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Nano and Grain-Orientated Ferroelectric Ceramics Produced by SPSLiu, Jing January 2007 (has links)
<p>Nano-powders of BaTiO<sub>3</sub>, SrTiO<sub>3</sub>, Ba<sub>0.6</sub>Sr<sub>0.4</sub>TiO<sub>3</sub>, a mixture of the composition (BaTiO<sub>3</sub>)<sub>0.6</sub>(SrTiO<sub>3</sub>)<sub>0.4</sub> with particle sizes in the range of 60 to 80 nm, and Bi<sub>4</sub>Ti<sub>3</sub>O<sub>12</sub> with an average particle size of 100 nm were consolidated by spark plasma sintering (SPS). The kinetics of reaction, densification and grain growth were studied. An experimental procedure is outlined that allows the determination of a “kinetic window” within which dense nano-sized compacts can be prepared. It is shown that the sintering behaviour of the five powders varies somewhat, but is generally speaking fairly similar. However, the types of grain growth behaviour of these powders are quite different, exemplified by the observation that the kinetic window for the (BaTiO<sub>3</sub>)<sub>0.6</sub>(SrTiO<sub>3</sub>)<sub>0.4</sub> mixture is 125 <sup>o</sup>C, ~75 <sup>o</sup>C for Bi<sub>4</sub>Ti<sub>3</sub>O<sub>12</sub>, ~25<sup>o</sup>C for BaTiO<sub>3</sub> and SrTiO<sub>3</sub>, while it is hard to observe an apparent kinetic window for obtaining nano-sized compacts of Ba<sub>0.6</sub>Sr<sub>0.4</sub>TiO<sub>3</sub>. During the densification of the (BaTiO<sub>3</sub>)<sub>0.6</sub>(SrTiO<sub>3</sub>)<sub>0.4</sub> mixture the reaction 0.6BaTiO<sub>3</sub>+0.4SrTiO<sub>3</sub> → Ba<sub>0.6</sub>Sr<sub>0.4</sub>TiO<sub>3</sub> takes place, and this reaction is suggested to have a self-pinning effect on the grain growth, which in turn explains why this powder has a large kinetic window. Notably, SPS offers a unique opportunity to more preciously investigate and monitor the sintering kinetics of nano-powders, and it allows preparation of ceramics with tailored microstructures.</p><p>The dielectric properties of selected samples of (Ba, Sr)TiO<sub>3</sub> ceramics have been studied. The results are correlated with the microstructural features of these samples, <i>e.g.</i> to the grain sizes present in the compacts. The ceramic with nano-sized microstructure exhibits a diffuse transition in permittivity and reduced dielectric losses in the vicinity of the Curie temperature, whereas the more coarse-grained compacts exhibit normal dielectric properties in the ferroelectric region.</p><p>The morphology evolution, with increasing sintering temperature, of bismuth layer-structured ferroelectric ceramics such as Bi<sub>4</sub>Ti<sub>3</sub>O<sub>12</sub> (BIT) and CaBi<sub>2</sub>Nb<sub>2</sub>O<sub>9</sub> (CBNO) was investigated. The subsequent isothermal sintering experiments revealed that the nano-sized particles of the BIT precursor powder grew into elongated plate-like grains within a few minutes, via a dynamic ripening mechanism.</p><p>A new processing strategy for obtaining highly textured ceramics is described. It is based on a<i> directional dynamic ripening mechanism</i> <i>induced by superplastic deformation</i>. The new strategy makes it possible to produce a <i>textured</i> microstructure within minutes, and it allows production of textured ferroelectric ceramics with tailored morphology and improved physical properties.</p><p>The ferroelectric, dielectric, and piezoelectric properties of the textured bismuth layer-structured ferroelectric ceramics have been studied, and it was revealed that all textured samples exhibited anisotropic properties and improved performance. The highly textured Bi<sub>4</sub>Ti<sub>3</sub>O<sub>12</sub> ceramic exhibited ferroelectric properties equal to or better than those of corresponding single crystals, and much better than those previously reported for grain-orientated Bi<sub>4</sub>Ti<sub>3</sub>O<sub>12</sub> ceramics. Textured CaBi<sub>2</sub>Nb<sub>2</sub>O<sub>9</sub> ceramics exhibited a very high Curie temperature, <i>d</i><i>33</i>-values nearly three times larger than those of conventionally sintered materials, and a high thermal depoling temperature indicating that it is a very promising material for high-temperature piezoelectric applications.</p>
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Nano and Grain-Orientated Ferroelectric Ceramics Produced by SPSLiu, Jing January 2007 (has links)
Nano-powders of BaTiO3, SrTiO3, Ba0.6Sr0.4TiO3, a mixture of the composition (BaTiO3)0.6(SrTiO3)0.4 with particle sizes in the range of 60 to 80 nm, and Bi4Ti3O12 with an average particle size of 100 nm were consolidated by spark plasma sintering (SPS). The kinetics of reaction, densification and grain growth were studied. An experimental procedure is outlined that allows the determination of a “kinetic window” within which dense nano-sized compacts can be prepared. It is shown that the sintering behaviour of the five powders varies somewhat, but is generally speaking fairly similar. However, the types of grain growth behaviour of these powders are quite different, exemplified by the observation that the kinetic window for the (BaTiO3)0.6(SrTiO3)0.4 mixture is 125 oC, ~75 oC for Bi4Ti3O12, ~25oC for BaTiO3 and SrTiO3, while it is hard to observe an apparent kinetic window for obtaining nano-sized compacts of Ba0.6Sr0.4TiO3. During the densification of the (BaTiO3)0.6(SrTiO3)0.4 mixture the reaction 0.6BaTiO3+0.4SrTiO3 → Ba0.6Sr0.4TiO3 takes place, and this reaction is suggested to have a self-pinning effect on the grain growth, which in turn explains why this powder has a large kinetic window. Notably, SPS offers a unique opportunity to more preciously investigate and monitor the sintering kinetics of nano-powders, and it allows preparation of ceramics with tailored microstructures. The dielectric properties of selected samples of (Ba, Sr)TiO3 ceramics have been studied. The results are correlated with the microstructural features of these samples, e.g. to the grain sizes present in the compacts. The ceramic with nano-sized microstructure exhibits a diffuse transition in permittivity and reduced dielectric losses in the vicinity of the Curie temperature, whereas the more coarse-grained compacts exhibit normal dielectric properties in the ferroelectric region. The morphology evolution, with increasing sintering temperature, of bismuth layer-structured ferroelectric ceramics such as Bi4Ti3O12 (BIT) and CaBi2Nb2O9 (CBNO) was investigated. The subsequent isothermal sintering experiments revealed that the nano-sized particles of the BIT precursor powder grew into elongated plate-like grains within a few minutes, via a dynamic ripening mechanism. A new processing strategy for obtaining highly textured ceramics is described. It is based on a directional dynamic ripening mechanism induced by superplastic deformation. The new strategy makes it possible to produce a textured microstructure within minutes, and it allows production of textured ferroelectric ceramics with tailored morphology and improved physical properties. The ferroelectric, dielectric, and piezoelectric properties of the textured bismuth layer-structured ferroelectric ceramics have been studied, and it was revealed that all textured samples exhibited anisotropic properties and improved performance. The highly textured Bi4Ti3O12 ceramic exhibited ferroelectric properties equal to or better than those of corresponding single crystals, and much better than those previously reported for grain-orientated Bi4Ti3O12 ceramics. Textured CaBi2Nb2O9 ceramics exhibited a very high Curie temperature, d33-values nearly three times larger than those of conventionally sintered materials, and a high thermal depoling temperature indicating that it is a very promising material for high-temperature piezoelectric applications.
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Evaluation of Zinc Oxide Nano-Microtetrapods for Biomolecule Sensing ApplicationsZhao, Wei January 2015 (has links)
Zinc oxide (ZnO) is a well-known II-VI semiconductor material that has gained renewed interest in the past decade due to the developments of growth technologies and the availability of high-quality ZnO bulk single crystals. Owing to a wide direct band gap (3.37 eV), large exciton binding energy (60 meV), and high electron mobility (440 cm2 V-1 s-1), ZnO has been used for applications including actuators, optoelectronics, and sensors. ZnO nanoparticles can be synthesized in a broad variety of morphologies, such as nanotetrapods, nanotubes, and nanowires. Among these nanostructures, the tetrapods have attracted significant attention due to their unique morphology consisting of four legs connected together in a tetrahedral symmetry. Recently, it has been reported that nano-microstructured ZnO tetrapods (ZnO-Ts) can be synthesized by flame transport synthesis (FTS) in a rapid and up-scalable approach. Compared to conventional ZnO nanoparticles, the nano-microstructured ZnO-Ts can reduce cellular uptake, while still exhibiting specific nanomaterial properties due to the nanoscale tips. Moreover, the anisotropic ZnO-Ts have the advantages of multiple electron transfer paths, chemical stability, and biocompatibility, which make the ZnO-Ts promising candidates for biomolecule sensing applications. This work herein reports a systematical study on the structural, optical and electrochemical properties of the ZnO-Ts, which were synthesized by FTS using precursor Zn microparticles. The morphology of the ZnO-Ts was confirmed by scanning electron microscopy (SEM) as joint structures of four single crystalline legs, of which the diameter of each leg is 0.7-2.2 μm in average from the tip to the stem. The ZnO-Ts were dispersed in glucose solutions to study the photoluminescence as well as photocatalytic activity in a mimicked biological environment. The photoluminescence (PL) intensity in the ultraviolet (UV) region decreased with linear dependence on the glucose concentration up to 4 mM. The ZnO-Ts were also attached with glucose oxidase (GOx) and over coated with Nafion® to form the active media for electrochemical glucose sensing. The active layers were confirmed by Fourier transform infrared spectroscopy (FT-IR). Furthermore, the current response of the active layers to glucose was studied by cyclic voltammetry (CV) in various glucose concentration conditions. Stable current response to glucose was detected with linear dependence on the glucose concentration up to 12 mM, which confirms the potential of ZnO-Ts for biomolecule sensing applications.
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