Nanotubular titanates were synthesized by a simple methodology using a commercial TiO2 (Degussa P25 containing anatase and rutile phases) and a base (KOH) solution. Prior to the removal of KOH, the samples of TiO2 were aged for three different time intervals (0, 2 days, 61 days). The freshly prepared synthetic samples were characterized for their structural and morphological properties by BET, XRD, Raman, TEM, HRTEM, EDX and SEM. Both TEM and SEM analysis revealed that ageing time influenced the tubular structure and morphology of the new materials. Raman and surface analysis data also showed that ageing time affected both the structural and surface properties of TiO2. The XRD results showed that the crystallinity of the TiO2 decreased with increasing ageing time. Energy dispersive Xray spectroscopy (EDX) showed that the tubes derived from TiO2 are comprised of potassium, titanium and oxygen. Catalysts A, B and C were prepared by the addition of 1 wt% Pd (wet impregnation) to the titanate formed after ageing of the TiO2 in KOH for 0, 2 and 61 days, respectively. The catalysts were tested for the vapour phase hydrogenation of phenol in a fixed-bed micro reactor within the temperature range of 165 to 300oC under atmospheric pressure. Of the three catalysts, catalyst B showed the best activity (conversion 97%) and total selectivity to cyclohexanone (99%). In contrast, catalyst C, which showed a moderate activity favoured selectivity to cyclohexanol. These results are attributed to differences in surface morphologies between the two catalysts B and C, associated with the surface area and a change in the surface acid-base properties. Catalyst B also showed a higher resistance towards deactivation and maintained a higher total selectivity to cyclohexanone than did catalyst C. A hydrothermal treatment of NaOH and TiO2 was employed to prepare two materials, TiO2-B and TiO2-C with relatively small crystallite size and large specific surface area. The hydrogenation of phenol was used to evaluate the activity of the catalysts Pd/TiO2-B and Pd/TiO2-C. The reaction proceeds in a single step and involves the formation of a partially hydrogenated product, namely cyclohexanone. The larger surface area catalyst (Pd/TiO2-C, 89 m2/g) showed better activity and selectivity to cyclohexanone than its counterpart (Pd/TiO2-B, 45 m2/g). The catalyst activity showed significant dependency on the surface area whereas the selectivity was greatly influenced by surface basicity. Titania derived nanotubes synthesized by treating P25 Degussa TiO2 with a concentrated KOH solution and aged for 2 days was used as a catalyst support for the hydrogenation of o-chloronitrobenzene (O-CNB) with Pd as the active phase. The vapour-phase hydrogenation of O-CNB was carried out in ethanol at 250 oC and atmospheric pressure over a Pd/TiO2 derived nanotube catalyst (Pd/TiO2-M). Pd/TiO2-M gave complete conversion (100%) of O-CNB with a selectivity to orthochloroaniline (O-CAN) of 86 %. The stability of the Pd/TiO2 catalyst was tested over 5 hours during which time the conversion slowly dropped to 80 % (selectivity 93 %) due to poisoning. TPR analysis revealed the existence of a strong palladium-support interaction and this was found to be crucial to the overall activity of the catalyst. It has been found that gold supported on potassium titanate, KTiO2(OH) can, under some circumstances, exhibit a superior performance for the oxidation of carbon monoxide, relative to that obtained with titania as a support. It appears that the dispersions of gold on the two types of support are sufficiently similar that other factors are responsible for the improved activity noted. It may be that the higher basic character and detailed structural features of the titanate surface play a role. The effect of the addition of alkali metal ions on the anatase to rutile transformation of titanium dioxide (P25 Degussa) was investigated using X-ray diffraction, Raman spectroscopy, and surface area measurements. Both Li and Cs ions accelerated the anatase to rutile transformation whereas Na and K ions did not show any effect. Furthermore, the effect was more pronounced after addition of the Li ions so that the transformation temperature dramatically decreased from ~800 oC for commercial TiO2 to ~600 oC. The surface area of the TiO2 material decreased with sintering due to the increase in crystalline size. Moreover, the acceleration of the transformation occurred at lower temperatures and at higher Li content. Mesoporous nanocrystalline TiO2 (HSA TiO2) was prepared by hydrothermal treatment of TiO2 with NaOH. The material was very amorphous and underwent the phase transformation from amorphous to anatase phase and subsequently from anatase to rutile phase with sintering. The anatase to rutile transformation was delayed after doping and grain growth was inhibited. After sintering at 800 oC the material (HSA TiO2) still contained a significant amount of the anatase phase. The complete transformation only occurred at ~1000 oC. The esterification of benzoic acid and butyric acid with propanol over alkali metal ions supported on TiO2 was investigated. K/TiO2-D showed the highest conversion for both benzoic acid and butyric acid. The selectivity to propylbenzoate and propylbutyrate was influenced by the basic nature of the catalysts. Butyric acid was found to be more reactive than benzoic acid. The difference in reactivity was explained in terms of steric and inductive effects. The differences in boiling points and pH values were also considered.

Thesis (Ph. D.)--University of Rhode Island, 2006. / Typescript. Includes bibliographical references (leaves 126-134).

Ph.D. / Materials Science and Engineering / Polytitanates in the BaO- TiO2 system with Ba:Ti ratios ranging from 1:2 to 1:5 were prepared using a low temperature technique developed by Pechini. The samples were heated at 600 to 1300°C in oxygen. Room temperature Raman spectroscopy was used to investigate the phase relations in this system. Results of this study indicate the following: except for BaTi4O9, the powders of these compounds were amorphous when heated at 600°C for 4hrs; the compound BaTi2O5 is a low temperature stable phase; Ba6Ti17O40 forms only at temperatures above 1100°C; Ba4Ti13O30 does not form below 1000°C; the single phase BaTi4O9 structure was observed at 1200°C'; the Ba2Ti9O20 phase is obtained only after long heat treatment at 1200°; BaTi5O11 was stable up to 1200°C, at which it decomposes into Ba2Ti4O20 and TiO2. After determination of stability relationships in this system, the electrical conductivities of these compounds were examined as a function of temperature and oxygen partial pressure. For all the temperatures (850-1150°C) studied, the conductivities of these compounds increased with decreasing oxygen partial pressure resulting in n-type properties throughout the whole P[subscript O2] range (10[superscript -19 - 1atm). The P[subscript O2] dependencies of the electrical conductivity were found to be linear for an extensive range of oxygen partial pressures. On the basis of structural considerations the conductivity data was described by a majority defect model consisting of both singly and doubly ionized oxygen vacancies. For lower oxygen partial pressure values a drastic change in the electrical conductivity was observed. This is believed to result from increasing defect interaction for larger departures from stoichiometry. A defect model based on this interaction is proposed to account for the observed sharp change in the electrical conductivity values.

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Recent interests on the plastic deformation of strontium titanate (SrTiO3) are derived from its unusual ductile-to-brittle-to-ductile transition (DBDT). The transition is divided into three regimes (A, B and C) corresponding to the temperature range of 113 K to 1053 K (-160oC to 780oC), 1053 K to ~ 1503 K (780oC to ~ 1230oC) and ~ 1503 K to 1873 K (~ 1230oC to 1600oC), discovered by Sigle and colleagues in the MPI-Stuttgart. We report the dislocation substructures in (001) single crystal SrTiO3 deformed by Vickers indentation at room temperature, studied by scanning and transmission electron microscopy (SEM and TEM). Dislocation dipoles of screw and edge character are observed and confirmed by inside-outside contrast using g-vector by weak-beam dark field imaging. They are formed by edge trapping, jog dragging and cross slip-pinching off. Similar to dipole breaking off in deformed sapphire (£\-Al2O3) at 1200oC and £^-TiAl intermetallic at room temperature, the dipoles pinch off at one end, and emit a string of loops at trail. Two sets of slip systems {110}<-11 0> and {100}<011> are activated under both 100 g and 1 kg load. The suggestion is that plastic deformation has reached the stage II work hardening, which is characterized by multiplication of dislocations through cross slip, interactions between dislocations, and operating of multiple slip systems. In nanoindentation experiments, it is generally believed that the shear stress at the onset of plasticity can approach the theoretical shear strength of an ideal. Here we report direct evidence that plasticity in a single crystal SrTiO3 can begin at very small forces, remarkably. However, the shear stresses associated with these very small forces is excess the theoretical shear strength of SrTiO3 (16.1 GPa). Our observations entail correlating quantitative load¡Vdisplacement measurements with individual stage microstructure during nanoindentation experiments in a transmission electron microscope. We also report direct evidence that with the prevalent notion that the first obvious displacement excursion in a nanoindentation test is indicative of the onset of plastic deformation. The SrTiO3 deforms elastically before the pop-in depth, but exhibits a plastic-elastic behavior after that. TEM observations reveal that the slip band is the predominant deformation mechanism in SrTiO3 during indentation. The cracks usually initiate at the intersection of slip bands to produce the sessile dislocations with Burger vectors [1-10] (or [110]) along the (110) (or (1-10)) crack plane. In addition, theoretical analysis confirms that the pop-in event is associated with the onset plasticity of SrTiO3. The plastic deformation of (001) single crystal SrTiO3 is investigated using compression along [001] at room temperature. A total plastic strain of ~19+2% is consistently obtained. The stress-strain curve exhibiting four work-hardening stages are describable using the stage 0 of axis rotation, the stage I ¡§easy glide¡¨, the stage II multiple slip and the wall-and-cell structure, and the stage III work softening and dynamic recovery before sample fracture takes place. It is revealed by analyzing the microstructure for each work-hardening stage that the plastic deformation of single crystal SrTiO3 closely resembles that of metals. The primary slip systems of [011](0-11) and [01-1](011) predominate in stage I where plastic deformation occurs by the migration of kink pairs in collinear partial dislocations. The activation of multiple slips including [101](-101) and [10-1](101), and [011](0-11) and [0-11](011) in stage II produces the cell-and-wall structure which is also characteristic of plastically deformed metals. In stage III with decreasing work-hardening rate, the bow-out dislocation interaction from opposite walls results in annihilation. The reaction between dislocations from adjacent walls produces the resultant dislocations with b = [-110] parallel to the load axis [001]. These dislocations are sessile, which eventually leads to sample fracture. We have analyzed the microstructure of <001> SrTiO3 single crystal deformed using compression at room temperature using transmission electron microscopy. A representative stress-strain (£m-£`) curve is established, similar to that for metals it consists of three hardening stages before failure occurs at a strain £` = 19+2%. Dislocation analysis suggests that the primary slip systems in [011](0-11) and [0-11](011) are activated in the £m-£` curve stress plateau region usually addressed as easy glide. Three characteristic features are identified from samples deformed to stage I hardening by easy glide: (a) rectangular glide loops, (b) collinear partials, and (c) kink pairs. Dislocations have predominantly pure edge character. Kink pairs are observed only on the edge segments suggesting that screw dislocations have higher mobility. In easy glide, the migration and annihilation of kink pairs occurring on both the trailing and leading partials lends support to a previous report by Castillo-Rodriguez and Sigle (2011) that dislocation glide is controlled by the long-segment limit of a kink-pair model. Pure edge dislocations are dissociated into collinear partials with b = 1/2[011] (or 1/2[0-11]) by glide in (0-11) (or(011)), and kink pairs are formed on both leading and trailing partials. The suggestion is that in the low-stress regime hardening by dislocation pile-up in stage I is compensated for by kink pair nucleation and migration. The overall hardening rate thus remains unchanged at approximately zero, resembling easy glide in the deformation of metals, over an increasing strain of £` ? 4% before reaching stage II hardening. Microcrack nucleation and propagation behavior in the crack tip was investigated by using transmission electron microscopy (TEM) through compressive test and Vickers indenter. Observation results showed that fracture process was completed in this <001> SrTiO3 single crystal material by connecting dislocations. The crack were nucleated and developed in the dislocation free zone (DFZ) or super thinned area ahead of crack tip under local high stress concentration. The cracks were linked with each other by mutual dislocation emission which expedites the propagation of crack tips effectively. We suggested a dislocation based the Hirsch et al. model of plastic-zone evolution in which dislocations emitted from the crack tip glide away to form a crack-tip plastic zone. Each emitted dislocation reduces the crack tip stress intensity via elastic interactions (the ¡¥¡¥shielding¡¨ effect).

We use the spin polarized pseudofunction(PSF) method with the local-spin-density approximation (LSDA) to calculate the electronic structures and the total and partial charge densities (TDOS, PDOS) of bulk Ba1-xSrxTiO3 (BSTO) with x = 0, 0.25, 0.5, 0.75, and 1. We find that the calculated direct energy gap Eg bows up as a function of the Sr concentration, which is related to the bowling downward of the Ti-O bond length inferred from the experimental lattice constants. The calculated partial densities of unoccupied O-p derived states (PDOS) agree well with the features observed in the O K-edge XANES spectra of BaTiO3 and SrTiO3. The calculated total densities of valence-band states (TDOS) and the valence-band widths for BaTiO3 and SrTiO3 agree well with the UPS spectra.

Secondary abnormal grain growth (SAGG) during sintering of barium titanate has been explained in terms of twin plane re-entrant edge (TPRE) growth mechanism by {111} double twin lamellae. But during sintering of Ti-excess barium titanate, {111} double twins lamellae are observed with out SAGG. In our group, Lin founded that when combine two different Ba/Ti ratio of powder to sintering above the eutectic temperature, the SAGG is observed in the interface between two different powders. Therefore, this thesis consists of three major researches: (a) {111} double twin, (b) Ba/Ti ratio, (c) liquid phase. In the experiment, we follow Lin¡¦s experiment to sinter the specimen contain with SAGG. And in this specimen, it can observe the specimen divided into three type of growth grain: (a) top surface with normal grain growth (NGG), (b) intermediate layer with abnormal grain growth (AGG), (c) bottom layer with secondary abnormal grain growth. It can all observed {111} double twin in these three different type of layer. This result confirmed that SAGG are not induced by TPRE growth mechanism. Then we used SEM/EDS to analysis the Ba/Ti ratio in the different type of grain growth layer. The Ba/Ti ratio in this analysis is not differing in NGG, AGG and SAGG. Therefore, we used OM, SEM, TEM to observe the grain boundary and triple grain junction in NGG, AGG and SAGG. It can observe that only the grain boundary and triple grain junction in SAGG are complete wetting. The experimental results shows that the grain growth behavior controlled by the liquid phase wetting degree.

A proposed design of the variable energy positron annihilation spectroscopy (VEPALS) system based on secondary electron (SE) emission from a thin carbon foil has been investigated practically. The SE yield and the positron transmission coefficient were investigated as a function of the positron beam energy, the annular electrode potentials, and the column lengths of the annular electrode. The positron lifetime spectra of single crystal p-type silicon(Si) sample under different annular electrode potentials were analyzed. The result gives a supposed annular electrode potential of 1.5 kV. In view of this, the positron lifetime spectra were measured under different positron beam energy by fixing the annular electrode potential. It can be seen that all the spectra have the main p-type Si bulk lifetime component of 234 ps occupying more than 60% intensities. The intensity of the 234 ps component reaches up to 84.5 ±1.3 % when the positron beam energy is 15 keV. Further, the origin of the satellite peaks in the positron lifetime spectra are also investigated. It has been shown that the satellite peaks is attributed to the overflowing positrons on the MCP detector. The single crystal strontium titanate (STO) substrates after vacuum annealing treatment have been investigated in detail by several experimental techniques. The crystallization changes induced by the vacuum annealing were investigated by X-ray diffraction(XRD). Secondary phases were occurred after annealing treatment. The measured X-ray photoelectron spectroscopy (XPS) at O1s and C1s core levels were analyzed. The additional peaks after annealing are attributed to hydroxyl species, C-OH compounds, and carbonates. The variable energy Doppler broadening spectroscopy (VEDBS) and the traditional coincidence positron annihilation lifetime spectroscopy (PALS) were used to probe defects in STO samples. For long annealing time samples, the S parameters decrease below the reference level. The S-Wplot suggests that almost the same type of vacancy defects were induced during the annealing treatment. The positron lifetime results suggest that the main defects in annealed samples are oxygen monovacancies or divacancies and Sr-O vacancy complexes. The sample with annealing time of 110h has minimum positron effective diffusion length and maximum average lifetime, which is attributed to the increase of the vacancy-type defects during the long annealing treatment. / published_or_final_version / Physics / Master / Master of Philosophy

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1992. / Vita. "x̳", "1̳-x", and "3̳" are subscripts. Abstract. Includes bibliographical references (leaves 120-128). Also available via the Internet.

Techn. Universiẗat, Diss., 2004--Dresden.