Quest for new materials: Inorganic chemistry plays a crucial role

There is an endless quest for new materials to meet the demands of advancing technology. Thus, we need new magnetic and metallic/semiconducting materials for spintronics, new low-loss dielectrics for telecommunication, new multi-ferroic materials that combine both ferroelectricity and ferromagnetism for memory devices, new piezoelectrics that do not contain lead, new lithium containing solids for application as cathode/anode/electrolyte in lithium batteries, hydrogen storage materials for mobile/transport applications and catalyst materials that can convert, for example, methane to higher hydrocarbons, and the list is endless! Fortunately for us, chemistry - inorganic chemistry in particular - plays a crucial role in this quest. Most of the functional materials mentioned above are inorganic non-molecular solids, while much of the conventional inorganic chemistry deals with isolated molecules or molecular solids. Even so, the basic concepts that we learn in inorganic chemistry, for example, acidity/basicity, oxidation/reduction (potentials), crystal field theory, low spin-high spin/inner sphere-outer sphere complexes, role of d-electrons in transition metal chemistry, electron-transfer reactions, coordination geometries around metal atoms, Jahn-Teller distortion, metal-metal bonds, cation-anion (metal-nonmetal) redox competition in the stabilization of oxidation states - all find crucial application in the design and synthesis of inorganic solids possessing technologically important properties. An attempt has been made here to illustrate the role of inorganic chemistry in this endeavour, drawing examples from the literature its well as from the research work of my group.

Magnetic Properties of Iron Particles Embedded in Multiwall Carbon Nanotubes

Iron nanoparticles are embedded in multiwall carbon nanotubes by the chemical vapor deposition, where benzene and ferrocene are taken as precursor materials. Varying quantity of iron particles are embedded in these tubes by taking different amount of ferrocene. These particles exhibit a magnetic moment up to 98 emu/g and an enhanced coercivity in the range of 500-2000 Oe. Negative magnetoresistance similar to 10% is observed in the presence of magnetic field up to 11 T applied at various temperatures in the range of 1.3 K-300 K. It is argued that the enhanced coercivity is due to the shape anisotropy. The negative magnetoresistance is believed to be due to the weak localization and spin dependent scattering of electrons by the ferromagnetic particles. In addition we also observe a dependence of the magnetoresistance on the direction of applied field and this is correlated with the shape anisotropy of the Fe particles.

Effect of magnetic and electrical fields on dendritic freezing of aqueous solutions of sodium chloride

Aqueous solutions of sodium chloride were solidified under the influence of magnetic and electrical fields using two different freezing systems. In the droplet system, small droplets of the solution are introduced in an organic liquid column at −20°C which acts as the heat sink. In the unidirectional freezing system the solutions are poured into a tygon tube mounted on a copper chill, maintained at −70°C, from which the freezing initiates. Application of magnetic fields caused an increase in the spacing and promoted side branching of primary ice dendrites in the droplet freezing system, but had no measurable effect on the dendrites formed in the unidirectional freezing system. The range of electric fields applied in this investigation had no measurable effect on the dendritic structure. Possible interactions between external magnetic and electrical fields have been reviewed and it is suggested that the selective effect of magnetic fields on dendrite spacings in a droplet system could be due to a change in the nucleation behaviour of the solution in the presence of a magnetic field.

X-ray spectroscopic studies of amorphous materials

Measurement of the chemical shifts ΔE of the K-absorption edge in both crystalline and amorphous states of several solids shows that ΔE is generally smaller in the amorphous state. More covalent solids appear to be associated with small values of ΔE.

Thermoelectric power in ultrathin films, quantum wires and carbon nanotubes under classically large magnetic field: Simplified theory and relative comparison

We study the thermoelectric power under classically large magnetic field (TPM) in ultrathin films (UFs), quantum wires (QWs) of non-linear optical materials on the basis of a newly formulated electron dispersion law considering the anisotropies of the effective electron masses, the spin-orbit splitting constants and the presence of the crystal field splitting within the framework of k.p formalism. The results of quantum confined III-V compounds form the special cases of our generalized analysis. The TPM has also been studied for quantum confined II-VI, stressed materials, bismuth and carbon nanotubes (CNs) on the basis of respective dispersion relations. It is found taking quantum confined CdGeAs2, InAs, InSb, CdS, stressed n-InSb and Bi that the TPM increases with increasing film thickness and decreasing electron statistics exhibiting quantized nature for all types of quantum confinement. The TPM in CNs exhibits oscillatory dependence with increasing carrier concentration and the signature of the entirely different types of quantum systems are evident from the plots. Besides, under certain special conditions, all the results for all the materials gets simplified to the well-known expression of the TPM for non-degenerate materials having parabolic energy bands, leading to the compatibility test. (C) 2009 Elsevier B.V. All rights reserved.

Effect of Al substitution on the magnetic properties of amorphous Fe73.5Cu1Mo3Si13.5-xAlxB9 alloy

We have synthesized FINEMET type amorphous Fe73.5Cu1Mo3Si13.5-xAlxB9 alloy by the single wheel melt spinning technique. The effect of Al substitution on the magnetic properties has been studied using a vibrating sample magnetometer, SQUID and Mossbauer spectroscopy. Magnetization and Curie temperature of the amorphous phase of the alloys were found to decrease with A] concentration. The results are attributed to the dilution effect of At on the magnetic moment of Fe and to the increase in Fe-Fe interaction distance resulting in the weakening of exchange interaction. (C) 2007 Elsevier B.V. All rights reserved.

Thermoelectric Power Under Strong Magnetic Field in Quantum Dots and Quantized Superlattices: Simplified Theory and Relative Comparison

In this paper, we study the thermoelectric power under strong magnetic field (TPSM) in quantum dots (QDs) of nonlinear optical, III-V, II-VI, GaP, Ge, Te, Graphite, PtSb2, zerogap, Lead Germanium Telluride, GaSb, stressed materials, Bismuth, IV-VI, II-V, Zinc and Cadmium diphosphides, Bi2Te3 and Antimony respectively. The TPSM in III-V, II-VI, IV-VI, HgTe/CdTe quantum well superlattices with graded interfaces and effective mass superlattices of the same materials together with the quantum dots of aforementioned superlattices have also been investigated in this context on the basis of respective carrier dispersion laws. It has been found that the TPSM for the said quantum dots oscillates with increasing thickness and decreases with increasing electron concentration in various manners and oscillates with film thickness, inverse quantizing magnetic field and impurity concentration for all types of superlattices with two entirely different signatures of quantization as appropriate in respective cases of the aforementioned quantized structures. The well known expression of the TPSM for wide-gap materials has been obtained as special case for our generalized analysis under certain limiting condition, and this compatibility is an indirect test of our generalized formalism. Besides, we have suggested the experimental method of determining the carrier contribution to elastic constants for nanostructured materials having arbitrary dispersion laws.

Manifestation of geometric frustration on magnetic and thermodynamic properties of the pyrochlores Sm2X2O7 (X=Ti,Zr)

We present here magnetization, specific heat, and Raman studies on single-crystalline specimens of the first pyrochlore member Sm2Ti2O7 of the rare-earth titanate series. Its analogous compound Sm2Zr2O7 in the rare-earth zirconate series is also investigated in the polycrystalline form. The Sm spins in Sm2Ti2O7 remain unordered down to at least T=0.5 K. The absence of magnetic ordering is attributed to very small values of exchange (θcw∼−0.26 K) and dipolar interaction (μeff∼0.15 μB) between the Sm3+ spins in this pyrochlore. In contrast, the pyrochlore Sm2Zr2O7 is characterized by a relatively large value of Sm-Sm spin exchange (θcw∼−10 K); however, long-range ordering of the Sm3+ spins is not established at least down to T=0.67 K due to frustration of the Sm3+ spins on the pyrochlore lattice. The ground state of Sm3+ ions in both pyrochlores is a well-isolated Kramers doublet. The higher-lying crystal field excitations are observed in the low-frequency region of the Raman spectra of the two compounds recorded at T=10 K. At higher temperatures, the magnetic susceptibility of Sm2Ti2O7 shows a broad maximum at T=140 K, while that of Sm2Zr2O7 changes monotonically. Whereas Sm2Ti2O7 is a promising candidate for investigating spin fluctuations on a frustrated lattice, as indicated by our data, the properties of Sm2Zr2O7 seem to conform to a conventional scenario where geometrical frustration of the spin excludes their long-range ordering.

Modeling of magnetostrictive materials and structures

The constitutive model for a magnetostrictive material and its effect on the structural response is presented in this article. The example of magnetostrictive material considered is the TERFENOL-D. As like the piezoelectric material, this material has two constitutive laws, one of which is the sensing law and the other is the actuation law, both of which are highly coupled and non-linear. For the purpose of analysis, the constitutive laws can be characterized as coupled or uncoupled and linear or non linear. Coupled model is studied without assuming any explicit direct relationship with magnetic field. In the linear coupled model, which is assumed to preserve the magnetic flux line continuity, the elastic modulus, the permeability and magneto-elastic constant are assumed as constant. In the nonlinear-coupled model, the nonlinearity is decoupled and solved separately for the magnetic domain and the mechanical domain using two nonlinear curves, namely the stress vs. strain curve and the magnetic flux density vs. magnetic field curve. This is performed by two different methods. In the first, the magnetic flux density is computed iteratively, while in the second, the artificial neural network is used, where in the trained network will give the necessary strain and magnetic flux density for a given magnetic field and stress level. The effect of nonlinearity is demonstrated on a simple magnetostrictive rod.

Influence of quantum confinement on the photoemission from superlattices of optoelectronic materials

We study the photoemission from quantum wire and quantum dot superlattices with graded interfaces of optoelectronic materials on the basis of newly formulated electron dispersion relations in the presence of external photo-excitation. Besides, the influence of a magnetic field on the photoemission from the aforementioned superlattices together with quantum well superlattices in the presence of a quantizing magnetic field has also been studied in this context. It has been observed taking into account HgTe/Hg1-xCdxTe and InxGa1-xAs/InP that the photoemission from these nanostructures increases with increasing photon energy in quantized steps and exhibits oscillatory dependences with the increase in carrier concentration. Besides, the photoemission decreases with increasing light intensity and wavelength, together with the fact that said emission decreases with increasing thickness exhibiting oscillatory spikes. The strong dependences of the photoemission on the light intensity reflects the direct signature of light waves on the carrier energy spectra. The content of this paper finds six applications in the fields of low dimensional systems in general. (C) 2010 Elsevier Ltd. All rights reserved.

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.

Synthesis, magnetic and electrical properties of Fe-containing SiO2 nanocomposite

Nanocrystalline Fe powders were synthesized by transmetallation reaction and embedded in silica to form Fe-SiO2 nanocomposite. Thermomagnetic study of the as-prepared Fe sample indicates the presence of Fe3O4 and Fe particles. Oxidation studies of Fe and Fe-SiO2 show an increased thermal stability of Fe-SiO2 nanocomposite over pure Fe. The Fe-SiO2 shows an enhanced oxidation temperature (i.e., 780 K) and a maximum saturation magnetization value of (135 emu/g) with 64 wt.% of Fe content in silica. Electrical and dielectric behaviour of the Fe-SiO2 nanocomposite has been investigated as a function of temperature and frequency. Low frequency ac conductivity and dielectric constants were found to be influenced by desorptions of chemisorbed moisture. High saturation magnetization, thermal stability, frequency-dependent conductivity and low power loss make Fe-silica a promising material for high frequency applications. (C) 2010 Elsevier B.V. All rights reserved.

Study of magnetic field effect on the specific heat and entropy in DyBa2Cu3O7-x

The change in the specific heat by the application of magnetic field up to 161 for high temperature superconductor system for DyBa2Cu3O7-x by Revaz et al. [23] is examined through the phenomenological Ginzburg-Landau(G-L) theory of anisotropic Type-II superconductors. The observed specific heat anomaly near T-c with magnetic field is explained qualitatively through the expression <Delta C > = (B-a/T-c) t/(1 - t)(alpha Theta(gamma)lambda(2)(m)(0)), which is the anisotropic formulation of the G-L theory in the London limit developed by Kogan and coworkers; relating to the change in specific heat Delta C for the variation of applied magnetic field for different orientations with c-axis. The analysis of this equation explains satisfactorily the specific heat anomaly near T-c and determines the anisotropic ratio gamma as 5.608, which is close to the experimental value 5.3 +/- 0.5given in the paper of Revaz et al. for this system. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, structure and magnetic properties of the polyoxovanadate cluster Zn-2(NH2(CH2)(2)NH2)(5)]{Zn(NH2(CH2)(2)NH2)(2)}(2){V18O42(H2O)\ ]center dot xH(2)O (x similar to 12), possessing a layered structure

A hydrothermal reaction of a mixture of ZnCl2, V2O5, ethylenediamine and water gave rise to a layered poly oxovanadate material. clusters. These clusters, with all the vanadium ions in the +4 state, are connected together through Zn(NH2(CH2)(2)NH2)(2) linkers forming a two-dimensional structure. The layers are also separated by distorted trigonal bipyramidal [Zn-2(NH2(CH2)(2)NH2)(5)] complexes. The Structure, thus, presents a dual role for the Zn-ethylenediamine complex. The magnetic susceptibility studies indicate that the interactions between the V centres in I are predominantly antiferromagnetic in nature and the compound shows highly frustrated behaviour. The magnetic properties are compared to the theoretical calculations based oil the Heisenberg model, in addition to correlating to the structure. Crystal data for the complexes are presented.

Electric and magnetic polarizabilities of hexagonal Ln(2)CuTiO(6)(Ln = Y, Dy, Ho, Er, and Yb)

We investigated the rare-earth transition-metal oxide series, Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb), crystallizing in the hexagonal structure with noncentrosymmetric P6(3)cm space group for possible occurrences of multiferroic properties. Our results show that while these compounds, except Ln = Y, exhibit a low-temperature antiferromagnetic transition due to the ordering of the rare-earth moments, the expected ferroelectric transition is frustrated by the large size difference between Cu and Ti at the B site. Interestingly, this leads these compounds to attain a rare and unique combination of desirable paraelectric properties with high dielectric constants, low losses, and weak temperature and frequency dependencies. First-principles calculations establish these exceptional properties result from a combination of two effects. A significant difference in the MO5 polyhedral sizes for M = Cu and M = Ti suppress the expected cooperative tilt pattern of these polyhedra, required for the ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against any temperature variation. Changes in the temperature stability of the dielectric constant among different members of this series are shown to arise from changes in relative contributions from soft polar modes.