Fe-based bulk metallic glasses (BMGs) have gained considerable interest due to their excellent soft magnetic properties with high saturation magnetization, high electrical resistivity, very good corrosion resistance, low materials cost, extremely high mechanical strength and hardness. In spite of having excellent strength, Fe-based BMGs are not used as structural materials in service, so far. The major obstacle is their inherent brittleness under mechanical loading, once a crack is developed the material fails catastrophically. Owing to the ever growing industrial demand for the materials with outstanding properties, aside from exploring new alloy compositions, it is pertinent to understand why or why-not the existing system work and how to improve their properties. Recent reports suggested that the plastic deformability can be enhanced by introducing different microstructural heterogeneities such as free volume enhanced regions, separated phases, nano-crystals, atomic clusters caused by for instance additions of small amount of soft elements. Understanding the effect of addition of soft elements to Fe-based BMGs on thermal stability, structural evolution, magnetic and mechanical properties are the main point which this work addresses. In this work, a study on two different soft ferromagnetic Fe-based glass forming alloys are presented, both of them known to have very high mechanical strength and excellent soft magnetic properties but so far have not been used in any industrial applications. The important issue is with the brittle behavior of this BMGs, particularly under mechanical loading. In each glass forming alloys, the aim was to find out the optimum quantity of the soft elements (Cu and Ga), which can be added to improve their room temperature plastic deformability without affecting the glass forming ability (GFA) and soft magnetic properties. The first glass forming alloy that is studied is Fe36Co36B19.2Si4.8Nb4. This glass forming alloy is highly sensitive to the impurities, only pure elements were used to form this alloy. The addition of only 0.5 at.% Cu completely changes the thermal stability and structural evolution but it also improves the mechanical properties. In case of Ga addition up to 1.5 at.% the crystallization behavior remains unaltered and the thermal stability improves marginally. The addition of Ga improves the plastic deformability of the glass by forming soft zones, whose melting point is much lower compared to rest of the alloy. These soft zones are responsible for the plastic deformation of this glass. Thus addition of Ga is very beneficial in improving the mechanical properties of this Fe-based BMG. In the second part, Fe74Mo4P10C7.5B2.5Si2 glass forming alloy is studied. Unlike the aforementioned alloy, this glass forming alloy is not very sensitive to the impurities, industrial grade alloy elements can also be used to form this alloy. In this alloy addition of Cu is beneficial only up to 0.5 at.%, beyond that Cu addition deteriorates GFA and magnetic properties. In case of Ga addition up to 2 at.% the crystallization behavior remains unaltered and the thermal stability improves marginally. Similar to the FeCoBSiNb glass, the addition of Ga in FeMoPCBSi glass also improves the plastic deformability of the glass by formation of soft zones. Addition of small at.% Ga proved be an viable solution to improve the plastic deformability in the ferromagnetic Fe-based metallic glasses without compromising on thermal and magnetic properties of the glass. In the final part we tried to cast the Fe74Mo4P10C7.5B2.5Si2 glass in a complex shape using an industrial high pressure die casting (HPDC) set up. The important issues were with the casting alloy temperature, casting speed and die material. The aim of our work was to optimize the die material suitable for casting the BMGs and then address the issues with casting temperature and casting speed. We have thus attempted to gain a basic knowledge in casting the Fe-based BMG in industrial scale. Our effort was tremendously successful, we were able to produce fully amorphous complex shaped samples with excellent surface finish. We have thus made a considerable advancement towards understanding the basics behind improving the room temperature plastic deformability in Fe36Co36B19.2Si4.8Nb4 and Fe74Mo4P10C7.5B2.5Si2 ferromagnetic BMGs. We have also made a considerable progress in industrialization of bulk ferromagnetic BMGs.

Este trabalho apresenta um estudo dos mecanismos de transporte iônico nos vidros fluorsilicatos de cádmio e chumbo de composição 40SiO2 40PbF2 20CdF2, e nos vidros boratos contendo LiF de composição 50B2O3 10PbO 40LiF. Estes materiais são importantes pela sua potencial utilização em dispositivos ópticos e eletrólitos sólidos. No vidro borato 50B2O3 10PbO 40LiF o estudo da forma de linha do 7Li mostrou que esta é influenciada tanto por interações dipolares quanto por quadrupolares. O estudo de RMN revelou que há dois F- presentes neste vidro, um deles em vizinhaças de Pb (F- incorporados à rede vítrea substituindo o oxigênio do grupo PbO), e o outro em vizinhanças de Li. A forma de linha de RMN dependente da temperatura para o lítio e para o flúor, e seus tempos de relaxação, exibem as características qualitativas associadas com a alta mobilidade do 7Li e do 19F neste sistema. Este estudo também mostrou que, neste vidro, tanto o Li+ como o F- contribuem para a condutividade medida, sendo que o 7Li é móvel a temperaturas mais baixas (a partir de 250 K), e o 19F começa a se mover em temperaturas mais altas (a partir de 400 K). No vidro 40SiO2 40PbF2 20CdF2, os resultados de RMN mostraram a alta mobilidade do flúor e evidenciaram duas dinâmicas diferentes dos íons flúor. Os dados da relaxação do flúor revelaram um máximo da taxa de relaxação spin-rede abaixo da temperatura de transição vítrea (Tg), indicando que a mobilidade do flúor, neste vidro, é comparável àquelas encontradas em condutores iônicos rápidos / This work presents a study of the ionic transport mechanisms in lead-cadmium fluorosilicate glasses, of composition 40SiO2 40PbF2 20CdF2, and in borate glasses containing LiF, of composition 50B2O3 10PbO 40LiF. These materiais are important due to theirs high potential applicability in optic devices and in solid electrolytes. In the borate glass 50B2O3 10PbO 40LiF, the line shape study of 7Li shows an influence of the dipolar and quadrupolar interactions. The NMR results showed that there are two kinds of F- ions in this glass, one in the Pb vicinity (F- in the glass lattice, in substitution of the PbO oxygen), and the other in the Li vicinity. The NMR line shape depends on the temperature for the 7Li and 19F atoms, and their relaxation times reflect qualitative features related to the high mobility of there nuclei. Also, this study shows that, in this glass, both, 7Li and 19F, play an important role in the electric conductivity. The 7Li is mobile for low temperatures (from 250 K), while the 19F is mobile for high temperatures (from 400 K). In the 40SiO2 40PbF2 20CdF2 glass, the NMR results showed the high mobility of the fluorine ions, indicating two different dynamics of those nuclei. The relaxation data of the 19F presented a spin-lattice relaxation rate maximum below the glass transition temperature (Tg, indicating that the 19F mobility in this glass is comparable to that of rapid ionic conducting glasses

Interest in Raman amplification has undergone a revival due to the rapidly increasing bandwidth requirements for communications transmission, both for long haul and local area networks, and recent developments in the telecom fiber industry and diode laser technology. In contrast to rare earth doped fiber amplifiers, for which the range of wavelengths is fixed and limited, Raman gain bandwidths are larger and the operating wavelength is fixed only by the pump wavelength and the bandwidth of the Raman active medium. In this context, glasses are the material of choice for this application due to their relatively broad spectral response, and ability of making them into optical fiber. This dissertation summarizes findings on different oxide-based glasses that have been synthesized and characterized for their potential application as Raman gain media. Two main glass families were investigated: phosphate-based glass matrices for broadband Raman gain application and TeO2-based glasses for high Raman gain amplification. A phosphate network was preferred for the broadband application since the phosphate Raman active modes can provide amplification above 1000 cm-1, whilst TeO2-based glasses were selected for the high gain application due to their enhanced nonlinearities and polarizabilities among the other oxide-based network formers. The results summarized in this dissertation show that phosphate-based glasses can provide Raman amplification bandwidths of up to 40 THz, an improvement of almost 5 times the bandwidth of SiO2. On the other hand, tellurite-based glasses appear to be promising candidates for high gain discrete Raman applications, providing peak Raman gain coefficients of up to 50 times higher than SiO2, at 1064 nm. Although, visible spontaneous Raman scattering cross-section measurement is the most frequently used tool for estimating the strength and spectral distribution of Raman gain in materials, especially glasses, there are some issues that one needs to be aware when conducting these measurements near the absorption band edge of the material. This led to the detection of an inherent frequency-dispersion in the Raman susceptibility and a resonant enhancement phenomenon when measurements were conducted near the absorption edge of the material.

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Transparent glasses embedded with TTB structured ferroelectric nano/micro crystals (K3Li2Nb5O15, Ba5Li2Ti2Nb8O30) were fabricated in various tellurite and borate based glass matrices and characterized for their physical properties. Nanocrystals of K3Li2Nb5O15 were successfully grown inside tellurite glass matrix via conventional heat-treatment route. Eventhough, tellurite glasses preferentially crystallize only on the surface, bulk uniform crystallization was achieved in the (100-x) TeO2 - x(1.5K2O-Li2O-2.5Nb2O5) system. Heat capacity studies revealed them to be thermodynamically less fragile than any other tellurite glasses ever reported in the literature. Pyroelectric and ferroelectric effects as well as second harmonic generation were demonstrated for the heat treated (glass nanocrystal composites) samples in this system. The conventional method of melt-quenching of constituent oxides could not yield Ba5Li2Ti2Nb8O30 crystallites. So, Ba5Li2Ti2Nb8O30 microcrystals were successfully formed in tellurite glass matrix by mixing pre-reacted Ba5Li2Ti2Nb8O30 ceramic powders with TeO2. The glass transition temperature was found to be the highest ever reported and this system was kinetically strong based on the fragility parameter. Dielectric studies revealed a frequency and temperature independent nature of the dielectric constant and very low dielectric loss. The SHG measurement which was carried out as a function of temperature demonstrated the incidence of blue second harmonic generation in the microcrystals present in the glass matrix. Ba5Li2Ti2Nb8O30 nanocrystals were successfully crystallized in the transparent glass system (100-x)Li2B4O7 – x(Ba5Li2Ti2Nb8O30). Dielectric constant increased while the dielectric loss decreased with the increase in Ba5Li2Ti2Nb8O30 content. Nuclear magnetic resonance spectroscopic studies were carried out to have an insight into the structure of this system. Transmission studies and refractive index measurements were performed and various optical parameters were calculated. Dielectric and transport properties were studied for the glasses and glass nano/microcrystal composites of all the systems reported in this thesis. Li+ ion was found to be responsible for conduction in all these systems. Evolution of self-organized nanopatterns of K3Li2Nb5O15 crystals has been demonstrated in the glass system (100-x) TeO2 - x(1.5K2O-Li2O-2.5Nb2O5) by excimer laser irradiation. The second harmonic signal observed by the Maker fringe technique has been attributed to the presence of well-aligned nano-sized grating structures in the glass system. Glasses belonging to the systems TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30 and V2Te2O9 undergo spinodal decomposition on exposing to KrF pulsed excimer laser. The spinodally phase separated structures were observed on all the surfaces of the samples. Ring shaped patterns were observed on several locations of the samples at higher frequency of laser pulses probably owing to the shock waves produced by the high intense laser beam. Line shaped patterns were found to originate on the sample surfaces when irradiated for longer periods.

The absence of long-range order in glassy chalcogenides provides the convenience of changing the elemental ratios and hence the properties over a wide range. The interesting properties exhibited by chalcogenide glasses make them suitable materials for Phase Change Memories (PCM) and other applications such as infrared optical devices, photo-receptors, sensors, waveguides, etc. One of the most remarkable properties of chalcogenides is their electrical switching behavior. Reversible (threshold type) or irreversible (memory type) switching from a high resistance OFF state to a low resistance ON state in glassy chalcogenides occurs at a critical voltage called the threshold/switching voltage (VT). Investigations on the switching behavior and its composition dependence throw light on the local structural effects of amorphous chalcogenide semiconductors and also help us in identifying suitable samples for PCM applications. Thermal analysis by Differential Scanning Calorimetry (DSC) has been extensively used in glass science, particularly for measurements of thermal parameters such as enthalpy of relaxation, specific heat change, etc., near glass transition. Quite recently, the conventional DSC has been sophisticated by employing a composite temperature profile for heating, resulting in the Temperature Modulated DSC (TMDSC) or Alternating DSC (ADSC). Measurements made using ADSC reveal thermal details with enhanced accuracy and resolution, and this has lead to a better understanding of the nature of glass transition. The thermal parameters obtained using DSC/ADSC are also vital for understanding the electrical switching behavior of glassy chalcogenides. The motivation of this thesis was twofold: The first was to develop a novel, high voltage programmable power supply for electrical switching analysis of samples exhibiting high VT, and second to investigate the thermal and electrical switching behavior of certain Se-Te based glasses with Ge and Sb additives. The thesis contains seven chapters: Chapter 1: This chapter provides an overview of amorphous semiconductors (a-SC) with an emphasis on preparation and properties of glassy chalcogenides. The various structural models and topological thresholds of a-SC are discussed with relations to the glass forming ability of materials. The electronic band models and defect states are also dealt with. The essentials of electrical switching behavior of chalcogenides are discussed suggesting the electronic nature of switching and the role of thermal properties on switching. Chapter 2: The second chapter essentially deals with theory and practice of the experimental techniques adopted in the thesis work. The details of the melt-quenching method of synthesizing glassy samples are provided. Considering the importance, the theory of thermal analysis by DSC & ADSC, are discussed in detail, highlighting the advantages of the latter method adopted in the thesis work. The instrumentation and electronics, developed and used for electrical switching analysis are also introduced at a block diagram level. Finally, the methods used for structural analysis are briefed. Chapter 3: This chapter is dedicated to the design and development details of the programmable High Voltage dc Power Supply (HVPS: 1750 V, 45 mA) undertaken in the thesis work. The guidelines used for power supply topology selection, the specifications and block diagram of the HVPS are provided in that sequence. The operation of the HVPS is discussed using the circuit diagram approach. The details of software control are also given. The performance validations of the HVPS, undertaken through voltage & current regulation tests, step & frequency response tests are discussed. Finally, the sample-test results on the electrical switching behavior of representative Al20As16Te64 and Ge25Te65Se10 samples, obtained using both the current & voltage sweep options of the HVPS developed are illustrated. Chapter 4: Results of the thermally induced transitions governed by structural changes which are driven by network connectivity in the GexSe35-xTe65 (17 ≤ x ≤ 25) glasses, as revealed by ADSC experiments, are discussed in this chapter. It is found that the GexSe35-xTe65 glasses with x ≤ 20 exhibit two crystallization exotherms (Tc1 & Tc2), whereas those with x ≥ 20.5, show a single crystallization reaction upon heating (Tc). The glass transition temperature of GexSe35-xTe65 glasses is found to show a linear, but not-steep increase, indicating a progressive and not an appreciable build-up in network connectivity with Ge addition. The exothermic reaction at Tc1 has been found to correspond to the partial crystallization of the glass into hexagonal Te and the reaction at Tc2 is associated with the additional crystallization of rhombohedral Ge-Te phase. It is also found that the first crystallization temperature Tc1 of GexSe35-xTe65 glasses of lower Ge concentrations (with x ≤ 20), increases progressively with Ge content and eventually merges with Tc2 at x = 20.5 (<r> = 2.41); this behavior has been understood on the basis of the reduction in Te-Te bonds of lower energy and an increase in Ge-Te bonds of higher energy, with increasing Ge content. Chapter 5: This chapter deals with the electrical switching studies on GexSe35-xTe65 (17 ≤ x ≤ 25) glasses, with an emphasis on the role of network connectivity/rigidity on the switching behavior. It is found that the switching voltage (VT) increases with Ge content, exhibiting a sudden jump at x=20, the Rigidity Percolation Threshold (RPT) of the system. In addition, the switching behavior changes from memory to threshold type at the RPT and the threshold switching is found to be repetitive for more than 1500 cycles. Chapter 6: In this chapter, the results of thermal analysis (by ADSC) and electrical switching investigations on SbxSe55-xTe45 (2 ≤ x ≤ 9) are discussed. It is found that the addition of trivalent Sb contributes very meagerly to network growth but directly affects the structural relaxation effects at Tg. Further, SbxSe55-xTe45 glasses exhibit memory type electrical switching, which is understood on the basis of poor thermal stability of the samples. The metallicity factor is observed to outweigh the network factor in the composition dependence of VT of SbxSe55-xTe45 glasses. Chapter 7: The chapter 7 summarizes the results obtained in the thesis work and provides the scope for future work. The references are cited in the text along with the first author’s name and year of publication, and are listed at the end of each chapter in alphabetical order.