the distribution of Fe3+ ions at both tetrahedral and octahedral sites.

Thermoelectric properties of chromium disilicide prepared by mechanical alloying

CrSi and Cr1-x Fe (x) Si particles embedded in a CrSi2 matrix have been prepared by hot pressing from CrSi1.9, CrSi2, and CrSi2.1 powders produced by ball milling using either WC or stainless steel milling media. The samples were characterized by powder X-ray diffraction, scanning, and transmission electron microscopy and electron microprobe analysis. The final crystallite size of CrSi2 obtained from the XRD patterns is about 40 and 80 nm for SS- and WC-milled powders, respectively, whereas the size of the second phase inclusions in the hot pressed samples is about 1-5 mu m. The temperature dependence of the electrical resistivity, Seebeck coefficient, thermal conductivity, and figure of merit (ZT) were analyzed in the temperature range from 300 to 800 K. While the ball-milling process results in a lower electrical resistivity and thermal conductivity due to the presence of the inclusions and the refinement of the matrix microstructure, respectively, the Seebeck coefficient is negatively affected by the formation of the inclusions which leads to a modest improvement of ZT.

Structural refinement, optical and electrical properties of Ba1-x Sm-2x/3](Zr0.05Ti0.95)O-3 ceramics

Samarium doped barium zirconate titanate ceramics with general formula Ba1-x Sm-2x/3](Zr0.05Ti0.95)O-3 x = 0, 0.01, 0.02, and 0.03] were prepared by high energy ball milling method. X-ray diffraction patterns and micro-Raman spectroscopy confirmed that these ceramics have a single phase with a tetragonal structure. Rietveld refinement data were employed to model BaO12], SmO12], ZrO6], and TiO6] clusters in the lattice. Scanning electron microscopy shows a reduction in average grain size with the increase of Sm3+ ions into lattice. Temperature-dependent dielectric studies indicate a ferroelectric phase transition and the transition temperature decreases with an increase in Sm3+ ion content. The nature of the transition was investigated by the Curie-Weiss law and it is observed that the diffusivity increases with Sm3+ ion content. The ferroelectric hysteresis loop illustrates that the remnant polarization and coercive field increase with an increase in Sm3+ ions content. Optical properties of the ceramics were studied using ultraviolet-visible diffuse reflectance spectroscopy.

Nanostructuring of p- and n-type skutterudites reaching figures of merit of approximately 1.3 and 1.6, respectively

Thermoelectric (TE) conversion of waste heat into useful electricity demands optimized thermal and electrical transport in the leg material over a wide temperature range. In order to gain a reasonably high figure of merit (ZT) as well as high thermal electric conversion efficiency, various conditions of the starting material were studied: industrially produced skutterudite powders of p-type DDy(Fe1-xCox)(4)Sb-12 (DD: didymium) and n-type (Mm, Sm)(y)Co4Sb12 (Mm: mischmetal) were used. After a rather fast reaction-melting technique, the bulk was crushed and sieved with various strainers in order to obtain particles below the respective mesh sizes, followed by ball-milling under three different conditions. The dependence of the TE properties (after hot pressing) on the micro/nanosized particles, grains and crystallites was investigated. Optimized conditions resulted in an increase of ZT for bulk material to current record-high values: from ZT similar to 1.1 to ZT similar to 1.3 at 775 K for p-type and from ZT similar to 1.0 to ZT similar to 1.6 at 800 K for n-type, resulting in respective efficiencies (300-850 K) of eta > 13% and eta similar to 16%. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

Effect of processing route on phase stability in equiatomic multicomponent Ti20Fe20Ni20Co20Cu20 high entropy alloy

The evolution of microstructure and phase formation in equiatomic Ti20Fe20Ni20Co20Cu20 high entropy alloy synthesised by conventional arc melting followed with suction casting and ball milling with spark plasma sintering route is distinctly different. The cast microstructure exhibits one body centre cubic and two face centre cubic high entropy phases based on titanium, cobalt and copper respectively along with a eutectic containing Ti2Ni type Laves phase. On the contrary, spinodal decomposed microstructure consisting of cobalt and copper solid solution is obtained in the sintered sample. However, long term annealing of cast sample at 950 degrees C reveals a eutectoid transformation with different phases than the cast sample. The aforementioned observations are discussed using CALPHAD thermodynamical approach and available literature.

Low thermal conductivity of endogenous manganese silicide/Si composites for thermoelectricity

Higher manganese silicide (HMS) based alloys with eutectic composition (Si-33.3 at% Mn) were prepared by arc-melting, melt-spinning and ball milling in order to evaluate the effect of microstructure on the thermal conductivity. Powder X-ray diffraction, SEM, EPMA and TEM analysis confirmed the presence of Si as a secondary phase distributed in the HMS matrix phase. Thermal properties of the samples were studied in the temperature range of 300-800 K. The microstructure refinement resulting from ball milling leads to a decrease of the thermal conductivity from 4.4 W/mK to 1.9 W/mK, whereas meltspinning is inefficient to this respect. The results show an opportunity to produce bulk higher manganese silicide alloys with reduced thermal conductivity in order to enhance its thermoelectric performance. (C) 2015 Elsevier B.V. All rights reserved.

In-doped multifilled n-type skutterudites with ZT=1.8

In this paper we maximize the thermoelectric (TE) figure of merit, ZT, of n-type skutterudites, (In,Sr,Ba,Yb)(y)Co4Sb12, via three different routes: (i) find the optimum fraction of In as fourth filler (ii) check the influence of powder particle, grain, and crystallite size on the TE properties and (iii) check thermal stability. Filled n-type (Sr, Ba, Yb)(y)Co4Sb12 was mixed in three different proportions with In0.4Co4Sb12, ball milled (regular or high-energy (HB) ball milling) and hot-pressed. Particle size analyses and SEM pictures of the broken surfaces of the hot pressed samples document that only HB produces uniform particles/grains with average crystallite sizes similar to 100 nm, proven by transmission electron microscopy. X-ray Rietveld refinements combined with EDX indicate that in all cases indium entered the icosahedral voids of the skutterudite. Temperature dependent physical properties of all three regularly ball-milled samples show that increasing In-content infers an increasing electrical resistivity, increasing Seebeck coefficient but a decreasing total thermal conductivity. Although ZT (823 K) is in the same range as for the sample without In, the ZT values in the whole temperature range are higher and consequently the TE-conversion efficiency, eta is at least 10% higher. Annealing the samples at 600 degrees C for three days shows minor changes in structure and thermoelectric properties, indicating TE stability. The HB sample, due to uniformly small particles, equally sized grains and crystallites, exhibits a high power factor (4.4 mW/m K-2 at 730 K) and a very low thermal conductivity leading to an outstanding high ZT = 1.8 at 823 K (eta(max) = 17.5%). (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Mechanical alloying of Fe-Mn and Fe-Mn-Si

The ball milling of Fe-24Mn and Fe-24Mn-6Si mixed powders has been performed by the high energy ball milling technique. By employing X-ray diffraction and Mossbauer measurements, the composition evolution during the milling process has been investigated. The results indicate the formation of paramagnetic Fe-Mn or Fe-Mn-Si alloys with a metastable fee phase as final products, which imply that the Fe and Mn proceed a co-diffusion mechanism through the surface of fragmented powders. The thermal stability and composition evolution of the as-milled alloys were discussed comparing with the bulk alloy. (C) 1999 Published by Elsevier Science S.A. All rights reserved.

Hard magnetic properties of Sm3Fe26.7VxN4 and Sm3Fe26.7VxCy

Sm3Fe26.7V2.3N4 nitrides and Sm3Fe26.7V2.3Cy carbides have been synthesized by gas-solid phase reaction. Their hard magnetic properties have been investigated by means of additional ball-milling at room temperature. The saturation magnetization of Sm3Fe26.7V2.3N4 almost decreases linearly with increasing ball-milling time t, but that of Sm3Fe26.7V2.3Cy has no obvious change when the ball-milling time increases from t = 1 to 28 h. As a preliminary result, the maximum remanence B-r of 0.94 and 0.88 T, the coercivity mu(0i)H(C) of 0.75 and 0.25 T, and the maximum energy product (BH) of 108.5 and 39.1 kJ/m(3) for their resin-bonded permanent magnets are achieved, respectively, by ball-milling at 293 K. (C) 1999 Published by Elsevier Science B.V. All rights reserved.

Thermomagnetic behavior and first order magnetization processes of Sm3Fe29-xTx and Sm3Fe29-xTxN4 (T = V and Cr)

A systematic investigation of structure and intrinsic magnetic properties of the compounds Sm3Fe29-xTx (T = V and Cr) and their nitrides has been performed. Nitrogenation resulted in remarkable improvements in the saturation magnetization and anisotropy fields at 4.2 K and room temperature. First order magnetization processes are observed at around 5.7 T for Sm3Fe26.7V2.3 and around 2.8 T for Sm3Fe24.0Cr5.0 and Sm3Fe24.0Cr5.0N4, respectively. The spin reorientation of the easy magnetization direction of Sm3Fe26.7V2.3 is observed at around 230 K. As a preliminary result, the maximum remanence B-r of 0.94 T, the coercivity mu(0)H(C) of 0.75 T, and the maximum energy product (BH) of 108.5 kJ/m(3) for the nitride magnet Sm3Fe26.7V2.3N4 are achieved by ball-milling at 293 K.