Gibbs energy formation of lead titanate

The Gibbs energy of formation of titania-saturated lead titanate has been determined by e.m.f. measurements on the solid state cell;Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt in the temperature range 1075–1350 K. The results obtained are significantly different from those reported in the literature based upon vapour pressure measurements, employing Knudsen effusion and transportation techniques, and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor pressure studies using mass spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead titanate which are in better agreement with those obtained in this study. Earlier electrochemical measurements by Mehrotra et al. and more recent electrochemical measurements by Schmahl et al. both employing CaO-ZrO2 solid electrolytes are in good agreement with the present study. The electro-chemical measurements by Schmahl et al. using PbF 2 solid electrolyte give a slightly more positive Gibbs energy of formation. There was no evidence supporting the formation of compounds other than Pb1−xTiO3−x from yellow PbO and rutile form of TiO2 in the temperature range covered in this study.Résumé L'enthalpie libre de formation du titanate de plomb saturé en oxyde de titane a été déterminée par des mesures de FEM de la pile: Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt dans le domaine de températures 1075–1350 K. Les résultats obtenus, different appréciablement de ceux publiés, déterminés par mesures de tensions de vapeur (techniques de transport et d'effusion de Knudsen) en supposant que la phase gazeuse etait uniquement constituée de molécules monomériques de PbO. Une réanalyse des résultats de la littérature, à partir de mesures par spectrométrie de masse sur les polymères de PbO gazeux, donne des enthalpies libres de formation du titanate de plomb se rapprochant de celles obtenues dans cette étude. Les mesures de Mehrotra et al. et plus récemment de Schmahl et al. utilisant toutes deux l'électrolyte CaO-ZrO2 concordent bien avec celles de la présente étude. Les mesures de Schmahl et al., à l'aide de l' électrolyte solide PbF2, donnent une enthalpie de formation légèrement plus positive. Pour la gammede températures étudiée, rien ne permet de supposer que des composés autres que Pb1−x TiO3−x puissent se former à partir du PbO Gaune) et du rutile (TiO2).

Thermodynamic properties of calcium titanates: CaTiO3, Ca4Ti3O10, and Ca3Ti2O7

The chemical potentials of CaO in two-phase fields (TiO2 + CaTiO3), (CaTiO3 + Ca4Ti3O10), and (Ca4Ti3O10 + Ca3Ti2O7) of the pseudo-binary system (CaO + TiO2) have been measured in the temperature range (900 to 1250) K, relative to pure CaO as the reference state, using solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells were operated under pure oxygen at ambient pressure. The standard Gibbs free energies of formation of calcium titanates, CaTiO3, Ca4Ti3O10, and Ca3Ti2O7, from their component binary oxides were derived from the reversible e.m.f.s. The results can be summarised by the following equations: CaO(solid) + TiO2(solid) → CaTiO3(solid), ΔG° ± 85/(J · mol−1) = −80,140 − 6.302(T/K); 4CaO(solid) + 3TiO2(solid) → Ca4Ti3O10(solid), ΔG° ± 275/(J · mol−1) = −243,473 − 25.758(T/K); 3CaO(solid) + 2TiO2(solid) → Ca3Ti2O7(solid), ΔG° ± 185/(J · mol−1) = −164,217 − 16.838(T/K). The reference state for solid TiO2 is the rutile form. The results of this study are in good agreement with thermodynamic data for CaTiO3 reported in the literature. For Ca4Ti3O10 Gibbs free energy of formation obtained in this study differs significantly from that reported by Taylor and Schmalzried at T = 873 K. For Ca3Ti2O7 experimental measurements are not available in the literature for direct comparison with the results obtained in this study. Nevertheless, the standard entropy for Ca3Ti2O7 at T = 298.15 K estimated from the results of this study using the Neumann–Koop rule is in fair agreement with the value obtained from low-temperature heat capacity measurements.

Role of electrolyte additives on in-vitro electrochemical behavior of micro arc oxidized titania films on Cp Ti

The present work is aimed at studying the influence of electrolyte chemistry on the voltage-time (V-T) response characteristics, phase structure, surface morphology, film growth rate and corrosion properties of titania films fabricated by micro arc oxidation (MAO) on Cp Ti. The titania films were developed with a sodium phosphate based reference electrolyte comprising the additives such as sodium carbonate (Na2CO3), sodium nitrite (NaNO2) and urea (CO(NH2)(2)). The phase composition, surface morphology, elemental composition and thickness of the films were assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The corrosion characteristics of the fabricated films were studied under Kokubo simulated body fluid (SBF) condition by potentiodynamic polarization, long term potential and linear polarization resistance (LPR) measurements and electrochemical impedance spectroscopy (EIS) methods. In addition, the corrosion characteristics of the grown films were analyzed by EIS curve fitting and equivalent circuit modeling. Salt spray test (SST) as per ASTM B 117 standard was also conducted to verify the corrosion resistance of the grown films. The XRD results showed that the titania films were composed of both anatase and rutile phases at different proportions. Besides, the films grown in carbonate and nitrite containing electrolyte systems showed an enhanced growth of their rutile phase in the 1 0 1] direction which could be attributed to the modifications introduced in the growth process by the abundant oxygen available during the process. The SEM-EDX and elemental mapping results showed that the respective electrolyte borne elements were incorporated and distributed uniformly in all the films. Among all the grown films under study, the film developed in carbonate containing electrolyte system exhibited considerably improved corrosion resistance due to suitable modifications in its structural and morphological characteristics. The rate of anatase to rutile phase transformation and the rutile growth direction were strongly influenced by the abundant oxidizing species available during the film growth process. (C) 2012 Elsevier B. V. All rights reserved.

Ultrahigh-temperature metamorphism from an unusual corundum plus orthopyroxene intergrowth bearing Al-Mg granulite from the Southern Marginal Zone, Limpopo Complex, South Africa

The Southern Marginal Zone of the Limpopo Complex is composed of granite-greenstone cratonic rocks reworked by a Neoarchean high-grade tectono-metamorphic event. Petrographic and mineral chemical characterization of an Al-Mg granulite from this zone is presented here. The granulite has a gneissic fabric with distinct Al-rich and Si-rich layers, with the former preserving the unusual lamellar (random and regular subparallel) intergrowths of corundum and symplectic intergrowth of spinel with orthopyroxene. The Al-rich layer preserves mineral assemblages such as rutile with orthopyroxene + sillimanite +/- A quartz, Al-rich orthopyroxene (similar to 11 wt%), spinel + quartz, and corundum in possible equilibrium with quartz, while the Si-rich layer preserves antiperthites and orthopyroxene + sillimanite +/- A quartz, all considered diagnostic of ultrahigh-temperature metamorphism. Application of Al-in-opx thermometry, ternary feldspar thermometry and construction of suitable pressure-temperature phase diagrams, compositional and model proportion isopleth results indicate P-T conditions as high as similar to 1,050-1,100 A degrees C, and similar to 10-12 kbars for the Al-Mg granulite. Our report of ultrahigh-temperature conditions is significant considering that the very high temperature was reached during decompression of an otherwise high-pressure granulite complex (clockwise P-T path), whereas most other ultrahigh-temperature granulites are linked to magma underplating at the base of the crust (counterclockwise P-T path).

Peraluminous sapphirine-cordierite pods in Mg-rich orthopyroxene granulite from southern India: Implications for lower crustal processes

Sapphirine-cordierite intergrowths occur as pods within garnet-absent, high-Mg orthopyroxene-granulite xenoliths in the Kambam valley, Madurai Block, southern India. Whereas the cores of the pods are composed of sapphirine (X-Mg = 0.871-0.897) - cordierite (X-Mg = 0.892-0.931) intergrowth along with rutile, zircon and monazite, the rims are characterized by cordierite, apatite, plagioclase, K-feldspar, quartz and minor calcite. The surrounding matrix comprises orthopyroxene (maximum Al2O3 4.1 wt.%, X-Mg 0.848-0.850), plagioclase, biotite and quartz, similar to the assemblage in the surrounding charnockites. Sapphirine in the Kambam rocks is characterized by high Al contents with an end-member composition in the range of 7:9:3 and 3:5:1. The occurrence of peraluminous sapphirine in association with cordierite and in the absence of phases such as sillimanite and garnet is distinct from ultrahigh-temperature assemblages in other localities within the Madurai Block. The peraluminous composition of the pods suggests that these domains could represent cryptic pathways through which aluminous melts migrated. The reaction of such peraluminous melts with Mg-rich orthopyroxene in the host granulite at temperatures of 1025 degrees C and pressures around 8 kbar as computed from phase equilibria modeling followed by an isobaric cooling is inferred to have generated the sapphirine-cordierite pods. The unusual high-Mg orthopyroxene granulite suggests interaction of supracrustal rocks with mafic magmas, which probably acted as the heat source for the partial melting of lower crust and UHT metamorphism.

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO2) nano-photocatalysts, with different phases, prepared using a modified sol-gel process were employed in the degradation of rhodamine at 10 mg L-1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450 degrees C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K-app) of 0.023 min(-1). The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024 min(-1) for 450, 500, 550 and 600 degrees C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017 min(-1), which is similar to that of the commercial titania.

Fabrication and characterization of micro-arc oxidized fluoride containing titania films on Cp Ti

The present study is focussed at establishing an appropriate electrolyte system for developing electrochemically stable and fluorine (F) containing titania (F-TiO2) films on Cp Ti by micro-arc oxidation (MAO) technique. To fabricate the F-TiO2 films on Cp Ti, different electrolyte solutions of chosen concentrations of tri-sodium orthophosphate (TSOP, Na3PO4 center dot I2H2O), potassium hydroxide (KOH) and various F-containing compounds such as ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF) and potassium fluorotitanate (K2TiF6) are employed. The structural and morphological characteristics, thickness and elemental composition of the developed films have been assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The in-vitro electrochemical corrosion behavior of the films was studied under Kokubo simulated body fluid (SBF) environment by potentiodynamic polarization, long term potential measurement and electrochemical impedance spectroscopy (EIS) methods. The XRD and SEM-EDS results show that the rutile content in the films vary in the range of 15-37 wt% and the F and P contents in the films is found to be in the range of 2-3 at% and 2.9-4.7 at% respectively, suggesting that the anatase to rutile phase transformation and the incorporation of F and P into the films are significantly controlled by the respective electrolyte solution. The SEM elemental mapping results show that the electrolyte borne F and P elements are incorporated and distributed uniformly in all the films. Among all the films under study, the film developed with 5 g TSOP+2 g KOH+3 g K2TiF6 electrolyte system exhibits considerably improved in-vitro corrosion resistance and therefore best suited for biomedical applications. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Structural, electrical and dielectric properties of sputtered TiO2 films for Al/TiO2/Si capacitors

Metal-oxide semiconductor capacitors based on titanium dioxide (TiO2) gate dielectrics were prepared by RF magnetron sputtering technique. The deposited films were post-annealed at temperatures in the range 773-1173 K in air for 1 hour. The effect of annealing temperature on the structural properties of TiO2 films was investigated by X-ray diffraction and Raman spectroscopy, the surface morphology was studied by atomic force microscopy (AFM) and the electrical properties of Al/TiO2/p-Si structure were measured recording capacitance-voltage and current-voltage characteristics. The as-deposited films and the films annealed at temperatures lower than 773 K formed in the anatase phase, while those annealed at temperatures higher than 973 K were made of mixtures of the rutile and anatase phases. FTIR analysis revealed that, in the case of films annealed at 1173 K, an interfacial layer had formed, thereby reducing the dielectric constant. The dielectric constant of the as-deposited films was 14 and increased from 25 to 50 with increases in the annealing temperature from 773 to 973 K. The leakage current density of as-deposited films was 1.7 x 10(-5) and decreased from 4.7 X 10(-6) to 3.5 x 10(-9) A/cm(2) with increases in the annealing temperature from 773 to 1173 K. The electrical conduction in the Al/TiO2/p-Si structures was studied on the basis of the plots of Schottky emission, Poole-Frenkel emission and Fowler-Nordheim tunnelling. The effect of structural changes on the current-voltage and capacitance-voltage characteristics of Al/TiO2/p-Si capacitors was also discussed.

Role of electrolyte chemistry on electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti

The primary objective of the present work was to study the electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti, fabricated independently in various electrolyte solutions consisting of anions such as phosphate (PO43-), borate (B4O72-), citrate (C6H5O73-) and silicate (SiO32-). Further the role of anions on the structural, morphological and compositional properties of the fabricated films was studied. All the titania films were developed by micro-arc oxidation (MAO) technique for a fixed treatment time of 8 min under constant current mode. The surface morphology, elemental distribution, composition and structural characteristics of the films were assessed by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The thermodynamic and kinetic corrosion properties of the films were studied under simulated body fluid (SBF) conditions (pH 7.4 and 37 degrees C) by conducting chronopotentiometric and potentiodynamic polarization tests. Electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit modelling was carried out to analyse the frequency response and Mott-Schottky analysis was performed to study the semiconducting (electronic) properties of the films. Salt spray fog accelerated corrosion test was conducted for 168h as per ASTM B117 standard to corroborate the corrosion and semiconducting properties of the samples based on the visual examination. The XRD results showed that the transformation from the metastable anatase phase to the thermodynamically stable rutile phase and the crystalline growth of the respective phases were strongly influenced by the addition of anions. The SEM-EDS results demonstrated that the phosphorous (P) content in the films varied from 2.4 at% to 5.0 at% indicating that the amount of P in the films could be modified by adding an appropriate electrolyte additive. The electrochemical corrosion test results showed that the film fabricated in citrate (C6H5O73-) containing electrolyte is thermodynamically and kinetically more stable compared to that of all the others. The results of the Mott-Schottky analysis indicated that all the fabricated films showed an n-type semiconducting behaviour and the film developed in citrate (C6H5O73-) containing electrolyte exhibited the lowest donor concentration and the most negative flat band potential that contributed to its highest corrosion resistance in SBF solution. The results of the salt spray accelerated corrosion tests were in agreement with those obtained from the electrochemical and Mott-Schottky analysis.

Ionothermal synthesis of TiO2 nanoparticles: Photocatalytic hydrogen generation

Rutile phase TiO2 nanoparticles have been successfully prepared at 120 degrees C for one day via the ionothermal method using imidazolium based functionalized ionic liquid. The obtained products have been characterized by various techniques. XRD pattern shows rutile phase with crystallite size similar to 15 nm. FTIR shows a band at similar to 410 cm(-1) assigned to Ti-O-Ti stretching vibrations and few other bands due to the presence of ionic liquid. UV-vis studies show maximum absorbance at similar to 215 nm due to the imidazolium moiety and a band at 316 nm due to TiO2 nanoparticles. TEM images show that the size of particle is similar to 30 nm. TG-DTA shows weight loss corresponding to the formation of stable TiO2 nanoparticles. The rutile TiO2 nanoparticle is a promising material for hydrogen generation through photocatalysis. (C) 2013 Elsevier B.V. All rights reserved.

Effect of chemical treatment on surface characteristics of sputter deposited Ti-rich NiTi shape memory alloy thin-films

NiTi thin-films were deposited by DC magnetron sputtering from single alloy target (Ni/Ti: 45/55 aL.%). The rate of deposition and thickness of sputter deposited films were maintained to similar to 35 nm min(-1) and 4 mu m respectively. A set of sputter deposited NiTi films were selected for specific chemical treatment with the solution comprising of de-ionized water, HF and HNO3 respectively. The influence of chemical treatment on surface characteristics of NiTi films before and after chemical treatment was investigated for their structure, micro-structure and composition using different analytical techniques. Prior to chemical treatment, the composition of NiTi films using energy dispersive X-ray dispersive spectroscopy (EDS), were found to be 51.8 atomic percent of Ti and 48.2 atomic percent of Ni. The structure and morphology of these films were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD investigations, demonstrated the presence of dominant Austenite (110) phase along with Martensite phase, for untreated NiTi films whereas some additional diffraction peaks viz. (100), (101), and (200) corresponding to Rutile and Anatase phase of Titanium dioxide (TiO2) along with parent Austenite (110) phase were observed for chemically treated NiTi films. FTIR studies, it can be concluded that chemically treated films have higher tendency to form metal oxide/hydroxide than the untreated NiTi films. XPS investigations, demonstrated the presence of Ni-free surface and formation of a protective metal oxide (TiO2) layer on the surface of the films, in both the cases. The extent of the formation of surface oxide layer onto the surface of NiTi films has enhanced after chemical treatment. (C) 2014 Elsevier B.V. All rights reserved.

Influence of sputter power on structural and electrical properties of TiO2 films for Al/TiO2/Si gate capacitors

Titanium dioxide (TiO2) thin films were deposited onto p-Si substrates held at room temperature by reactive Direct Current (DC) magnetron sputtering at various sputter powers in the range 80-200W. The as-deposited TiO2 films were annealed at a temperature of 1023K. The post-annealed films were characterized for crystallographic structure, chemical binding configuration, surface morphology and optical absorption. The electrical and dielectric properties of Al/TiO2/p-Si structure were determined from the capacitance-voltage and current-voltage characteristics. X-ray diffraction studies confirmed that the as-deposited films were amorphous in nature. After post-annealing at 1023K, the films formed at lower powers exhibited anatase phase, where as those deposited at sputter powers >160W showed the mixed anatase and rutile phases of TiO2. The surface morphology of the films varied significantly with the increase of sputter power. The electrical and dielectric properties on the air-annealed Al/TiO2/p-Si structures were studied. The effect of sputter power on the electrical and dielectric characteristics of the structure of Al/TiO2/p-Si (metal-insulator-semiconductor) was systematically investigated. Copyright (c) 2014 John Wiley & Sons, Ltd.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

Analyzing the kinetic response of tin oxide-carbon and tin oxide-CNT composites gas sensors for alcohols detection

Tin oxide nanoparticles are synthesized using solution combustion technique and tin oxide - carbon composite thick films are fabricated with amorphous carbon as well as carbon nanotubes (CNTs). The x-ray diffraction, Raman spectroscopy and porosity measurements show that the as-synthesized nanoparticles are having rutile phase with average crystallite size similar to 7 nm and similar to 95 m(2)/g surface area. The difference between morphologies of the carbon doped and CNT doped SnO2 thick films, are characterized using scanning electron microscopy and transmission electron microscopy. The adsorption-desorption kinetics and transient response curves are analyzed using Langmuir isotherm curve fittings and modeled using power law of semiconductor gas sensors. (C) 2015 Author(s).

Synthesis, characterization and field emission properties of tin oxide nanowires

Tin oxide (SnO2) nanowires are synthesized by Au catalyzed chemical vapor deposition of Sn and C mixture at 900 degrees C by employing a continuous flow of Ar: O-2 (10:1) for an hour. X-ray diffraction and Raman spectroscopy studies indicate that the as-grown SnO2 nanowires are crystalline in nature with tetragonal rutile phase. Electron microscopy studies reveal towards high aspect ratio of nanowires. The field emission studies show that SnO2 nanowires grown on Si substrate exhibit low turn-on field of 1.75 V/mu m (at 0.1 mu A/cm(2)) and long-term emission stability over a period of more than 50 h with a current density of 4 mu A/cm(2) at a constant electric field of 2.25 V/mu m. Hardly any considerable degradation in the emission current is noticed even after 50 h which may be attributed to the high crystallinity of SnO2 nanowires. (C) 2015 Elsevier B.V. All rights reserved.