Дисертації з теми "CALCIUM BISMUTH"

Ferroelectric materials are very promising for a variety of applications such as high-permittivity capacitors, ferroelectric memories, pyroelctric sensors, piezoelectric and electrostrictive transducers and electro-optic devices, etc. In the area of ferroelectric ceramics, lead-based compounds, which include lead zirconatetitanate (PZT) solid solutions, occupy an important place because of their superior physical properties. However, due to the toxicity of lead, there is an increasing concern over recycling and disposing of the devices made out of these compounds, which has compelled the researchers around the globe to search for lead-free compounds with promising piezo and ferroelectric properties. Ferroelectric materials that belong to Aurivillius family of oxides have become increasingly important from the perspective of industrial applications because of their high Curie-temperatures, high resistivity, superior polarization fatigue resistanceand stable piezoelectric properties at high temperatures. These bismuth layer-structured ferroelectrics (BLSF) comprise an intergrowth of [Bi2O2]2+ layers and [An+1Bn O3n+1]2- pseudo-perovskite units, where ‘n’ represents the number of perovskite-like layers stacked along the c-axis. ‘A’ stands for a mono-, di- or trivalent ions or a combination of them, ‘B’ represents a small ion with high valencysuch as Ti4+, Nb5+, Ta5+or a combination of them.Ferroelectricity in the orthorhombic phase of these compounds was generally attributed to the cationic displacement along the polar a-axis and the tilting of octahedra around the a- and c-axes. Sr2Bi4Ti5O18(SBT) is ann = 5 member of the Aurivillius family and possess promising ferroelectric and piezoelectric properties that could be exploited for a wide range of applications, including ferroelectric random access memories (FeRAM), piezoelectric actuators, transducers and transformers. Reports in the literaturereveal that the ferroelectricand piezoelectric properties of these oxides can be tuned depending on synthesis routes vis-a-vis micro-structural aspects (texture, grain size) and site specific dopant substitutions.In the present study, textured SBT ceramics were fabricated using pre-reacted precursors and their anisotropic dielectric, piezoelectric and ferroelectric properties were demonstrated. Grain size tunability with regard to their physical properties was accomplished in the ceramics, fabricated using fine powders obtained from citrate assisted sol-gel synthesis. The grain size dependent second harmonic generation activity of SBT ceramics was investigated. Enhancement in the piezoelectric and ferroelectric properties of SBT ceramics was achieved by substituting A site ions (Sr2+) with a combination of Na+ and Bi3+. From the perspective of non-linear optical device applications, physical properties associated with the SBT crystallized in a transparent lithium borate glass matrix were studied. The results obtained in the present investigations are organized as follows, Chapter 1 gives a brief exposure to the field of ferroelectrics. The emphasis has been on the ferroelectric oxides belonging to the Aurivillius family. Structural aspects and the underlying phenomena associated with ferroelectricity in these compounds are discussed. A brief introduction to the glasses, thermodynamic aspects of glass formation and fabrication of glass- ceramics are included. Basic principles involved in the non-linear optical activities are highlighted. Chapter 2 describes the various experimental techniques that were employed to synthesize and characterize the materials under investigation. The experimental details pertaining to the measurement of various physical properties are included. Chapter 3 deals with the fabrication of Sr2Bi4Ti5O18 ceramics using the pre-reacted Bi4Ti3O12 and SrTiO3 powders viasolid-state reaction route. These in stoichiometric ratio were uniaxially pressed and sintered at 1130oC for 3 h resulting in textured Sr2Bi4Ti5O18 ceramics. The obtained dense ceramics exhibited crystallographic anisotropy with prominent c-axis oriented grains (Lotgering factor of 0.62) parallel to the uniaxially pressed direction. The resultant anisotropy in the ceramics was attributed to the reactive template-like behavior of Bi4Ti3O12 that was used as a precursor to fabricate Sr2Bi4Ti5O18 ceramics. Dielectric, ferro and piezoelectric properties measured on the ceramics in the direction perpendicular to the uniaxially pressed axis were found to be superior to that measured in the parallel direction. Chapter 4 reports the details pertaining to the synthesis of strontium bismuth titanate (Sr2Bi4Ti5O18) powders comprising crystallites of average sizes in the range of 94–1400 nm via citrate-assisted sol-gel route. X-ray powder diffraction, Transmission Electron Microscopy (TEM) and Raman spectroscopy were employed for the structural studies. A crystallite size-dependent variation in the lattice parameters and the shift in the Raman vibration modes were observed. Second harmonic signal (532 nm) intensity of the Sr2Bi4Ti5O18 powders increased with the increase in the average crystallite size and the maximum intensity obtained in the reflection mode was 1.4 times as high as that of the powdered KH2PO4. Piezo force microscopic analyses carried out on an isolated crystallite of size 74 nm, established its single domain nature with the coercive field as high as 347 kV/cm. There was a systematic increase in the d33 value with an increase in the size of the crystallite and a high piezoelectric coefficient of ~27 pm/V was obtained from an isolated crystallite of size 480 nm. Chapter 5 illustrates the details concerning the fabrication of Sr2Bi4Ti5O18(SBT) ceramics with different grain sizes (93 nm–1.42 μm) using nano-crystalline powders synthesized via citrate assisted sol-gel method. The grain growth in these powder compacts was found to be controlled via the grain boundary curvature mechanism, associated with anactivation energy of 181.9 kJ/mol. Interestingly with a decrease in grain size there was an increase in the structural distortion which resulted in a shift of Curie-temperature (phase transition) towards higher temperatures than that of conventional bulk ceramics. Extended Landau phenomenological theory for the ferroelectric particles was invoked to explain experimentally observed size dependent phase transition temperature and the critical size for SBT is predicted to be 11.3 nm. Grain size dependent dielectric, ferroelectric and piezoelectric properties of the SBT ceramics were studied and the samples comprising average grain size of 645 nm exhibited superior physical properties that include remnant polarization (2Pr) = 16.4 μC cm-2, coercive field (Ec) = 38 kV cm-1, piezoelectric coefficient (d33) = 22 pC N-1 and planar electromechanical coupling coefficient (kp) = 14.8 %. In Chapter 6, the studies pertaining to the fabrication of Sr(2-x)(Na0.5Bi0.5)xBi4Ti5O18 (SNBT) ceramics for various x values (0, 0.1, 0.25, 0.3, 0.4 and 0.5), using fine powders synthesized via sol-gel route are dealt with. X-ray powder diffraction, transmission electron microscopy and Raman spectroscopic studies were carried out to confirm composition dependent structural changes taking place in the SNBT ceramics. Scanning electron microscopic studies carried out on ceramics revealed that dopants played an important role in inhibiting the grain growth. Dielectric constants of the ceramics were found to decrease with an increase in ‘x’. The increase in Curie temperature with increase in ‘x’ is attributed to the decrease in the tolerance factor. Particularly,x = 0.3 composition of the SNBT ceramics exhibited better piezo and ferroelectric properties with a higher Curie-temperature (569 K). The piezoelectric coefficient (d33) and the planar electromechanical coupling coefficient (kp) of SNBT(x = 0.3) were enhanced by 25% and 42% respectively as compared to that of the undoped ceramics. Chapter 7 deals with the glasses in the system (100 –x) {Li2O + 2B2O3} ─x {2SrO + 2Bi2O3 +5TiO2} (where, x = 10, 25 and 35) fabricated via conventional melt-quenching technique. The amorphous and glassy characteristics of the samples were confirmed respectively using X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods. All the compositions under investigation exhibited two distinct crystallization peaks (exothermic peaks in the DSC traces): the first peak at ~ 545 °C and the second at ~610 °C that were found to be associated with the crystallization of the phases (as confirmed from the XRD studies) Sr2Bi4Ti5O18 (SBT)and Li2B4O7 (LBO) respectively. Non-isothermal crystallization kinetics (using modified Ozawa-type plots) for SBT crystallization in the LBO glass matrix for the compositions x = 10 and 35, indicated three dimensional growth of the crystallites from pre-existing nuclei present in the as-quenched samples and their effective activation energies for crystallization were found to be around 686 ± 85 kJ/mol and 365 ± 53 kJ/mol, respectively. The optical band gap of the as-quenched glasses for the composition x = 35 was 2.52 eV, is less than that of the composition x = 10 (2.91 eV). The Urbach energies for the as-quenched glasses of compositions x = 10, 25 and 35 were found to be 118 ± 2 meV, 119 ± 2 meV and 192 ± 1 meV respectively.The glasses associated with the composition x = 35, on controlled heat-treatment at 515 °C for various durations (1―20 h), yielded glass-ceramics comprising SBT nano-crystals (18―28 nm) embedded in the LBO glass matrix. Compressive strain in the nano-crystallites of SBT, analyzed using Williamson-Hall method was found to decrease with an increase in the crystallite size. The second harmonic generation signal (532 nm) intensity emanating from glass-nanocrystal composites comprising 22.1 nm SBT crystallites was nearly 0.3 times that of a KDP single crystal. Although each chapter is provided with conclusions and a list of references, thesis ends with a separate summary and conclusions.

Ferroelectric materials are very promising for a variety of applications such as high-permittivity capacitors, ferroelectric memories, pyroelctric sensors, piezoelectric and electrostrictive transducers and electro-optic devices, etc. In the area of ferroelectric ceramics, lead-based compounds, which include lead zirconatetitanate (PZT) solid solutions, occupy an important place because of their superior physical properties. However, due to the toxicity of lead, there is an increasing concern over recycling and disposing of the devices made out of these compounds, which has compelled the researchers around the globe to search for lead-free compounds with promising piezo and ferroelectric properties. Ferroelectric materials that belong to Aurivillius family of oxides have become increasingly important from the perspective of industrial applications because of their high Curie-temperatures, high resistivity, superior polarization fatigue resistanceand stable piezoelectric properties at high temperatures. These bismuth layer-structured ferroelectrics (BLSF) comprise an intergrowth of [Bi2O2]2+ layers and [An+1Bn O3n+1]2- pseudo-perovskite units, where ‘n’ represents the number of perovskite-like layers stacked along the c-axis. ‘A’ stands for a mono-, di- or trivalent ions or a combination of them, ‘B’ represents a small ion with high valencysuch as Ti4+, Nb5+, Ta5+or a combination of them.Ferroelectricity in the orthorhombic phase of these compounds was generally attributed to the cationic displacement along the polar a-axis and the tilting of octahedra around the a- and c-axes. Sr2Bi4Ti5O18(SBT) is ann = 5 member of the Aurivillius family and possess promising ferroelectric and piezoelectric properties that could be exploited for a wide range of applications, including ferroelectric random access memories (FeRAM), piezoelectric actuators, transducers and transformers. Reports in the literaturereveal that the ferroelectricand piezoelectric properties of these oxides can be tuned depending on synthesis routes vis-a-vis micro-structural aspects (texture, grain size) and site specific dopant substitutions.In the present study, textured SBT ceramics were fabricated using pre-reacted precursors and their anisotropic dielectric, piezoelectric and ferroelectric properties were demonstrated. Grain size tunability with regard to their physical properties was accomplished in the ceramics, fabricated using fine powders obtained from citrate assisted sol-gel synthesis. The grain size dependent second harmonic generation activity of SBT ceramics was investigated. Enhancement in the piezoelectric and ferroelectric properties of SBT ceramics was achieved by substituting A site ions (Sr2+) with a combination of Na+ and Bi3+. From the perspective of non-linear optical device applications, physical properties associated with the SBT crystallized in a transparent lithium borate glass matrix were studied. The results obtained in the present investigations are organized as follows, Chapter 1 gives a brief exposure to the field of ferroelectrics. The emphasis has been on the ferroelectric oxides belonging to the Aurivillius family. Structural aspects and the underlying phenomena associated with ferroelectricity in these compounds are discussed. A brief introduction to the glasses, thermodynamic aspects of glass formation and fabrication of glass- ceramics are included. Basic principles involved in the non-linear optical activities are highlighted. Chapter 2 describes the various experimental techniques that were employed to synthesize and characterize the materials under investigation. The experimental details pertaining to the measurement of various physical properties are included. Chapter 3 deals with the fabrication of Sr2Bi4Ti5O18 ceramics using the pre-reacted Bi4Ti3O12 and SrTiO3 powders viasolid-state reaction route. These in stoichiometric ratio were uniaxially pressed and sintered at 1130oC for 3 h resulting in textured Sr2Bi4Ti5O18 ceramics. The obtained dense ceramics exhibited crystallographic anisotropy with prominent c-axis oriented grains (Lotgering factor of 0.62) parallel to the uniaxially pressed direction. The resultant anisotropy in the ceramics was attributed to the reactive template-like behavior of Bi4Ti3O12 that was used as a precursor to fabricate Sr2Bi4Ti5O18 ceramics. Dielectric, ferro and piezoelectric properties measured on the ceramics in the direction perpendicular to the uniaxially pressed axis were found to be superior to that measured in the parallel direction. Chapter 4 reports the details pertaining to the synthesis of strontium bismuth titanate (Sr2Bi4Ti5O18) powders comprising crystallites of average sizes in the range of 94–1400 nm via citrate-assisted sol-gel route. X-ray powder diffraction, Transmission Electron Microscopy (TEM) and Raman spectroscopy were employed for the structural studies. A crystallite size-dependent variation in the lattice parameters and the shift in the Raman vibration modes were observed. Second harmonic signal (532 nm) intensity of the Sr2Bi4Ti5O18 powders increased with the increase in the average crystallite size and the maximum intensity obtained in the reflection mode was 1.4 times as high as that of the powdered KH2PO4. Piezo force microscopic analyses carried out on an isolated crystallite of size 74 nm, established its single domain nature with the coercive field as high as 347 kV/cm. There was a systematic increase in the d33 value with an increase in the size of the crystallite and a high piezoelectric coefficient of ~27 pm/V was obtained from an isolated crystallite of size 480 nm. Chapter 5 illustrates the details concerning the fabrication of Sr2Bi4Ti5O18(SBT) ceramics with different grain sizes (93 nm–1.42 μm) using nano-crystalline powders synthesized via citrate assisted sol-gel method. The grain growth in these powder compacts was found to be controlled via the grain boundary curvature mechanism, associated with anactivation energy of 181.9 kJ/mol. Interestingly with a decrease in grain size there was an increase in the structural distortion which resulted in a shift of Curie-temperature (phase transition) towards higher temperatures than that of conventional bulk ceramics. Extended Landau phenomenological theory for the ferroelectric particles was invoked to explain experimentally observed size dependent phase transition temperature and the critical size for SBT is predicted to be 11.3 nm. Grain size dependent dielectric, ferroelectric and piezoelectric properties of the SBT ceramics were studied and the samples comprising average grain size of 645 nm exhibited superior physical properties that include remnant polarization (2Pr) = 16.4 μC cm-2, coercive field (Ec) = 38 kV cm-1, piezoelectric coefficient (d33) = 22 pC N-1 and planar electromechanical coupling coefficient (kp) = 14.8 %. In Chapter 6, the studies pertaining to the fabrication of Sr(2-x)(Na0.5Bi0.5)xBi4Ti5O18 (SNBT) ceramics for various x values (0, 0.1, 0.25, 0.3, 0.4 and 0.5), using fine powders synthesized via sol-gel route are dealt with. X-ray powder diffraction, transmission electron microscopy and Raman spectroscopic studies were carried out to confirm composition dependent structural changes taking place in the SNBT ceramics. Scanning electron microscopic studies carried out on ceramics revealed that dopants played an important role in inhibiting the grain growth. Dielectric constants of the ceramics were found to decrease with an increase in ‘x’. The increase in Curie temperature with increase in ‘x’ is attributed to the decrease in the tolerance factor. Particularly,x = 0.3 composition of the SNBT ceramics exhibited better piezo and ferroelectric properties with a higher Curie-temperature (569 K). The piezoelectric coefficient (d33) and the planar electromechanical coupling coefficient (kp) of SNBT(x = 0.3) were enhanced by 25% and 42% respectively as compared to that of the undoped ceramics. Chapter 7 deals with the glasses in the system (100 –x) {Li2O + 2B2O3} ─x {2SrO + 2Bi2O3 +5TiO2} (where, x = 10, 25 and 35) fabricated via conventional melt-quenching technique. The amorphous and glassy characteristics of the samples were confirmed respectively using X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods. All the compositions under investigation exhibited two distinct crystallization peaks (exothermic peaks in the DSC traces): the first peak at ~ 545 °C and the second at ~610 °C that were found to be associated with the crystallization of the phases (as confirmed from the XRD studies) Sr2Bi4Ti5O18 (SBT)and Li2B4O7 (LBO) respectively. Non-isothermal crystallization kinetics (using modified Ozawa-type plots) for SBT crystallization in the LBO glass matrix for the compositions x = 10 and 35, indicated three dimensional growth of the crystallites from pre-existing nuclei present in the as-quenched samples and their effective activation energies for crystallization were found to be around 686 ± 85 kJ/mol and 365 ± 53 kJ/mol, respectively. The optical band gap of the as-quenched glasses for the composition x = 35 was 2.52 eV, is less than that of the composition x = 10 (2.91 eV). The Urbach energies for the as-quenched glasses of compositions x = 10, 25 and 35 were found to be 118 ± 2 meV, 119 ± 2 meV and 192 ± 1 meV respectively.The glasses associated with the composition x = 35, on controlled heat-treatment at 515 °C for various durations (1―20 h), yielded glass-ceramics comprising SBT nano-crystals (18―28 nm) embedded in the LBO glass matrix. Compressive strain in the nano-crystallites of SBT, analyzed using Williamson-Hall method was found to decrease with an increase in the crystallite size. The second harmonic generation signal (532 nm) intensity emanating from glass-nanocrystal composites comprising 22.1 nm SBT crystallites was nearly 0.3 times that of a KDP single crystal. Although each chapter is provided with conclusions and a list of references, thesis ends with a separate summary and conclusions.