Academic literature on the topic 'Tetragonal Tungsten Bronzes (TTB)'

A series of vanadium substituted potassium hexagonal tungsten bronzes KxVyW1-yO3 (K-HTB) were prepared by conventional solid state method at 800 °C with compositions of x = 0.30 and 0.00 ? y ? 0.15. A mixture of K-HTB and non bronze phases with y ? 0.20 was observed. The proportion of this non bronze phase increases with increasing vanadium content. The non bronze phases in the mixture could not be indexed yet. In contrast, a very small amount of vanadium can be substituted in potassium tetragonal tungsten bronzes (K-TTB) at 800 °C with x = 0.50 and 0.00 ? y ? 0.02, however at 700 °C vanadium substituted K-TTB can be prepared with 0.00 ? y ? 0.05. Further substitution of vanadium in K-TTB decomposes to K-HTB and non-bronze phases. Keywords: Tungsten bronzes; Vanadium substituted bronze; Bronzoids. © 2012 JSR Publications. ISSN: 2070-0237 (Print); 2070-0245 (Online). All rights reserved. doi: http://dx.doi.org/10.3329/jsr.v4i2.9349 J. Sci. Res. 4 (2), 507-514 (2012)

The phosphate niobium bronzes form a large family of structures characterized by pentagonal or hexagonal tunnels. The host lattices of these oxides, involving a mixed valency of niobium Nb(V)-Nb(IV) are described here. The close relationships with pure octahedral structures, mainly perovskites, hexagonal tungsten bronzes (HTB) and tetragonal tungsten bronzes (TTB), and K 3 Nb 8 O 21 are studied.

Possibilities for `simple' octahedral tilting in the hexagonal and tetragonal tungsten bronzes (HTB and TTB) have been examined, making use of group theory as implemented in the computer programISOTROPY. For HTB, there is one obvious tilting pattern, leading to a structure in space groupP63/mmc. This differs from the space groupP63/mcmfrequently quoted from X-ray studies – these studies have in effect detected only displacements of the W cations from the centres of the WO6octahedra. The correct space group, taking account of both W ion displacement and the octahedral tilting, isP6322 – structures in this space group and matching this description have been reported. A second acceptable tilting pattern has been found, leading to a structure inP6/mmmbut on a larger `2 × 2 × 2' unit cell – however, no observations of this structure have been reported. For TTB, a search at the special points of the Brillouin zones revealed only one comparable tilting pattern, in a structure with space-group symmetryI4/mon a `21/2 × 21/2by 2' unit cell. Given several literature reports of larger unit cells for TTB, we conducted a limited search along the lines of symmetry and found structures with acceptable tilt patterns inBbmmon a `21/22 × 21/2 × 2' unit cell. A non-centrosymmetric version has been reported in niobates, inBbm2 on the same unit cell.

Tetragonal tungsten bronze (TTB) oxides are one of the most important classes of ferroelectrics. Many of these framework structures undergo ferroelastic transformations related to octahedron tilting deformations. Such tilting deformations are closely related to the rigid unit modes (RUMs). This paper discusses the whole set of RUMs in an ideal TTB lattice and possible crystal structures which can emerge owing to the condensation of some of them. Analysis of available experimental data for the TTB-like niobates lends credence to the obtained theoretical predictions.

A series of compounds KxTayW1-yO3 with x = 0.30, 0.00 ? y ? 0.30 and x = 0.55, 0.00 ? y ? 0.10 were synthesized by conventional solid-state method. The samples were characterized using XRD and FTIR spectroscopy. X-ray powder patterns reveal that the samples with compositions x = 0.30, y ? 0.30 show hexagonal tungsten bronze (HTB) type phase and the samples with x = 0.55, 0.02 ? y ? 0.10 show a mixture of two phases (K-HTB and tetragonal potassium tungsten bronze, K-TTB). The samples of the system, K0.30TayW1-yO3 with 0.00 ? y ? 0.15 shows no significant change in the cell parameters. However, for the composition y > 0.15, the cell parameter a decreases and c increases with increasing Ta content, which may be explained by the ordering of Ta for y > 0.15 suggesting the transformation to another space group. The appearance of absorption peak in the infrared absorption spectra of K0.3TayW1-yO3, y > 0.10 samples indicate the transition to non-metallic phase. DOI: http://dx.doi.org/10.3329/jbcs.v25i1.11770 Journal of Bangladesh Chemical Society, Vol. 25(1), 38-45, 2012

Orange-red lead titanate thin films are examined by high-resolution transmission electron microscopy and diffraction. It is remarkable that the structure is based on that of tetragonal-tungsten-bronze (TTB) rather than perovskite-type. The chemical basis for this result is examined, it is deduced that the TTB structure is stabilized by inclusion of hydroxyl ions during synthesis by a sol–gel route involving hydrolysis of n-Butyl titanate.

The evaluation of HAADF-STEM images of a sample with the composition Nb18W16O93 provided new insights into its real structure. The basic structure comprises an intact octahedral framework of the tetragonal tungsten bronze (TTB) type. The partial occupation of the pentagonal tunnels (PT) by metal–oxygen strings determines the oxygen-to-metal ratio (O/ΣM with M = Nb,W). For a large area, the O/ΣM was determined to be 2.755, which is bigger than the value of Nb18W16O93, which is O/ΣM = 2.735. To a large extent, the three-fold TTB superstructure of Nb8W9O47 with a high oxygen content is present (O/ΣM = 2.765). In addition, a new four-fold TTB superstructure was found in small domains. Nb12W11O63 with an O/ΣM = 2.739 obviously accommodates part of the sample’s metal excess compared to the stable phase Nb8W9O47.

Two superstructures of the TTB type (tetragonal tungsten bronze) exist in the system Nb2O5/WO3. They are caused by an ordered arrangement of pentagonal tunnels filled with metal–oxygen strings. Besides the well known 4:9 phase (Nb8W9O47), which has a tripled b axis, evidence for a new orthorhombic structure, Nb6W8O39 (a = b = 27.3 Å), has been found. The oxidation products of Nb7W10O47 and Nb4W13O47 frequently comprise less-ordered arrangements of filled tunnels, causing diffuse scattering. In Nb7W10O47.5 the electron diffraction patterns (along [001]) of many crystal fragments show circular diffuse scattering, which appears around the main reflections of the TTB substructure with two distinct radii (r*). r* \simeq 0.33a* indicates the predominance of 4:9-type domains, whereas r* \simeq 0.41a* corresponds to Nb6W8O39. In Nb4W13O49 the diffuse scattering pattern is cross-shaped; this is due to the presence of long slabs of diamond-linked pentagonal columns. Structure models for these particular states of order have been derived from high-resolution transmission electron microscopy images. Some general principles for the formation of the different arrangements are deduced. Apparently, two distinct types of link between the filled pentagonal tunnels are important features which lead to the stability of these structures.

Niobates with tetragonal tungsten bronze TTB-type structure have presented great technological potential due to their dielectric, ferroelectric, pyroelectric properties. The preparation by the modified polyol method and structural characterization of K2Nd(1-x)EuxNb5O15 nanopowders, where x = 0; 0.0025; 0.025; 0.05 e 0.1, were investigated. The structural parameters were analyzed as a function of concentration of europium ions in the K2NdNb5O15 host structure using the Rietveld method. From structural parameters was determined the TTB-type structure with tetragonal symmetry, where the pentagonal sites is occupied by K+ and Eu3+ ions and tetragonal sites is occupied only by Nd3+ ions. The addition of europium in the host structure led to a decrease in the lattice parameters, compatible with the increasing degree of distortion of NbO6 polyhedra. The average crystallite size showed values between 18.25 and 26nm.

CBN crystals show a one- and a two-dimensionally modulated modification. The former is isotypic with orthorhombic Ba4Na2Nb10O30and the latter with the tetragonal tungsten bronze type of crystal structure. The orthorhombic form irreversibly transforms to the tetragonal polymorph at the ferroelectric phase transition near 603 K. Orthorhombic and tetragonal CBN24 slightly differ in the distribution of the Ba and Ca atoms over the incompletely filled Me1 and Me2 sites. The tetragonal symmetry is further broken in orthorhombic CBN24 by different amplitudes of the positional modulations of O atoms which are symmetrically equivalent in the TTB structure. A similar orthorhombic phase of CBN31 could be obtained by quenching from 1473 K.

Les travaux présentés dans cette thèse concernent l'élaboration et la caractérisation des matériaux diélectriques sans plomb, capables d'emmagasiner directement de l'énergie électrostatique, thermiquement stables et facile à intégrer dans des circuits électriques. Au cours de ce travail, nous nous sommes intéressés à une nouvelle famille de matériaux ferroélectriques de structure de type Bronze oxygéné de tungstène quadratique (TTB). L'intérêt porté à cette famille réside dans le fait que la structure TTB présente trois types de tunnels de section pentagonale, carré et triangulaire, capables d'accueillir différents types d’élément chimiques. Ainsi, les travaux que nous avons réalisés ont porté des céramiques de formule générale Ba2Na1-xNdx/3Nb5O15 et Ba(2-x)Nd(2x/3)NaNb5O15 préparées par la technique de réaction à l'état solide. Ces travaux nous ont permis d'obtenir des phases pures de structures TTB et de délimiter l'étendue de solutions solides. Les études effectuées par diffraction des rayons X (DRX), par microscope électronique à balayage (MEB) ainsi que les investigations par spectroscopie Raman ont permis de contrôler la pureté de nos céramiques et de mettre en évidence la stabilisation d'une structure TTB. Les mesures diélectriques en fonction de la température et de la fréquence ont montré que : * la solution solide Ba2(Na1-xNdx/3)Nb5O15 (x=0.3; 0.5; 0.7) se distingue par un comportement ferroélectrique classique quelle que soit la valeur de x. * la solution solide Ba(2-x)Na(2x/3)NaNb5O15 montre trois types d'attitudes qui dépendent de x : - pour x=0.3 (Ba1.7Nd0.2NaNb5O15) est ferroélectrique classique, - pour x=0.5 (Ba1.5Nd0.33NaNb5O15) est ferroélectrique classique avec une valeur de TC =120°C et ferroélectrique relaxeur en dessous de Tm (= 20 °C à f = 10 kHz), - pour x=0.7 (Ba1.3Nd0.46NaNb5O15) et x=1 (Ba1Nd0.66NaNb5O15) qui sont de type ferroélectrique relaxeurs. Les résultats obtenus au cours de ce travail indiquent clairement que l'introduction de Nd dans la matrice BNN produit une modification de la structure et des propriétés physiques de ces composés : - La substitution en site carré de Na+ par l’ion trivalent Nd3+ conduit à une amélioration de la densité de stockage d'énergie électrique, - La substitution en site pentagonale de Ba2+ par l'ion trivalent Nd3+ conduit à l'apparition d'un matériau ferroélectrique relaxeur susceptible de fournir un potentiel élevé de stockage d'énergie électrique par rapport au ferroélectrique<br>The work presented in this thesis concerns the elaboration and characterization of lead-free dielectric materials, capable of directly storing electrostatic energy, thermally stable and easy to integrate in electrical circuits. In this work, we are interested in a new family of ferroelectric materials with a quadratic tungsten oxide bronze (TTB) structure. The interest in this family lies in the fact that the TTB structure presents three types of tunnels of pentagonal, square and triangular section, able to accommodate different types of chemical elements. Thus, the work that we have done has involved ceramics of general formulas Ba2Na1-xNdx/3Nb5O15 and Ba(2-x)Nd(2x/3)NaNb5O15 prepared by the solid state reaction technique. X-ray diffraction (XRD), scanning electron microscopy (SEM) and investigations by Raman spectroscopy allowed us to control the purity of our ceramics and to demonstrate the stabilization of a TTB structure. Dielectric measurements as a function of temperature and frequency showed that: * The solid solution Ba2Na1-xNdx/3Nb5O15 (x=0.3; 0.5; 0.7) is distinguished by a classical ferroelectric behavior whatever the value of x. * The solid solution Ba(2-x)Nd(2x/3)NaNb5O15 shows three types of attitudes depending on x : - For x=0.3 (Ba1.7Nd0.2NaNb5O15) is classical ferroelectric, - For x=0.5 (Ba1.5Nd0.33NaNb5O15) is classical ferroelectric with a value of Tc =120 °C and relaxor ferroelectric below Tm (= 20 °C at f = 10 kHz), - For x=0.7 (Ba1.3Nd0.46NaNb5O15) and x=1 (Ba1Nd0.66NaNb5O15) which are relaxor ferroelectric. The results obtained during this work clearly indicate that the introduction of Nd in the BNN matrix produces a modification of the structure and physical properties of these compounds: - The square site substitution of Na+ by the trivalent ion Nd3+leads to an improvement of the electrical energy storage density, - The pentagonal site substitution of Ba2+ by the trivalent ion Nd3+ leads to the appearance of a relaxor ferroelectric material able to provide a high potential of electric energy storage compared to the ferroelectric

Les travaux présentés dans ce manuscrit concernent des niobates de formulation Ba2LnNb4O15 (Ln = La ou Nd) et de structure "Tetragonal Tungsten Bronze" (TTB). Ces travaux se situent à la charnière de la chimie et de la physique des matériaux diélectriques et visent à mettre en relation structure cristalline et propriétés diélectriques. L'étude a été menée sur des TTB élaborés sous forme céramique et monocristalline. Après détermination de conditions optimales de croissance, par fusion de zone en four à image, des sections monocristallines ont été obtenues et caractérisées. Les résultats obtenus suggèrent des liens étroits entre composition, modulations structurales apériodiques et comportement diélectrique. Dans le même temps, deux nouvelles solutions solides céramiques ont été explorées, avec des schémas de substitution différents menant notamment à une réflexion très large sur les liens cristallochimie-ferroélectricité dans cette famille de TTB. Ces solutions solides présentent un crossover relaxeur-ferroélectrique, un comportement original et déjà observé dans d'autres solutions solides issues de cette famille de TTB. Des caractérisations avancées (mesures pyro- et piézoélectriques, cycles de polarisation) et des études structurales résolues en composition et en température ont permis d'établir des diagrammes de phases diélectriques montrant l'existence d'un état ferroélectrique métastable. Finalement, la présence d’une modulation structurale bidimensionnelle a pu être confirmée, dans les monocristaux et dans les céramiques, et l'ensemble des résultats obtenus pointent son implication dans les comportements cristallochimiques originaux rencontrés dans ces TTB<br>The present work deals with Ba2LnNb4O15 (Ln = La ou Nd) niobates crystallizing with the "Tetragonal Tungsten Bronze" (TTB) structure. These researches, at the interface of chemistry and physics of dieletrics, aim at establishing structure / dielectric properties relationships. They were performed on TTB materials elaborated in ceramic and single crystal forms. Following optimization of growth parameters with an image furnace, single crystals were obtained and characterized. The results obtained suggest that composition, aperiodically modulated structure and dielectric behavior are closely tied in TTBs. Meanwhile, two new ceramic solid solutions with different substitutions schemes were investigated, deepening the insight on crystal-chemistry and ferroelectricity of TTBs. These solid solutions exhibit a relaxor-ferroelectric crossover, an original behaviour previously observed in solid solutions derived from the same family of TTB niobates. Advanced physical characterization (ferro-, pyro- and piezoelectric measurements, polarization loops), and composition/temperature resolved structural studies, allowed for the determination of a dielectric phase diagrams showing the presence of a metastable ferroelectric state. Finally, the existence of a two-dimensional structural modulation in single crystals and ceramics has been confirmed, and the whole set of experimental results points towards its implication in the original dielectric behavior observed in these TTBs

Transition metal fluorides represent an important family of complex solids displaying a variety of different properties and interesting phenomena. Despite their remarkable behaviour, these classes of materials have not received much attention and the rationalization of their behaviour is still lacking a systematic approach. This thesis aims to contribute to the field by examining previously unknown or understudied complex fluorides. The compounds were selected for their intriguing physical properties that range from superconductivity to multiferroism. The discovery of superconductivity in the iron pnictides sparked new interest in materials with layered ZrCuSiAs-type structure. Herein the properties of one of these systems, namely SrFeAsF, will be discussed. We have found that it behaves as a poor metal and undergoes a tetragonal (P4/nmm) to orthorhombic (Cmma) structural transition at T = 180 K, accompanied by a spin density wave in magnetic susceptibility and electrical resistivity. Below T < 150 K, the Fe moments order in antiferromagnetic spin-stripes. Electron doping with La3+ is a successful route to obtain superconducting phases, with maximum Tc = 27 K (x = 0.2). The isostructural AeMnPnF series (Ae = Sr, Ba; Pn = P, As, Sb) was also investigated to elucidate the influence of transition metal d-electrons and size effects of Ae and Pn on the physical properties. The isoelectronic replacement of Ae and Pn leads to a significant distortion in the tetragonal building blocks. All d5 Mn fluorides investigated here are insulating antiferromagnets with TN ~ 350 K. Due to the coexistence of electronic and magnetic ordering, the tetragonal tungsten bronze (TTB) materials KxM2+ xM3+ 1-xF3 (x = 0.4 – 0.6; M = transition metal) are potential multiferroics. The type of structural distortion adopted by these systems is strongly dependant on the M2+/M3+ ratio. For instance, our high-resolution diffraction study on K0.5Mn0.5Cr0.5F3 has revealed a small orthorhombic distortion, which indicates full chemical order of Mn2+ and Cr3+ on all crystallographic sites. K0.5Mn0.5Cr0.5F3 remains orthorhombic Ccc2 on cooling through the ferromagnetic transition at TN = 23 K. On heating, the structure is acentric up to T = 373 K, where a change to tetragonal P42/mbc symmetry marks the transition from ferroelectric (polar) to paraelectric (apolar) states. High-pressure diffraction experiments have shown that the Ccc2 structure is robust upon pressurization with anisotropic axial compressibility up to the maximum pressure applied p = 18 GPa. The crystal structure of related mixed-valence TTB fluoride K0.6Cr2+ 0.6Cr3+ 0.4F3 is influenced by the presence of Jahn-Teller active Cr2+. The structural analysis described here revealed the presence of a small polar monoclinic distortion (P112) providing a clear signature of full charge order (CO). On heating, the gradual loss of CO leads to two consecutive structural phase transitions to orthorhombic (Pba2, T = 423 K) and then tetragonal (P42/mbc, T = 823 K) lattices, the latter is the signature of the ferro- to paraelectric transition. Below T = 150 K, increased X-ray exposure time leads to CO-melting and the stabilization of a new, charge-disordered orthorhombic phase (Cmm2), with a phenomenology similar to the CO manganites. In highpressure diffraction experiments, a further transition to tetragonal P4bm symmetry is found at p = 6 GPa. The magnetic susceptibility points towards a complex spin arrangement, with two transitions at TN = 33 K and 6 K. The results presented herein show the richness of the structural, electronic and magnetic phase diagrams of transition metal fluorides and clearly demonstrate that systematic studies on these systems will greatly enhance our current understanding of the underlying mechanisms of important phenomena such as superconductivity and ferroelectricity.

Des recherches très importantes ont été dédiées à l'étude des composés ferroélectriques de type bronze de tungstène quadratique (TTB). Cette thèse concerne la synthèse et la caractérisation de 7 matériaux TTB de formule générale A6M2M'8O30 (A = Sr2+, Ba2+ ou Pb2+, M = Ti4+, Zr4+ ou HF4+; M' = Nb5+ ou Ta5+). Ces composés cristallins de grande taille ∼100 nm ont été synthétisés sous forme de poudre. Les moyennes expérimentales : diffractions des rayons X, spectroscopie Raman, la microscopie électronique MEB et MET, l'optique non linéaire ONL, ont permis d'établir des relations étroites entre structure et propriétés physiques. Les susceptibilités optiques non linéaires de 2eme et 3eme ordres, χ(2), χ(3) de chaque composés ont été déterminées et les valeurs résultantes du χ(3) ne montrent pas les mêmes caractéristiques que χ(2), car le signal de THG est moins dépendant de structure que SHG qui requiert un milieu non-centrosymétrique. Le décalage fréquentiel (Δσ) des modes de vibrations entre les structures à base de strontium(Sr) et celles à base de Barium(Ba) a été constaté afin d'identifier les signatures propres de ces composés. L'interprétation de ces poudres n'était pas facile car les pics sont très délicats. Nos mesures expérimentales montrent clairement que les positions des pics peuvent être modifiées par le changement cationique au sein des matériaux, plus la maille cristalline est rigide, plus on a des pics plus discernables. La différence est nettement visible là ou l'émission est autour de 808 cm-1 pour la structure (Sr), alors que pour le (Br) elle est autour de 780cm-1. Nous attribuons ce Δσ (28cm-1) à la transition de groupe de symétrie spatiale de Pba2 vers P4bm. L'ensemble des résultats décrits dans ce travail ont montrés la grande variété des paramètres sur lesquels il est possible d'agir afin d'optimiser les compositions en vue d'une application spécifique<br>Recently, very significant research has been devoted to the study of ferroelectric compounds of tetragonal tungsten bronze (TTB). This thesis deals with the synthesis and characterization of 7 TTB's material with general formula A6M2M'8O30 (A = Sr2+, Ba2+ or Pb2+, M = Ti4+, Zr4+ or HF4+, M '= Nb5+ or Ta5+). These crystalline compounds of large size ~ 100 nm were synthesized in powder form. The experimental Technics: X-ray diffraction, Raman spectroscopy, scanning electron microscopy SEM and TEM and nonlinear optics NLO, allowed us to establish close relationships between structure and physical properties. The nonlinear 2nd and 3rd order optical susceptibility χ(2), χ(3) of all compounds were determined and the resulting values of χ(3) did not show the same characteristics as measures of χ(2) because the THG signal is less dependent on the structure where SHG signal requires a non-centro-symmetric medium. The frequency shift between the vibration modes of structures containing strontium (Sr) and those based on Barium (Ba) has been detailed to identify signatures of these specific compounds. The interpretation of these powders wasn't that easy as these peaks are very delicate but our experimental results clearly show that the positions of the peaks can be modified by the change in cation materials, as long as the crystal lattice is more rigid, more we get discernible Raman modes. This difference is clearly visible where the emission is around 808 cm-1 for the structure Sr, whereas the Br it is centered around 780cm-1. We attribute these Δσ (28cm-1) to the transition of spatial symmetry group from Pba2 to P4bm. Results showed the wide variety of settings in which it is possible to act in order to optimize the compositions for a specific application

La structure bronze quadratique de tungstène, grâce à sa flexibilité cristallochimique, est une candidate légitime pour le développement de matériaux fonctionnels. L'étude des propriétés diélectriques, pyroélectriques, et ferroélectriques de céramiques de formulation Ba2NdFeNb4-xTaxO15 montre un crossover relaxeur-ferroélectrique-paraélectrique, avec une hystérèse thermique de la transition ferroélectrique. L'étude structurale des monocristaux relaxeurs Ba2LnFeNb4O15 (Ln=La, Pr, Nd, Sm, Eu), obtenus par la méthode du flux, a mis en évidence une structure modulée. L'affinement de la structure de base prouve l'existence de moments dipolaires dans le plan ab (dus à une distorsion des octaèdres [NbO6]). Afin d'établir un lien entre la structure cristalline et les propriétés d'un composé dérivé du multiferroïque MnWO4, la croissance en four à image de Mn0,85Mg0,15WO4 a été entreprise avec succès.

In this work, in-depth structural and electrical characterisation is used to study a family of “empty” tetragonal tungsten bronzes (TTBs), A2₄A1₂B1₂B2₈O₃₀. An initial investigation into the effect of the A1-cation size on the properties of empty Ba₄R₀.₆₇◻₁.₃₃Nb₁₀O₃₀ TTBs (where R is the A1-cation and R = La, Nd, Sm, Gd, Dy and Y; ◻ = vacancy) was performed. These were determined to be metrically tetragonal by powder x-ray diffraction, with decreasing R cation size inducing increased crystal anisotropy. This tetragonal structural distortion, driven by contraction in the ab-plane, is shown to stabilise c-axis ferroelectricity; a direct correlation between tetragonality and the ferroelectric Curie temperature, T[sub]C, is demonstrated. Further examination of the relaxor ferroelectric (RFE) to ferroelectric (FE) crossover in Ba₄(La₁₋ₓNdₓ)₀.₆₇◻₁.₃₃Nb₁₀O₃₀ TTBs using detailed structural studies employing variable temperature, high resolution neutron, synchrotron X-ray and electron diffraction revealed a common superstructure with 2√2 × √2 × 2 cell with respect to the basic tetragonal aristotype cell. However, they display different degrees of order/disorder which can disrupt polar order (ferroelectricity). La-rich analogues exhibit a disordered regime between the low and high temperature ferroelectric and non-polar phases. Although polar, this disordered regime is non-ferroelectric, however, large polarisation may be established with an applied electric field, but relaxes back to the disordered phase upon removal of the field. Substitution of Nd for La at the A1-site leads to destabilisation of the disordered phase and reintroduces “normal” ferroelectric behaviour. Finally, isovalent substitution of Sr²⁺∙ for Ba²⁺ is shown to lead to the development of relaxor behaviour at higher dopant concentrations in Ba₄₋ₓSrₓDy₀.₆₇◻₁.₃₃Nb₁₀O₃₀, (x = 0, 0.25, 0.5, 1, 2, 3; ◻ = vacancy). With increasing x the unit cell contracts in both the ab- plane and c-axis coinciding with a decrease in T[sub]C and development of relaxor behaviour for x ≥ 2. This observation is rationalised by differing cation occupancies: for x ≤ 1, Sr²⁺ principally occupies the A2-site while for x ≥ 2 significant Sr²⁺ occupation of the A1-site leads to the observed RFE characteristics. The FE to RFE crossover is discussed in the context of a previously proposed TTB crystal chemical framework with the A1-site tolerance factor identified as the dominant influence on relaxor behaviour.

Les multiferroïques sont des matériaux dans lesquels plusieurs propriétés ferroïques peuvent coexister, e. g. ferromagnétisme et ferroélectricité. La recherche de tels matériaux fait l'objet d'une activité croissante en raison de l’enjeu majeur qu’ils représentent dans de nombreux domaines (mémoires, spintronique…). Les matériaux qui possèdent les propriétés nécessaires pour des applications futures sont cependant peu nombreux. Des niobates de formule Ba2LnFeNb4O15 (Ln = lanthanide), de structure bronze quadratique (TTB) susceptibles de présenter un ordre ferroélectrique et un ordre magnétique ont été synthétisés. Les propriétés magnétiques des céramiques proviennent d'une phase secondaire, faisant d’eux des composites multiferroïques. Leur souplesse cristallochimique permet de contrôler les propriétés composites par substitutions cationiques dans la matrice TTB. Afin de compléter l'étude cristallochimique, la croissance de monocristaux de TTB a été entreprise avec succès<br>Multiferroics are materials which possess several ferroic properties, e.g. ferroelectricity, ferromagnetism. The search for multiferroics arises a growing activity, due to their potential applications in memories, spintronic… Yet the materials displaying the adequate properties for future application are very few. Niobates with the formula Ba2LnFeNb4O15, potentially ferroelectric and ferromagnetic, have been synthesized. The magnetic properties of the ceramics are related to a secondary phase, thus making them composite multiferroics. Their crystal-chemical flexibility allows for the composites properties tuning by cationic substitutions into the TTB framework. To complete the crystal-chemical study, the growth of TTB single-crystals was successfully engaged

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.