Effects Of Disorder On Physical Properties Of Selected Transition Metal Oxides

Disorder in materials often brings in new and exotic physical properties along with it. It is thus very important to study different kinds of disorder and their implications on various material properties. In this thesis, we study selected transition metal oxide families of compounds, each being associated with a specific kind of disorder and investigate effects of that disorder on their dielectric and magnetic properties. In Chapter1, we have given brief introductions on the origin of magnetic and dielectric properties in materials and have also discussed various mechanism which give rise to multiferroism in materials which exhibit both spontaneous magnetic ordering and spontaneous electric ordering in the same phase of the material. In Chapter2,we describe the various methodologies adopted in this thesis. In Chapter3,we mainly study the effect of cationic size-disorder in deciding un-usually robust dielectric properties of Ln2CuTiO6(Ln=Y,Dy,Ho,Er,Yb) family of compounds. We discover that these materials, in addition to possessing large dielectric constant values, also exhibit exceptional stabilities of their dielectric constants with respect to large changes in temperature and frequency. We further find that this class of materials are non-ferroelectrics though its hares the same non-centrosymmetric space group, P63cm,with the well-known multiferroic YMnO3 that undergoes a ferroelectric transition at 940K. Using first principles calculations, we establish that exceptional dielectric properties result from a combination of two separate effects. Extensive size disorders at the Cu/Ti B-site suppress the expected 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 temperature variations. In Chapter4, we study the effect of cation anti-site disorder on the magnetic, electric and dielectric properties of the solid solution series of (x)Fe2O3-(1-x)FeTiO3 for several values of x. For intermediate values of x, these solid solution members are found to be strong ferrimagnets. Anti-site cation disorder, between Fe and Ti, however strongly reduces the magnetic moment values. By tuning the degree of cation anti-site disorder, we attain multi-functionality in these samples. We have performed detailed characterizations of valence states of Fe and Ti across the solid solution series using x-ray photoelectron spectroscopy and x-ray absorption spectroscopy. Using x-ray magnetic circular dichroism, we validate the microscopic model of magnetism and suggest a microscopic picture of the anti-site cation disorder for these samples. In Chapter5,we study the effects of controlled chemical disorder in SrTiO3 lattice, by performing site-specific doping of Mn in SrTiO3. We find that site specific Mn doping has decisive influence on their dielectric properties with qualitatively and quantitatively different behaviors between these doped samples .Using electron paramagnetic resonance experiments, we establish the site specific doping of Mn in SrTiO3 lattice. We find that while Mn doping at Ti site continues to remain paraelectric, Mn doping at the Sr site becomes a relaxor ferroelectric. We find samples having Mn substituted at both Sr and Ti sites simultaneously to be also relaxor ferroelectrics. Combining experiments with first principles calculations, we understand the origin for the high temperature dielectric properties of various Mn doped SrTiO3 samples. We show that Mn ions doped at the Sr sites off-centers and gives a significant dipolar contribution to their dielectric constants. While demonstrating the superior dielectric properties of Mn doped SrTiO3 ceramics ,we also elucidate their magnetic properties in details. In Chapter6,we study the effect of cation anti-site disorder on the magnetic and dielectric properties of undoped and Lu doped La2NiMnO6 samples. Using detailed spectroscopic characterizations of these samples with x-ray absorption experiments, coupled with d.c.magnetization and a.c.susceptibility measurements, we demonstrate that while the doped samples are ferromagnetic, the undoped samples exhibit re-entrant spin-glass magnetism. We also show that the dielectric properties of undoped La2NiMnO6,crys-tallizing in monoclinic and rhombohedral phases are distinctly different and we study their dielectric relaxations in details. We also demonstrate multiferroism in Lu doped La2NiMnO6 samples. In Appendix A, we study the electronic origin of ferroelectric polarization in the spin spiral compound ,MnWO4. Using x-ray absorption spectroscopy on synthesized MnWO4 samples, coupled with configuration interaction calculations, we establish quantitatively a significant population of Mn 3d states beyond the expected half filling and provide a critical insight into the significant presence of spin-orbit coupling and consequent finite polarization in this system. In Appendix B, we study charge-transfer doping in few-layer grapheme covered with electron acceptor (Tetracyanoethylene) and donor (Tetrathiafulvalene) molecules using x-ray photoelectron spectroscopy. We give quantitative estimates of the extent of doping in these samples and thereby elucidate the origin of unusual shifts of their Raman G bands in contrast to electrochemically doping schemes. In conclusion, we investigate, in this thesis, properties of different classes of compounds in presence of distinctly different kinds of disorder and establish the critical role of disorder in each case in tuning their desirable physical properties

XPS evidence for molecular charge-transfer doping of graphene

By employing x-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping.Comment: 15 pages, 5 figure

Electric and magnetic polarizabilities of hexagonal Ln2CuTiO6 (Ln=Y, Dy, Ho, Er and Yb)

We investigated the rare-earth transition metal oxide series, Ln2CuTiO6 (Ln=Y, Dy, Ho, Er and Yb), crystallizing in the hexagonal structure with non-centrosymmetric P63cm 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 co-operative 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 amongst different members of this series are shown to arise from changes in relative contributions from soft polar modes.Comment: Accepted for publication in Phys. Rev. B (21 pages, 2 Table, 8 Figures

Progress of protective gear in preventing sports injuries

Protective sports gear has progressively safeguarded athletes by considerably decreasing injuries throughout time. This examination explores the groundbreaking developments, viability, and prospective advancements in safety equipment crosswise over different game classifications. It evaluates how cutting-edge innovations, materials, and customized highlights affect player security and execution upgrades. The integration of keen innovation in games security gear is investigated, considering its potential to reform damage counteraction and recovery. Historically, key breakthroughs and notable developments in helmets, mouthguards, and pads have upgraded shields. Moreover, fusing propelled substances, sensors, customization, and savvy innovation in defensive gear is examined, emphasizing the need to adjust execution with wellbeing. The investigation underscores consistent inquiries about association and development in advancing protective gear to guarantee that competitors perform at their most noteworthy potential while diminishing damage dangers

Mathematical modeling and harmonic analysis of SISFCL

Purpose - A saturated iron core superconducting fault current limiter (SISFCL) has an important role to play in the present-day power system, providing effective protection against electrical faults and thus ensuring an uninterrupted supply of electricity to the consumers. Previous mathematical models developed to describe the SISFCL use a simple flux density-magnetic field intensity curve representing the ferromagnetic core. As the magnetic state of the core affects the efficient working of the device, this paper aims to present a novel approach in the mathematical modeling of the device with the inclusion of hysteresis. Design/methodology/approach - The Jiles-Atherton\u27s hysteresis model is utilized to develop the mathematical model of the limiter. The model is numerically solved using MATLAB. To support the validity of model, finite element model (FEM) with similar specifications was simulated. Findings - Response of the limiter based on the developed mathematical model is in close agreement with the FEM simulations. To illustrate the effect of the hysteresis, the responses are compared by using three different hysteresis characteristics. Harmonic analysis is performed and comparison is carried out utilizing fast Fourier transform and continuous wavelet transform. It is observed that the core with narrower hysteresis characteristic not only produces a better current suppression but also creates a higher voltage drop across the DC source. It also injects more harmonics in the system under fault condition. Originality/value - Inclusion of hysteresis in the mathematical model presents a more realistic approach in the transient analysis of the device. The paper provides an essential insight into the effect of the core hysteresis characteristic on the device performance. © 2016 Emerald Publishing Limited.Embargo Period 12 month

Engineering room-temperature multiferroicity in Bi and Fe codoped BaTiO3

Fe doping into BaTiO3, stabilizes the paraelectric hexagonal phase in place of the ferroelectric tetragonal one [P. Pal et al. Phys. Rev. B, 101, 064409 (2020)]. We show that simultaneous doping of Bi along with Fe into BaTiO3 effectively enhances the magnetoelectric (ME) multiferroic response (both ferromagnetism and ferroelectricity) at room-temperature, through careful tuning of Fe valency along with the controlled-recovery of ferroelectric-tetragonal phase. We also report systematic increase in large dielectric constant values as well as reduction in loss tangent values with relatively moderate temperature variation of dielectric constant around room-temperature with increasing Bi doping content in Ba1-xBixTi0.9Fe0.1O3 (0<x<0.1), which makes the higher Bi-Fe codoped sample (x=0.08) promising for the use as room-temperature high-k dielectric material. Interestingly, x=0.08 (Bi-Fe codoped) sample is not only found to be ferroelectrically (~20 times) and ferromagnetically (~6 times) stronger than x=0 (only Fe-doped) at room temperature, but also observed to be better insulating (larger bandgap) with indirect signatures of larger ME coupling as indicated from anomalous reduction of magnetic coercive field with decreasing temperature. Thus, room-temperature ME multiferroicity has been engineered in Bi and Fe codoped BTO (BaTiO3) compounds.Comment: 16 pages, 17 figure

On Bootstrapping Lasso in Generalized Linear Models and the Cross Validation

Generalized linear models or GLM constitutes an important set of models which generalizes the ordinary linear regression by connecting the response variable with the covariates through arbitrary link functions. On the other hand, Lasso is a popular and easy to implement penalization method in regression when all the covariates are not relevant. However, Lasso generally has non-tractable asymptotic distribution and hence development of an alternative method of distributional approximation is required for the purpose of statistical inference. In this paper, we develop a Bootstrap method which works as an approximation of the distribution of the Lasso estimator for all the sub-models of GLM. To connect the distributional approximation theory based on the proposed Bootstrap method with the practical implementation of Lasso, we explore the asymptotic properties of K-fold cross validation-based penalty parameter. The results established essentially justifies drawing valid statistical inference regarding the unknown parameters based on the proposed Bootstrap method for any sub model of GLM after selecting the penalty parameter using K-fold cross validation. Good finite sample properties are also shown through a moderately large simulation study. The method is also implemented on a real data set

A Roadmap for Strengthening Panchayati Raj Institutions in Bihar

Preparation of plan for utilization of resources and making appropriate interventions for the wellbeing of the people is an essential component of any government. Planning by the Panchayats is, therefore, very important. Planning at the Gram Panchayat level is even more important since the people can directly participate in preparation and implementation of the plans for their own development. Recommendation of the 14th Finance Commission that the entire amount to be transferred to the Panchayats will be made available to the Gram Panchayats for improving basic services have further increased the importance of planning at that level and involvement of the people in the process