Academic literature on the topic 'Lead Free Sodium Bismuth Titanate'

Numerous questions regarding the nature of BNT-derived relaxor ferroelectrics are addressed on the basis of a broad experimental foundation including electrical characterization, diffraction, piezoresponse force microscopy, and mechanical measurements. In order to check the general validity of the approach two materials were investigated: the model system (1-y)(0.94Bi1/2Na1/2TiO3-0.06BaTiO3)-yK0.5Na0.5NbO3 (BNT-6BT-100yKNN) and the newly developed (1-y)((1-x)Bi1/2Na1/2TiO3-xBi1/2K1/2TiO3)-yBiZn1/2Ti1/2O3 (BNT-100xBKT-100yBZT). The field-dependent polarization and strain are demonstrated to bear phenomenological similarities to well-known relaxor ferroelectrics like PLZT or PMN. Compositions with zero y are hypothesized to be nonergodic relaxors featuring partially correlated polar nano-regions (PNRs) in a nominally pseudocubic matrix. These PNRs are the consequence of random fields due to a mixed A-site of the perovskite lattice, i.e., Bi3+ and Na+ in addition to Ba2+ or K+. This compositional disorder is associated with augmented random electric fields caused by charge disorder and random strain fields generated by different ion sizes. Upon application of a sufficiently high electric field the PNRs coalesce into ferroelectric domains that percolate the sample. Eventually, the poled material is macroscopically almost indistinguishable from conventional ferroelectrics, exhibiting a butterfly-shaped strain loop and rectangular polarization loop. With y>0, additional heterovalent ions are incorporated into the A- and/or B-site, giving rise to enhanced random fields that increase the required threshold field necessary to induce long-range order. At a critical value of y stable long-range order cannot be induced and the material is eventually ergodic. High electric fields, however, still cause the growth of PNRs, which results in high electrostrictive coefficients as well as high maximum polarization and strain. There may still be a threshold field where a reversible formation of micron-sized domains occurs. This transition is reflected by a clear bend in P(E) loops, indicating a change in mechanism. The establishment of an ’unstable’ long-range order at high electric fields is observed for BNT-6BT-3KNN, but not for BNT-20BKT-4BZT for fields <6 kV•mm-1. While S(E) and P(E) saturate in the former case, the latter material may exhibit rapidly increasing large-field parameters even beyond 6 kV•mm-1. For y higher than the critical value, Pmax and Smax decay, which is attributed to the diminished volume fraction of electrically active polar regions. Consequently, a higher electric field is required to achieve the same polarization and strain. The field-dependent small-signal parameters of piezoelectric constant d33(E) and permittivity εr;33(E) support this image. In nonergodic relaxor compositions, a stable piezoelectricity arises with the emergence of ferroelectric domains and the concurrent alignment thereof with respect to the electric field. At the same time, zero-field permittivity decreases, which is attributed to a diminished domain wall density. Compositions with elevated y, also referred to as ’incipient piezoceramics’, feature a sizable piezoelectric constant only under strong electric fields. Eventually, for a high concentration of heterovalent ions, d33 depends almost linearly on the electric field and permittivity is virtually field-independent. Further insight into the relaxor properties is provided by diffraction. The initial structure is seemingly cubic on the average, which is ascribed to the small size of the polar regions below the coherence length of the XRD or NRD experiment. Consequently, PNRs do not contribute to the Bragg reflections in the diffraction pattern and the average symmetry appears non-polar, i.e., metrically cubic. For nonergodic relaxor compositions, the field-induced establishment of longrange order is demonstrated by a peak broadening and the emergence of notable non-cubicity. In the case of BNT-20BKT, the application of an electric field >3.7 kV•mm-1 induces tetragonal and rhombohedral distortions. A small addition (y=0.02) of BZT increases the threshold field, indicated by the reflection broadening setting in at 4.6 kV•mm-1. The ergodic BNT-20BKT-4BZT, on the other hand, remains pseudocubic, suggesting that the PNRs may grow but remain too small for detection. Therefore, diffraction is in line with large-signal measurements that likewise suggest the lack of ferroelectric domains. The observation of pseudocubicity in the initial, unbiased state implies the absence of domains, which is confirmed by PFM measurements. It is concluded that PNRs have a size below the lateral resolution limit of the PFM, i.e., well below 10 nm. Also, the establishment of long-range order as suggested by in situ diffraction is directly observed after application of a DC tip bias. Inversion of the polarity of the DC voltage proved the capability for polarization reversal. As suggested by macroscopic measurements, the tip bias required for the formation and switching of domains is strongly affected by y, here representing the KNN content. Higher y results in a higher threshold and switching voltage. Interestingly, local switching loops can be obtained even for strongly ergodic relaxors such as BNT-6BT-18KNN, albeit only at highest electric fields. The polarization relaxation is furthermore reflected in a temporal decay of piezoresponse that obeys a stretched exponential function, confirming a broad distribution of relaxation times. This distribution of relaxation times is manifested in the frequency dependence of large-signal properties. The pseudocubic structure is maintained up to high temperatures as demonstrated by temperatureinvariant X-ray and neutron diffraction patterns, which only feature an increase in lattice spacing due to thermal expansion. Nonlinearities in the temperature-dependent Young’s modulus Y(T) indicate that structural changes take place on a limited, local scale. In contrast to phase transitions as in PZT, where Y strongly increases within a narrow temperature range, the variations in Y(T) for the investigated lead-free materials are small and spread out across a broad temperature range of several hundreds of degrees centigrade. It is, therefore, concluded that only a fraction of the volume is affected. The PNRs transform into a high-temperature cubic phase, which displays a higher Young’s modulus. Owing to the random fields, the stability of the PNRs varies, which eventually gives rise to the observed wide temperature range of non-linearly varying Y . At the same time, the permittivity exhibits an intricate thermal evolution. A low-temperature frequency-dispersive shoulder in εr;33(T) indicates the slowing down of dipolar motion, associated with the distribution of PNR correlation length and accordingly distributed relaxation times. A peak at higher temperatures indicates a slight frequency dependence albeit inverted, i.e., higher frequencies cause a decrease in tanδ. Approaches to rationalize the εr;33(T) curve include aging, space charge relaxation or a frustrated domain state, where two PNR species are present and consequently two relaxation temperature ranges exist. None of these hypothesis can presently be rejected and it is likely that all three effects contribute to some extent to the overall dielectric response as a function of temperature. The thermally induced depoling process is elucidated by contrasting in situ d33(T) measurements with high-temperature second-harmonic generation. Almost all piezoelectricity in poled nonergodic BNT-20BKT has vanished at 140 °C, while SHG measurements still yield non-zero intensity, proving the existence of residual polar volume. This finding suggests that the depoling process consists of two simultaneous contributions. On the one hand, a randomization of polarization vectors takes place, resulting in the disappearance of net polarization and piezoelectricity. On the other hand, domains break up into PNRs, which shrink upon further heating. This means that the polar volume is reduced with increasing temperature. Consequently, it is demonstrated by means of non-zero SHG intensity that polar volume in the form of PNRs exists not only far beyond depolarization temperature, but also in the unpoled and the ergodic relaxor state. Both lead-free BNT-based material systems are demonstrated to excel in certain applications. Under high electric fields, the strain ratio Smax•Emax-1 surpasses even soft PZT. Moreover, the achievable maximum stress, termed blocking stress, can be up to 60 % higher. Both the large strain and the high blocking stress are beneficial for actuator applications. Moreover, the large and almost temperature-insensitive permittivity for BNT-6BT-100yKNN with high y depicts an attractive starting point for the development of high-capacity, high-temperature capacitor materials. Such a capacitor is, for example, required for automotive applications, where power converters require charge storage for power conditioning at high temperatures. These specialized, tailored solutions may not only reduce the amount of hazardous substances in consumer products but also broaden the horizons of today’s technology.

Ferroelectric and piezoelectric materials, especially the polycrystalline ceramics, are promising candidates for application in pressure sensors, actuators, transducers, ultrasonic motors, energy storage capacitors, ferroelectric memories, electrooptic devices and PTC thermistors. Lead zirconate titanate PbZr1-xTixO3 (PZT) based ferroelectric and piezoelectric ceramics have dominated the market owing to their superior electromechanical properties. However, the toxicity of lead has compelled researchers to search for a suitable lead-free alternative which show similar if not superior properties in comparison to lead based ones. Sodium bismuth titanate Na0.5Bi0.5TiO3 (NBT)-based piezoceramics are among the key contenders to replace lead based piezoceramics. Numerous studies in the past have focused attention on the chemical substitution effects in improving the electromechanical response of NBT-based piezoelectrics. Some studies have shown that off-stoichiometry also considerably influences the electromechanical response of NBT-based piezoceramics. However, structure-property correlations in off-stoichiometric NBT-based systems have not received detailed attention. In this thesis we have investigated this aspect extensively. The focus has been on NBT and its solid solution with BaTiO3 (BT); more specifically the compositions close to the morphotropic phase boundary, i.e., 94NBT-0.06BT. In addition to the off-stoichiometric studies, the work has been extended to understand the role of grain size on the dielectric, ferroelectric and piezoelectric properties and the depolarization temperature of NBT and NBT-BT. The ceramics were synthesized via the conventional ceramic synthesis route and characterized by a host of techniques like scanning electron microscopy (SEM), x-ray diffraction, Raman spectroscopy, impedance spectroscopy, ferroelectric, dielectric, piezoelectric and depolarization measurements. While the better resolution of the laboratory x-ray powder diffraction data was used to understand the nature of lattice distortions (spontaneous strain) on the global scale, wherever required, neutron powder diffraction study was also undertaken. The large elastic scattering cross-section of oxygen for thermal neutrons made it possible to capture the subtle structural features such as the subtle in-phase octahedral tilt (not possible to capture with XRD data). This provided new structural insights to explain the property trends as a function of off-stoichiometry and grain size. For example, a correlation between grain size and volume fraction of the structural disorder caused by the in-phase tilt, and its effect on the piezoelectric and depolarization temperature has been unambiguously established in this work. In the end, it is shown that chemical modification of NBT-BT with BiFeO3 (BF) and K0.5Na0.5NbO3 (KNN) yield compositions which are interesting for energy storage applications.

Bismuth layer-structured ferroelectrics have received significant attention recently due to their fairly high TC and good fatigue endurance which make them important candidates for non-volatile ferroelectric random access memories (Fe-RAMs) as well as for the piezoelectric device applications at high temperatures. Structure of these compounds is generally described as the pseudo-perovskite block (An-1BnO3n+1)2- sandwiched between the bismuth oxide layers (Bi2O2)2+ along the c-axis, where n represents the number of corner sharing BO6 octahedra forming the perovskite-like slabs. Only a few compounds belonging to this family show relaxor behavior (frequency dependent diffuse phase transition). Relaxor ferroelectrics are very attractive for a variety of applications, such as capacitors, sensors, actuators, and integrated electromechanical systems. The present work attempts to understand the mechanism of relaxor behavior in Aurivillius oxides as well as to improve the piezoelectric and ferroelectric properties of some of the known phases. Details pertaining to the fabrication and characterization of BaBi4Ti4O15 (n = 4 member of Aurivillius family of oxides) ceramics are presented. X-ray diffraction, Raman spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to probe the structural and microstructural details. The contribution of irreversible domain wall movement to the room temperature dielectric constant and polarization was quantitatively evaluated using the nonlinear dielectric response. Dielectric dispersion and conduction mechanism of these ceramics are also explicated using the complex impedance spectroscopy. The effects of La3+ and Ca2+ doping on the phase transition behavior and other properties of BaBi4Ti4O15 are investigated. La3+ doping for Bi3+ was found to strengthen the relaxor behavior. New compounds such as CaNaBi2Nb3O12, SrNaBi2Nb3O12, Na0.5La0.5Bi4Ti4O12, etc. belonging to the Aurivillius family of oxides have been synthesized and investigations concerning their structural, dielectric and ferroelectric properties are presented. Rietveld refinement of room temperature X-ray powder data suggested that CaNaBi2Nb3O12 and SrNaBi2Nb3O12crystallize in the orthorhombic space group B2cb. SrNaBi2Nb3O12 ceramics exhibited frequency-dependent Tm which follows the Vogel-Fulcher relation implying a relaxor nature. No frequency dependence of Tm was observed for CaNaBi2Nb3O12 ceramics. Polarization - electric field hysteresis loops recorded well above Tm confirmed the coexistence of polar and non-polar domains in SrNaBi2Nb3O12 ceramics. Dielectric anomaly observed around 675 K for CNBN corresponds to the ferroelectric to paraelectric phase transition which is accompanied by the change in crystal structure from orthorhombic to tetragonal. Fe and Nb co-doped Bi4Ti3O12 ceramics were fabricated and characterized for their structural, electrical and magnetic properties.

Bismuth layer-structured ferroelectrics have received significant attention recently due to their fairly high TC and good fatigue endurance which make them important candidates for non-volatile ferroelectric random access memories (Fe-RAMs) as well as for the piezoelectric device applications at high temperatures. Structure of these compounds is generally described as the pseudo-perovskite block (An-1BnO3n+1)2- sandwiched between the bismuth oxide layers (Bi2O2)2+ along the c-axis, where n represents the number of corner sharing BO6 octahedra forming the perovskite-like slabs. Only a few compounds belonging to this family show relaxor behavior (frequency dependent diffuse phase transition). Relaxor ferroelectrics are very attractive for a variety of applications, such as capacitors, sensors, actuators, and integrated electromechanical systems. The present work attempts to understand the mechanism of relaxor behavior in Aurivillius oxides as well as to improve the piezoelectric and ferroelectric properties of some of the known phases. Details pertaining to the fabrication and characterization of BaBi4Ti4O15 (n = 4 member of Aurivillius family of oxides) ceramics are presented. X-ray diffraction, Raman spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to probe the structural and microstructural details. The contribution of irreversible domain wall movement to the room temperature dielectric constant and polarization was quantitatively evaluated using the nonlinear dielectric response. Dielectric dispersion and conduction mechanism of these ceramics are also explicated using the complex impedance spectroscopy. The effects of La3+ and Ca2+ doping on the phase transition behavior and other properties of BaBi4Ti4O15 are investigated. La3+ doping for Bi3+ was found to strengthen the relaxor behavior. New compounds such as CaNaBi2Nb3O12, SrNaBi2Nb3O12, Na0.5La0.5Bi4Ti4O12, etc. belonging to the Aurivillius family of oxides have been synthesized and investigations concerning their structural, dielectric and ferroelectric properties are presented. Rietveld refinement of room temperature X-ray powder data suggested that CaNaBi2Nb3O12 and SrNaBi2Nb3O12crystallize in the orthorhombic space group B2cb. SrNaBi2Nb3O12 ceramics exhibited frequency-dependent Tm which follows the Vogel-Fulcher relation implying a relaxor nature. No frequency dependence of Tm was observed for CaNaBi2Nb3O12 ceramics. Polarization - electric field hysteresis loops recorded well above Tm confirmed the coexistence of polar and non-polar domains in SrNaBi2Nb3O12 ceramics. Dielectric anomaly observed around 675 K for CNBN corresponds to the ferroelectric to paraelectric phase transition which is accompanied by the change in crystal structure from orthorhombic to tetragonal. Fe and Nb co-doped Bi4Ti3O12 ceramics were fabricated and characterized for their structural, electrical and magnetic properties.

Ferroelectric ceramics are very promising materials for a variety of piezoelectric applications such as high permittivity dielectrics, piezoelectric sensors, piezoelectric/electrostrictive transducers, actuators, electro-optic devices, etc. Among the commercially viable ferroelectric ceramics, the lead-zircon ate-titivate Pb(Zr1-xTix)O3 (PZT) based ceramics have dominated the market due to their superior piezoelectric and dielectric property along with other advantages like high electromechanical coupling, ease of processing and low cost. However, the toxicity of lead based materials, and its volatility at processing temperatures is a serious health and environmental concern. Several legislations against lead-based products have been passed all over the world in order to encourage identification of alternative lead-free materials for these applications. As a consequence, there has been a remarkable surge in efforts by researchers on identifying lead-free alternatives for piezoelectric applications. A larger emphasis has been placed on perovskite based ceramics since in addition to possessing excellent properties, their relatively simple structure facilitates understanding structure-property relationships which are important for developing novel high performance materials. Na1/2Bi1/2TiO3 (NBT) and its solid solutions are one of the leading classes of perovskite ceramics, which show promising ferroelectric, piezoelectric and dielectric property thereby having the potential to replace PZT based ferroelectrics. The parent compound NBT is ferroelectric with large ferroelectric polarization (~40 C/cm2), promising piezoelectric properties with 0.08% maximum strain and longitudinal piezoelectric coefficient (d33) ~ 80 pC/N. Though NBT was discovered nearly six decades ago, a clear understanding of its structure remained elusive for a long time since different characterization techniques yielded contradicting reports on its structure and nature of phase transformation. However, rapid advances in characterization techniques in recent years have led to uncovering of new results, thereby shedding light on the true structure of NBT. X-ray and neutron diffraction studies in the past have shown that NBT exhibits rhombohedral (R3c) structure at room temperature, which undergoes a gradual transformation into tetragonal (P4bm) structure at ~230oC. However, recent characterization of both single crystal and powder of NBT using high resolution x-ray diffraction showed that the room temperature structure is not purely rhombohedral and the structure can be better modeled with a monoclinic (Cc) structure. In contrast to x-ray and neutron diffraction, electron diffraction studies have shown evidence for the presence of planar disorders, corresponding to in-phase octahedral tilts in the sample which cannot be accounted for by either R3c or Cc structure. In addition, EXAFS, x-ray and neutron total scattering studies, diffuse scattering studies, etc. have shown that the structural parameters obtained from bulk diffraction techniques are significantly different from the local structure of the material. Similar ambiguities have been observed even in NBT based solid solutions like BaTiO3, K1/2Bi1/2TiO3, etc. which show enhanced properties at the morphotropic phase boundary (MPB). A major breakthrough in understanding the structural complexity involved in NBT based solid solutions was achieved when it was found that the structure of the MPB compositions were sensitive to electric field. This led to solving the mystery behind the appearance of cubic-like phase at some of the MPB compositions where the application of electric-field resulted in the transformation of the structure into a co-existence of rhombohedral and tetragonal phases. Observation of an electric-field-induced structural transition at the MPB compositions was expected, because the MPB signifies instability in the system and even a minor external force can significantly influence the system. However, we have found that the structure of even pure NBT is significantly influenced by electric field and the framework of this thesis is based on this particularly important result. The intrinsic tendency of the electric field to affect the structure of NBT is a major factor which needs to be considered when studying similar phase transitions in the MPB compositions of NBT-substituted systems also. This was not taken into account by other research groups, and they assumed that the instability associated with the MPB was the only major factor involved in the electric-field induced transitions. A simple but highly effective strategy of grinding the electrically poled pellet into fine powder and then collecting x-ray diffraction patterns, facilitated elimination of preferred orientation in the sample. Thus, structural analysis by Rietveld refinement was possible even on the poled sample, which has not been carried out by any other groups on any ferroelectric ceramics so far. The initial part of the thesis deals with addressing the structural complexity of pure NBT, wherein the effect of electric field on the bulk structure as well as the local structure was studied in great detail. Later on, similar concepts are used to investigate BaTiO3 and K1/2Bi1/2TiO3 substituted NBT also. The first chapter of the thesis provides a brief introduction to the field of ferroelectrics, perovskite structure and their phase transition. An exposure to concepts like relaxor ferroelectrics, morphotrophic phase boundary, octahedral tilting, etc. has been provided. Then, a detailed overview of the existing literature related to the structure of NBT and its phase transition studies with temperature has been discussed. The details of the experimental procedures, characterization techniques used, and some theory behind these techniques have been provided in chapter 2. The third chapter deals with the room temperature structural characterization of pure NBT using techniques like x-ray diffraction, neutron diffraction, electron diffraction and EXAFS analysis. The results of these structural characterizations are also complemented with first-principles calculation study of the ground state structure of NBT, dielectric and ferroelectric characterization, and ageing studies. While x-ray and neutron diffraction clearly established electric-field induced structural transition from a monoclinic (Cc) to rhombohedral (R3c) structural transition, first principles calculation showed that the monoclinic phase is not stable and hence cannot be the ground state structure of NBT. Also, the possibility of the monoclinic features appearing in the x-ray diffraction solely due to micro structural effects by nano-sized domains was discussed. Comparison of electron diffraction of poled and unpoled samples of NBT showed that the in-phase tilted regions were greatly suppressed in the poled samples. Even HRTEM images showed that the unpoled samples had a very high concentration of strain heterogeneity in them, which was absent in the poled samples. This gave a direct evidence of correlation between observation of monoclinic phase and the presence of in-phase tilted regions in the unpoled samples. It was proposed that the strain caused by these in-phase tilted disorders caused distortion in the original rhombohedral lattice thereby making the structure appear monoclinic. Application of electric field causes the in-phase octahedral tilt disorders to vanish, thereby even the monoclinic features observed in the XRD also disappear. The fourth chapter discusses the consequences of poling on the high temperature phase transition behavior of NBT. We have used temperature dependent x-ray and neutron diffraction, Raman spectroscopy and EXAFS analysis whose results were correlated with the anomalies observed in temperature dependent dielectric and polarization studies. We found that the poled sample shows a sharp anomaly at the depolarization temperature (Td) in all the characterization techniques used, in contrast to a diffuse or negligible effect seen in the unpoled sample. The depolarization temperature was found to be associated with introduction of structural disorder in the sample in the form of in-phase octahedral tilts. This also gave rise to a normal to relaxor ferroelectric transition at Td, and this relaxor behavior persisted even after cooling the sample to room temperature. An intermediate cubiclike phase was observed from x-ray diffraction at around 300C wherein the rhombohedral phase vanishes and the tetragonal phase begins to appear. Even single crystal study of NBT in the past showed sudden disappearance of the domains at 300C, even though they were visible at both above and below this temperature. This effect was called isotropization, and was postulated to arise due to extremely small domains which made the system isotropic. However, our neutron diffraction pattern showed that in-phase tilted superlattice reflections persisted at this temperature which meant that the structure was not truly cubic at this temperature. Further, a neutron diffraction study at higher temperatures showed that the in-phase tilted superlattice reflections persisted even above the cubic phase transition temperature, in corroboration with similar reports from high temperature electron diffraction. Chapter five deals with the BaTiO3 substituted NBT system, which has gained tremendous interest in the last decade as a viable piezoelectric ceramic for commercial applications. Though a large number of groups have already carried out exhaustive studies on this system, most of the work concentrated mainly on the MPB compositions which showed enhanced piezoelectric properties. In this chapter, we highlight some important findings in the pre-MPB and post-MPB compositions. Using room-temperature and high temperature x-ray diffraction, we show that there exists a subtle compositional phase boundary at x = 0.03, which disappears upon poling the sample. While the monoclinic phase in pure NBT becomes cubiclike at this composition, the depolarization temperature (Td) also slightly increases up to this composition and then decreases upon further Ba substitution. Similar studies were also carried out with compositions containing slightly excess bismuth in them (0.1 mol %), whose purpose was to negate the effects of Bi-vaporization during sintering. It was found that while the compositional phase boundary remained essentially unchanged, there was a decrease in Td for all the compositions. It was also realized that the addition of excess bismuth improved the overall piezoelectric property of the system. Studies on higher compositions of Ba in the post-MPB regions further revealed two additional compositional phase boundaries. A criticality in the coercive field and spontaneous tetragonal strain was observed at x = 0.2, which was found to be associated with crossover from a long-period modulated tetragonal phase (for x < 0.2) to a no modulated tetragonal phase (for x > 0.2). Near the BT rich end (x ~ 0.7), the system exhibits a crossover from normal to a diffuse/relaxor ferroelectric transition with increasing Na1/2Bi1/2 substitution. The onset of relaxor state by Na1/2Bi1/2 substitution on the Ba-site, was shown to increase the spontaneous tetragonal strain in the system. This was because of the enhancement in the covalent character of the A-O bond by virtue of the Bi+3 6s2 lone pair effect, and it also led to a sudden increase in the tetragonal-to-cubic transition temperature. This was in contrast to other chemical modifications of BT reported in the past (like Zr, Sn, Sr, etc.) where the relaxor state is accompanied by a weakening of the ferroelectric distortion and a decrease in the critical temperature. Finally, chapter six covers the effect of electric field induced phase transition in K1/2Bi1/2TiO3 substituted NBT. Visual observation showed that while the compositions (x < 0.2) behaved similar to pure NBT, wherein the structure became purely rhombohedral upon poling, the effect of electric field was negligible in the post-MPB compositions (x > 0.2). In addition, the peaks in the annealed samples were considerably overlapping which made identifying the structural transitions at the MPB compositions difficult using Rietveld analysis. However, comparison of the FWHM of the {200}pc peaks of compositions x < 0.2 showed that the FWHM began to increase suddenly for x > 0.15 indicating emergence of the tetragonal phase. Also, all the compositions showed an increase in the {200}pc peak FWHM by 0.03 after poling. The depolarization temperature showed only slight variation in the pre-MPB compositions, but showed a minimum at the MPB compositions. Temperature dependent dielectric studies further showed that for the post-MPB compositions, the system remains relaxor even after poling.

Ferroelectric ceramics are very promising materials for a variety of piezoelectric applications such as high permittivity dielectrics, piezoelectric sensors, piezoelectric/electrostrictive transducers, actuators, electro-optic devices, etc. Among the commercially viable ferroelectric ceramics, the lead-zircon ate-titivate Pb(Zr1-xTix)O3 (PZT) based ceramics have dominated the market due to their superior piezoelectric and dielectric property along with other advantages like high electromechanical coupling, ease of processing and low cost. However, the toxicity of lead based materials, and its volatility at processing temperatures is a serious health and environmental concern. Several legislations against lead-based products have been passed all over the world in order to encourage identification of alternative lead-free materials for these applications. As a consequence, there has been a remarkable surge in efforts by researchers on identifying lead-free alternatives for piezoelectric applications. A larger emphasis has been placed on perovskite based ceramics since in addition to possessing excellent properties, their relatively simple structure facilitates understanding structure-property relationships which are important for developing novel high performance materials. Na1/2Bi1/2TiO3 (NBT) and its solid solutions are one of the leading classes of perovskite ceramics, which show promising ferroelectric, piezoelectric and dielectric property thereby having the potential to replace PZT based ferroelectrics. The parent compound NBT is ferroelectric with large ferroelectric polarization (~40 C/cm2), promising piezoelectric properties with 0.08% maximum strain and longitudinal piezoelectric coefficient (d33) ~ 80 pC/N. Though NBT was discovered nearly six decades ago, a clear understanding of its structure remained elusive for a long time since different characterization techniques yielded contradicting reports on its structure and nature of phase transformation. However, rapid advances in characterization techniques in recent years have led to uncovering of new results, thereby shedding light on the true structure of NBT. X-ray and neutron diffraction studies in the past have shown that NBT exhibits rhombohedral (R3c) structure at room temperature, which undergoes a gradual transformation into tetragonal (P4bm) structure at ~230oC. However, recent characterization of both single crystal and powder of NBT using high resolution x-ray diffraction showed that the room temperature structure is not purely rhombohedral and the structure can be better modeled with a monoclinic (Cc) structure. In contrast to x-ray and neutron diffraction, electron diffraction studies have shown evidence for the presence of planar disorders, corresponding to in-phase octahedral tilts in the sample which cannot be accounted for by either R3c or Cc structure. In addition, EXAFS, x-ray and neutron total scattering studies, diffuse scattering studies, etc. have shown that the structural parameters obtained from bulk diffraction techniques are significantly different from the local structure of the material. Similar ambiguities have been observed even in NBT based solid solutions like BaTiO3, K1/2Bi1/2TiO3, etc. which show enhanced properties at the morphotropic phase boundary (MPB). A major breakthrough in understanding the structural complexity involved in NBT based solid solutions was achieved when it was found that the structure of the MPB compositions were sensitive to electric field. This led to solving the mystery behind the appearance of cubic-like phase at some of the MPB compositions where the application of electric-field resulted in the transformation of the structure into a co-existence of rhombohedral and tetragonal phases. Observation of an electric-field-induced structural transition at the MPB compositions was expected, because the MPB signifies instability in the system and even a minor external force can significantly influence the system. However, we have found that the structure of even pure NBT is significantly influenced by electric field and the framework of this thesis is based on this particularly important result. The intrinsic tendency of the electric field to affect the structure of NBT is a major factor which needs to be considered when studying similar phase transitions in the MPB compositions of NBT-substituted systems also. This was not taken into account by other research groups, and they assumed that the instability associated with the MPB was the only major factor involved in the electric-field induced transitions. A simple but highly effective strategy of grinding the electrically poled pellet into fine powder and then collecting x-ray diffraction patterns, facilitated elimination of preferred orientation in the sample. Thus, structural analysis by Rietveld refinement was possible even on the poled sample, which has not been carried out by any other groups on any ferroelectric ceramics so far. The initial part of the thesis deals with addressing the structural complexity of pure NBT, wherein the effect of electric field on the bulk structure as well as the local structure was studied in great detail. Later on, similar concepts are used to investigate BaTiO3 and K1/2Bi1/2TiO3 substituted NBT also. The first chapter of the thesis provides a brief introduction to the field of ferroelectrics, perovskite structure and their phase transition. An exposure to concepts like relaxor ferroelectrics, morphotrophic phase boundary, octahedral tilting, etc. has been provided. Then, a detailed overview of the existing literature related to the structure of NBT and its phase transition studies with temperature has been discussed. The details of the experimental procedures, characterization techniques used, and some theory behind these techniques have been provided in chapter 2. The third chapter deals with the room temperature structural characterization of pure NBT using techniques like x-ray diffraction, neutron diffraction, electron diffraction and EXAFS analysis. The results of these structural characterizations are also complemented with first-principles calculation study of the ground state structure of NBT, dielectric and ferroelectric characterization, and ageing studies. While x-ray and neutron diffraction clearly established electric-field induced structural transition from a monoclinic (Cc) to rhombohedral (R3c) structural transition, first principles calculation showed that the monoclinic phase is not stable and hence cannot be the ground state structure of NBT. Also, the possibility of the monoclinic features appearing in the x-ray diffraction solely due to micro structural effects by nano-sized domains was discussed. Comparison of electron diffraction of poled and unpoled samples of NBT showed that the in-phase tilted regions were greatly suppressed in the poled samples. Even HRTEM images showed that the unpoled samples had a very high concentration of strain heterogeneity in them, which was absent in the poled samples. This gave a direct evidence of correlation between observation of monoclinic phase and the presence of in-phase tilted regions in the unpoled samples. It was proposed that the strain caused by these in-phase tilted disorders caused distortion in the original rhombohedral lattice thereby making the structure appear monoclinic. Application of electric field causes the in-phase octahedral tilt disorders to vanish, thereby even the monoclinic features observed in the XRD also disappear. The fourth chapter discusses the consequences of poling on the high temperature phase transition behavior of NBT. We have used temperature dependent x-ray and neutron diffraction, Raman spectroscopy and EXAFS analysis whose results were correlated with the anomalies observed in temperature dependent dielectric and polarization studies. We found that the poled sample shows a sharp anomaly at the depolarization temperature (Td) in all the characterization techniques used, in contrast to a diffuse or negligible effect seen in the unpoled sample. The depolarization temperature was found to be associated with introduction of structural disorder in the sample in the form of in-phase octahedral tilts. This also gave rise to a normal to relaxor ferroelectric transition at Td, and this relaxor behavior persisted even after cooling the sample to room temperature. An intermediate cubiclike phase was observed from x-ray diffraction at around 300C wherein the rhombohedral phase vanishes and the tetragonal phase begins to appear. Even single crystal study of NBT in the past showed sudden disappearance of the domains at 300C, even though they were visible at both above and below this temperature. This effect was called isotropization, and was postulated to arise due to extremely small domains which made the system isotropic. However, our neutron diffraction pattern showed that in-phase tilted superlattice reflections persisted at this temperature which meant that the structure was not truly cubic at this temperature. Further, a neutron diffraction study at higher temperatures showed that the in-phase tilted superlattice reflections persisted even above the cubic phase transition temperature, in corroboration with similar reports from high temperature electron diffraction. Chapter five deals with the BaTiO3 substituted NBT system, which has gained tremendous interest in the last decade as a viable piezoelectric ceramic for commercial applications. Though a large number of groups have already carried out exhaustive studies on this system, most of the work concentrated mainly on the MPB compositions which showed enhanced piezoelectric properties. In this chapter, we highlight some important findings in the pre-MPB and post-MPB compositions. Using room-temperature and high temperature x-ray diffraction, we show that there exists a subtle compositional phase boundary at x = 0.03, which disappears upon poling the sample. While the monoclinic phase in pure NBT becomes cubiclike at this composition, the depolarization temperature (Td) also slightly increases up to this composition and then decreases upon further Ba substitution. Similar studies were also carried out with compositions containing slightly excess bismuth in them (0.1 mol %), whose purpose was to negate the effects of Bi-vaporization during sintering. It was found that while the compositional phase boundary remained essentially unchanged, there was a decrease in Td for all the compositions. It was also realized that the addition of excess bismuth improved the overall piezoelectric property of the system. Studies on higher compositions of Ba in the post-MPB regions further revealed two additional compositional phase boundaries. A criticality in the coercive field and spontaneous tetragonal strain was observed at x = 0.2, which was found to be associated with crossover from a long-period modulated tetragonal phase (for x < 0.2) to a no modulated tetragonal phase (for x > 0.2). Near the BT rich end (x ~ 0.7), the system exhibits a crossover from normal to a diffuse/relaxor ferroelectric transition with increasing Na1/2Bi1/2 substitution. The onset of relaxor state by Na1/2Bi1/2 substitution on the Ba-site, was shown to increase the spontaneous tetragonal strain in the system. This was because of the enhancement in the covalent character of the A-O bond by virtue of the Bi+3 6s2 lone pair effect, and it also led to a sudden increase in the tetragonal-to-cubic transition temperature. This was in contrast to other chemical modifications of BT reported in the past (like Zr, Sn, Sr, etc.) where the relaxor state is accompanied by a weakening of the ferroelectric distortion and a decrease in the critical temperature. Finally, chapter six covers the effect of electric field induced phase transition in K1/2Bi1/2TiO3 substituted NBT. Visual observation showed that while the compositions (x < 0.2) behaved similar to pure NBT, wherein the structure became purely rhombohedral upon poling, the effect of electric field was negligible in the post-MPB compositions (x > 0.2). In addition, the peaks in the annealed samples were considerably overlapping which made identifying the structural transitions at the MPB compositions difficult using Rietveld analysis. However, comparison of the FWHM of the {200}pc peaks of compositions x < 0.2 showed that the FWHM began to increase suddenly for x > 0.15 indicating emergence of the tetragonal phase. Also, all the compositions showed an increase in the {200}pc peak FWHM by 0.03 after poling. The depolarization temperature showed only slight variation in the pre-MPB compositions, but showed a minimum at the MPB compositions. Temperature dependent dielectric studies further showed that for the post-MPB compositions, the system remains relaxor even after poling.