Towards Realization of Magnetocaloric and Magnetoelectric Applications based on Bulk and Thin film forms of Sodium substituted Lanthanum Manganites

The present thesis work focuses on hole doped lanthanum manganites and their thin film forms. Hole doped lanthanum manganites with higher substitutions of sodium are seldom reported in literature. Such high sodium substituted lanthanum manganites are synthesized and a detailed investigation on their structural and magnetic properties is carried out. Magnetic nature of these materials near room temperature is investigated explicitly. Magneto caloric application potential of these materials are also investigated. After a thorough investigation of the bulk samples, thin films of the bulk counterparts are also investigated. A magnetoelectric composite with ferroelectric and ferromagnetic components is developed using pulsed laser deposition and the variation in the magnetic and electric properties are investigated. It is established that such a composite could be realized as a potential field effect device. The central theme of this thesis is also on manganites and is with the twin objectives of a material study leading to the demonstration of a device. This is taken up for investigation. Sincere efforts are made to synthesize phase pure compounds. Their structural evaluation, compositional verification and evaluation of ferroelectric and ferromagnetic properties are also taken up. Thus the focus of this investigation is related to the investigation of a magnetoelectric and magnetocaloric application potentials of doped lanthanum manganites with sodium substitution. Bulk samples of sodium substituted lanthanum manganites. Bulk samples of sodium substituted lanthanum manganites with Na substitution ranging from 50 percent to 90 percent were synthesized using a modified citrate gel method and were found to be orthorhombic in structure belonging to a pbnm spacegroup. The variation in lattice parameters and unit cell volume with sodium concentration were also dealt with. Magnetic measurements revealed that magnetization decreased with increase in sodium concentrations.

Exploitation of a pulsed neutron source for the structural study of anisotropic polymer films

A novel but simple time-of-flight neutron scattering geometry which allows structural anisotropy to be probed directly, simultaneously and thus unambiguously in polymeric and other materials is described. A particular advantage of the simultaneous data collection when coupled to the large area of the beam is that it enables thin films (< 10 μm < 10 mg) to be studied with relative ease. The utility of the technique is illustrated by studies on both deformed poly(styrene) glasses and on thin films of electrical conducting polymers. In the latter case, the power of isotopic substitution is illustrated to great effect. The development of these procedures for use in other areas of materials science is briefly discussed.

The effect of dopant molecules on the molecular order of electrically-conducting films of polypyrrole

X-ray scattering curves have been measured for a range of electrochemically-prepared conducting polypyrrole films employing a variety of counterions in aqueous solutions. Films containing counterions based on aromatic rings exhibit an anisotropic molecular organization. The degree of anisotropy is enhanced through the use of highly planar counterions. The electrical conductivity of such films is also improved if the charge/volume ratio of the counterion is maintained at a high level. Polypyrrole films prepared using ‘spherically’ shaped counterions such as SO42− do not display such anisotropic molecular organizations, and exhibit lower electrical conductivities. The competing structural roles of the counterions within these molecular composites are discussed.

The importance of anisotropic Coulomb interaction in LaMnO3

In low-temperature anti-ferromagnetic LaMnO3, strong and localized electronic interactions among Mn 3d electrons prevent a satisfactory description from standard local density and generalized gradient approximations in density functional theory calculations. Here we show that the strong on-site electronic interactions are described well only by using direct and exchange corrections to the intra-orbital Coulomb potential. Only DFT+U calculations with explicit exchange corrections produce a balanced picture of electronic, magnetic and structural observables in agreement with experiment. To understand the reason, a rewriting of the functional form of the +U corrections is presented that leads to a more physical and transparent understanding of the effect of these correction terms. The approach highlights the importance of Hund’s coupling (intra-orbital exchange) in providing anisotropy across the occupation and energy eigenvalues of the Mn d states. This intra-orbital exchange is the key to fully activating the Jahn-Teller distortion, reproducing the experimental band gap and stabilizing the correct magnetic ground state in LaMnO3. The best parameter values for LaMnO3 within the DFT(PBEsol)+U framework are determined to be U = 8 eV and J = 1.9 eV.

Reentrant quantum Hall effect in bilayer system at high filling factors

We report on the measurements of the quantum Hall effect states in double quantum well structures at the filling factors v = 4N + 1 and 4N + 3, where N is the Landau index number, in the presence of the in-plane magnetic field. The quantum Hall states at these filling factors vanish and reappear several times. Repeated reentrance of the transport gap occurs due to the periodic vanishing of the tunneling amplitude in the presence of the in-plane field. When the gap vanishes, the transport becomes anisotropic. The anisotropy persist at half-odd filling factors, when bilayer quantum Hall states are recovered with increase of the tilt angle. (C) 2007 Elsevier B.V. All rights reserved.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

Direct current electric potential in an anisotropic half-space with vertical contact containing a conductive 3D body

Detailed studies of anomalous conductors in otherwise homogeneous media have been modelled. Vertical contacts form common geometries in galvanic studies when describing geological formations with different electrical conductivities on either side. However, previous studies of vertical discontinuities have been mainly concerned with isotropic environments. In this paper, we deal with the effect on the electric potentials, such as mise-`a-la-masse anomalies, due to a conductor near a vertical contact between two anisotropic regions. We also demonstrate the interactive effects when the conductive body is placed across the vertical contact. This problem is normally very difficult to solve by the traditional numerical methods. The integral equations for the electric potential in anisotropic half-spaces are established. Green’s function is obtained using the reflection and transmission image method in which five images are needed to fit the boundary conditions on the vertical interface and the air-earth surface. The effects of the anisotropy of the environments and the conductive body on the electric potential are illustrated with the aid of several numerical examples.

Anisotropic wetting characteristics on submicrometer-scale periodic grooved surface

Submicrometer-scale periodic structures consisting of parallel grooves were prepared on azobenzene-containing multiarm star polymer films by laser interference. The wetting characteristics on the patterned surfaces were studied by contact angle measurements. Macroscopic distortion of water drops was found on such small-scale surface structures, and the contact angles measured from the direction parallel to the grooves were larger than those measured from the perpendicular direction. A thermodynamic model was developed to calculate the change in the surface free energy as a function of the instantaneous contact angle when the three-phase contact line (TPCL) moves along the two orthogonal directions. It was found that the fluctuations, i.e., energy barriers, on the energy versus contact angle curves are crucial to the analysis of wetting anisotropy and contact angle hysteresis. The calculated advancing and receding contact angles from the energy versus contact angle curves were in good agreement with those measured experimentally. Furthermore, with the groove depth increasing, both the degree of wetting anisotropy and the contact angle hysteresis perpendicular to the grooves increased as a result of the increase in the energy barrier. The theoretical critical value of the groove depth, above which the anisotropic wetting appears, was determined to be 16 nm for the grooved surface with a wavelength of 396 nm. On the other hand, the effect of the groove wavelength on the contact angle hysteresis perpendicular to the grooves was also interpreted on the basis of the thermodynamic model. That is, with the wavelength decreasing, the contact angle hysteresis increased due to the increase in the number of energy barriers. These results may provide theoretical evidence for the design and application of anisotropic wetting surface.

The effect of coordinating and non-coordinating additives on the transport properties in ionic liquid electrolytes for lithium batteries

In the present study we expand our analysis of using two contrasting organic solvent additives (toluene and THF) in an ionic liquid (IL)/Li NTf 2 electrolyte. Multinuclear Pulsed-Field Gradient (PFG) NMR, spin-lattice (T1) relaxation times and conductivity measurements over a wide temperature range are discussed in terms of transport properties and structuring of the liquid. The conductivity of both additive samples is enhanced the most at low temperatures, with THF slightly more effective than toluene. Both the anion and lithium self-diffusivity are enhanced in the same order by the additives (THF > toluene) while that of the pyrrolidinium cation is marginally enhanced. 1H spin-lattice relaxation times indicate a reasonable degree of structuring and anisotropic motion within all of the samples and both 19F and 7Li highlight the effectiveness of THF at influencing the lithium coordination within these systems.

Anisotropic hardening model based on non-associated flow rule and combined nonlinear kinematic hardening for sheet materials

 A material model for more effective analysis of plastic deformation of sheet materials is presented in this paper. The model is capable of considering the following aspects of plastic deformation behavior of sheet materials: the anisotropy in yielding stresses in different directions by using a quadratic yield function (based on Hill’s 1948 model and stress ratios), the anisotropy in work hardening by introducing non-constant flow stress hardening in different directions, the anisotropy in plastic strains in different directions by using a quadratic plastic potential function and non-associated flow rule (based on Hill’s 1948 model and plastic strain ratios, r-values), and finally some of the cyclic hardening phenomena such as Bauschinger’s effect and transient behavior for reverse loading by using a coupled nonlinear kinematic hardening (so-called Armstrong-Frederick-Chaboche model). Basic fundamentals of the plasticity of the model are presented in a general framework. Then, the model adjustment procedure is derived for the plasticity formulations. Also, a generic numerical stress integration procedure is developed based on backward-Euler method (so-called multistage return mapping algorithm). Different aspects of the model are verified for DP600 steel sheet. Results show that the new model is able to predict the sheet material behavior in both anisotropic hardening and cyclic hardening regimes more accurately. By featuring the above-mentioned facts in the presented constitutive model, it is expected that more accurate results can be obtained by implementing this model in computational simulations of sheet material forming processes. For instance, more precise results of springback prediction of the parts formed from highly anisotropic hardened materials or that of determining the forming limit diagrams is highly expected by using the developed material model.

On the strength of dislocation interactions and their effect on latent hardening in pure Magnesium

This study is dedicated to the quantification of latent hardening and its effect on the plasticity of pure hexagonal magnesium. To this end, discrete dislocation dynamics simulations are used to (1) extract latent hardening parameters coupling different slip systems, and to (2) assess the validity of two existing constitutive models linking slip system strength to dislocation densities on all slip systems. As hexagonal materials deform via activation of different slip modes, each with different mobilities and lattice friction stress, the effects of the latter on latent hardening evolution are also investigated. It is found that the multi-slip formulation proposed by Franciosi and Zaoui gives accurate predictions when multiple interactions are involved while the formulation suggested by Lavrentev and Pokhil systematically overestimates the flow stress. Similar to FCC materials, it is also found that collinear interactions potentially contribute the most to latent hardening. Basal/pyramidal c + a interactions are found to be very strong, while interactions involving second-order pyramidal c + a primary dislocations appear to be the weakest ones. Finally, the latent hardening parameters, extracted from the discrete dislocation dynamics simulations, are used in polycrystal simulations and the impact of finely accounting for latent hardening on predictions of the macroscopic anisotropic response is shown to be of significant importance.

A non-associated plasticity model with anisotropic and nonlinear kinematic hardening for simulation of sheet metal forming

A material model for more thorough analysis of plastic deformation of sheet materials is presented in this paper. This model considers the following aspects of plastic deformation behavior of sheet materials: (1) the anisotropy in yield stresses and in work hardening by using Hill's 1948 quadratic yield function and non-constant stress ratios which leads to different flow stress hardening in different directions, (2) the anisotropy in plastic strains by using a quadratic plastic potential function and non-associated flow rule, also based on Hill's 1948 model and r-values, and (3) the cyclic hardening phenomena such as the Bauschinger effect, permanent softening and transient behavior for reverse loading by using a coupled nonlinear kinematic hardening model. Plasticity fundamentals of the model were derived in a general framework and the model calibration procedure was presented for the plasticity formulations. Also, a generic numerical stress integration procedure was developed based on backward-Euler method, so-called multi-stage return mapping algorithm. The model was implemented in the framework of the finite element method to evaluate the simulation results of sheet metal forming processes. Different aspects of the model were verified for two sheet metals, namely DP600 steel and AA6022 aluminum alloy. Results show that the new model is able to accurately predict the sheet material behavior for both anisotropic hardening and cyclic hardening conditions. The drawing of channel sections and the subsequent springback were also simulated with this model for different drawbead configurations. Simulation results show that the current non-associated anisotropic hardening model is able to accurately predict the sidewall curl in the drawn channel sections.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO4 Crystals and Their Optical Properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optically anisotropic and photoconducting Langmuir-Blodgett films of neat poly(3-hexylthiophene)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)