Processing Response of Boron Modified Ti-6Al-4V Alloy In (alpha plus beta) Working Regime

Titanium alloys like Ti-6A-4V are the backbone materials for aerospace, energy and chemical industries. Hypoeutectic boron addition to Ti-6Al-4V alloy produces a reduction in as-cast grain size by roughly an order of magnitude resulting in the possibility of avoiding ingot breakdown step and thereby reducing the processing cost. In the present study, ISM processed as-cast boron added Ti-6Al-4V alloy is deformed in (alpha+beta)-phase field, where alpha-lath bending seemed to be the dominating deformation mechanism.

Exfoliated graphite–ruthenium oxide composite electrodes for electrochemical supercapacitors

The performance of exfoliated graphite (EG)–ruthenium oxide (RuOx) composites as binderless electrodes is evaluated for electrochemical capacitors (ECs). A composite of EG–RuOx is prepared by a modified sol–gel process. The material is characterized using X-ray diffraction and microscopy. Electrochemical capacitors with the composite electrodes in the presence of aqueous sulfuric acid (H2SO4) electrolyte are evaluated using voltammetry, impedance and charge–discharge studies. Cyclic voltammetry reveals very stable current–voltage behaviour up to several thousands of cycles, as well as high specific capacitances, e.g., a few hundreds of farads per gram for the composite that contains 16.5 wt.% RuOx.

The significance of brittle reaction layers in fusing of dental ceramics to titanium

This thesis comprises four intercomplementary parts that introduce new approaches to brittle reaction layers and mechanical compatibility of metalloceramic joints created when fusing dental ceramics to titanium. Several different methods including atomic layer deposition (ALD), sessile drop contact angle measurements, scanning acoustic microscopy (SAM), three-point bending (TPB, DIN 13 927 / ISO 9693), cross-section microscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS) were employed. The first part investigates the effects of TiO2 layer structure and thickness on the joint strength of the titanium-metalloceramic system. Samples with all tested TiO2 thicknesses displayed good ceramics adhesion to Ti, and uniform TPB results. The fracture mode was independent of oxide layer thickness and structure. Cracking occurred deeper inside titanium, in the oxygen-rich Ti[O]x solid solution surface layer. During dental ceramics firing TiO2 layers dissociate and joints become brittle with increased dissolution of oxygen into metallic Ti and consequent reduction in the metal plasticity. To accomplish an ideal metalloceramic joint this needs to be resolved. The second part introduces photoinduced superhydrophilicity of TiO2. Test samples with ALD deposited anatase TiO2 films were produced. Samples were irradiated with UV light to induce superhydrophilicity of the surfaces through a cascade leading to increased amount of surface hydroxyl groups. Superhydrophilicity (contact angle ~0˚) was achieved within 2 minutes of UV radiation. Partial recovery of the contact angle was observed during the first 10 minutes after UV exposure. Total recovery was not observed within 24h storage. Photoinduced ultrahydrophilicity can be used to enhance wettability of titanium surfaces, an important factor in dental ceramics veneering processes. The third part addresses interlayers designed to restrain oxygen dissolution into Ti during dental ceramics fusing. The main requirements for an ideal interlayer material are proposed. Based on these criteria and systematic exclusion of possible interlayer materials silver (Ag) interlayers were chosen. TPB results were significantly better in when 5 μm Ag interlayers were used compared to only Al2O3-blasted samples. In samples with these Ag interlayers multiple cracks occurred inside dental ceramics, none inside Ti structure. Ag interlayers of 5 μm on Al2O3-blasted samples can be efficiently used to retard formation of the brittle oxygen-rich Ti[O]x layer, thus enhancing metalloceramic joint integrity. The most brittle component in metalloceramic joints with 5 μm Ag interlayers was bulk dental ceramics instead of Ti[O]x. The fourth part investigates the importance of mechanical interlocking. According to the results, the significance of mechanical interlocking achieved by conventional surface treatments can be questioned as long as the formation of the brittle layers (mainly oxygen-rich Ti[O]x) cannot be sufficiently controlled. In summary in contrast to former impressions of thick titanium oxide layers this thesis clearly demonstrates diffusion of oxygen from sintering atmosphere and SiO2 to Ti structures during dental ceramics firing and the following formation of brittle Ti[O]x solid solution as the most important factors predisposing joints between Ti and SiO2-based dental ceramics to low strength. This among other predisposing factors such as residual stresses created by the coefficient of thermal expansion mismatch between dental ceramics and Ti frameworks can be avoided with Ag interlayers.

Pd and Pt ions as highly active sites for the water-gas shift reaction over combustion synthesized zirconia and zirconia-modified ceria

Noble metal substituted ionic catalysts were synthesized by solution combustion technique. The compounds were characterized by X-ray diffraction, FT-Raman spectroscopy, and X-ray photoelectron spectroscopy. Zirconia supported compounds crystallized in tetragonal phase. The solid solutions of ceria with zirconia crystallized in fluorite structure. The noble metals were substituted in ionic form.The water-gas shift reaction was carried out over the catalysts.Negligible conversions were observed with unsubstituted compounds. The substitution of a noble metal ion was found to enhance the reaction rate. Equilibrium conversion was obtained below 250 degrees C in the presence of Pt ion substituted compounds. The formation of Bronsted acid-Bronsted base pairs was proposed to explain the activity of zirconia catalysts. The effect of oxide ion vacancies on the reactions over substituted ceria-zirconia solid solutions was established. (c)2010 Elsevier B.V. All rights reserved.

Free energy of mixing of divalent basic oxides with silica

An expression derived for the free energy of mixing of a divalent basic oxide (MO) with SiO2 based on a model of silicate structure, takes into account the distribution of O2- (from MO) into the silica network, the mixing of silicate ions with O2- and the enthalpy of mixing. The resulting expression is ΔGmix=RT{N11n (2N1-N)2/4N1(1-N)+N21n N 2-N/1-N}, where N={(β+N1)-√(β+N 1)2-8βN1N2}/2β β=characteristic constant for the system N1=mol fraction of silica N2=mol fraction of MO. For the proper choice of β, calculated values of the activity of MO for the system PbO-SiO2, MnO-SiO2, FeO-SiO2 and CaO-SiO2 are in good agreement with experiment. The model predicts that the activity of the basic oxide decreases with increase in temperature.

Low-temperature polymer precursor-based synthesis of nanocrystalline particles of lanthanum calcium manganese oxide (La0.67Ca0.33MnO3) with enhanced ferromagnetic transition temperature

We report a simple modified polymeric precursor route for the synthesis of highly crystalline and homogenous nanoparticles of lanthanum calcium manganese oxide (LCMO). The LCMO phase formation was studied by thermal analysis, x-ray powder diffraction, and infrared spectroscopy at different stages of heating. These nanocrystallites (average particle size of 30 nm) possess ferromagnetic-paramagnetic transition temperature (T-c) of 300 K, nearly 50 K higher than that of a single crystal. The Rietveld analysis of the powder x-ray diffraction data of the nanopowders reveals significant lattice contraction and reduction in unit cell anisotropy-these structural changes are correlated to the enhancement in T-c.

Spectral studies on pyridinium hexafluorotitanate(IV)

Pure samples of pyridinium hexafluorotitanate(IV) [(C5H5N+H)2TiF=6] were prepared by the reaction of pyridinium poly(hydrogen fluoride) and titanium tetrachloride. The i.r. spectral data in the range 4000–200 cm−1 and 1H, 19F, and 13CNMR spectra for this compound are reported.

Microwave Assisted Synthesis of Nanostructured Titanium Dioxide with High Photocatalytic Activity

TiO2 (anatase) was synthesized using a microwave-irradiation-assisted chemical method. The reaction conditions were varied to obtain unique nanostructures of TiO2 comprising nanometric spheres giving the materials a very porous morphology. The oxide was characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). The specific surface area and porosity were quantified by the BET method, and the degradation of dyes was carried out using these materials. The photocatalytic activity of the nanometric TiO2 was significantly higher than that of commercially available TiO2 (Degussa P25) for the degradation of the dyes.

Studies in biogas technology. Part IV. A novel biogas plant incorporating a solar water-heater and solar still

A reduction in the heat losses from the top of the gas holder of a biogas plant has been achieved by the simple device of a transparent cover. The heat losses thus prevented have been deployed to heat a water pond formed on the roof of the gas holder. This solar-heated water is mixed with the organic input for ‘ hot-charging ’ of the biogas plant. A thermal analysis of such a solar water-heater ‘ piggy-backing ’ on the gas holder of a biogas plant has been carried out.To test whether the advantages indicated by the thermal analysis can be realised in practice, a biogas plant of the ASTRA design was modified to incorporate a roof-top solar water-heater. The operation of such a modified plant, even under ‘ worst case ’ onditions, shows a significant improvement in the gas yield compared to the unmodified plant. Hence, the innovation reported here may lead to drastic reductions in the sizes and therefore costs of biogas plants. By making the transparent cover assume a tent-shape, the roof-top solar heater can serve the additional function of a solar still to yield distilled water. The biogas plant-cum-solar water-heater-cum-solar still described here is an example of a spatially integrated hybrid device which is extremely cost-effective.

Microstructural changes induced by ternary additions in a hypo-eutectic titanium-silicon alloy

Hypo-eutectic Ti-6.5 wt % Si alloy modified by separate additions of misch metal and low surface tension elements (Na, Sr, Se and Bi) has been examined by microscopic study and thermal analysis. Addition of third element led to modification of microstructure with apparently no significant enhancement of tensile ductility, with the exception of bismuth. Bismuth enhanced the ductility of the alloy by a factor of two and elastic-plastic fracture toughness to 9 MPa m–1/2 from a value of almost zero. The improved ductility of bismuth modified alloy is attributed to the reduced interconnectivity of the eutectic suicide, absence of significant suicide precipitation in the eutectic region and increase in the volume fraction of uniformly distributed dendrites. These changes are accompanied by a decrease in the temperature of eutectic solidification.

On characterization of deformation microstructure in Boron modified Ti-6Al-4V alloy

Addition of boron in small quantities to various titanium alloys have shown significant improvement in mechanical behavior of materials. In the present study, electron back-scatter diffraction (EBSD) techniques have been applied to investigate the deformation microstructure evolution in boron modified two-phase titanium alloy Ti-6Al-4V. The alloy was hot compressed at 750 degrees C up to 50% height reduction at two different strain rates (10(-3) s(-1) and 1 s(-1)). The EBSD analyses indicated significant differences in deformed microstructure of the base alloy and the alloy containing boron. A strong subgrain formation tendency was observed along with inhomogeneous distribution of dislocations inside large a colonies of Ti64. In contrast, a colonies were relatively strain free for Ti64 + B, with more uniform dislocation density distribution. The observed difference is attributed to microstructural modifications viz, grain size refinement and presence of TiB particles at grain boundary produced due to boron addition. (C) 2010 Elsevier B.V. All rights reserved.

Direct Growth of Gold Nanorods on Gold and Indium Tin Oxide Surfaces: Spectral, Electrochemical, and Electrocatalytic Studies

The surfactant-assisted seed-mediated growth method was used for the formation of gold nanorods (GNRs) directly on gold (Au) and indium tin oxide (ITO) surfaces. Citrate-stabilized similar to 2.6 nm spherical gold nanoparticles (AuNPs) were first self-assembled on ITO or Au surfaces modified with (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film and then immersed in a cationic surfactant growth solution to form GNRs. The growth of GNRs on the MPTS sol gel film modified ITO surface was monitored by UV-visible spectroscopy. The ITO surface with the attached spherical AuNPs shows a surface plasmon resonance band at 550 nm. The intensity of this absorption band increases while increasing the immersion time of the AuNP-modified ITO surface into the growth solution, and after 5 h, an additional shoulder band around 680 nm was observed. The intensity of this shoulder band increases, and it was shifted to longer wavelength as the immersion time of the AuNP-modified ITO surface into the growth solution increases. After 20 h, a predominant wave at 720 nm was observed along with a band at 550 nm. Further immersion of the modified ITO surface into the growth solution did not change the absorption characteristics. The bands observed at 550 and 720 nm were characteristics of GNRs, corresponding to transverse and longitudinal waves, respectively. The AFM images showed the presence of GNRs on the surface of the MPTS sol gel modified ITO surface with a typical length of similar to 100-120 nm and a width of similar to 20-22 nm in addition to a few spherical AuNPs, indicating that seeded spherical AuNPs were not completely involved in the GNRs' formation. Finally, the electrocatalytic activity of the surface-grown GNRs on the MPTS sol gel film modified Au electrode toward the oxidation of ascorbic acid (AA) was studied. Unlike a polycrystalline Au electrode, the surface-grown GNR-modified electrode shows two well-defined voltammetric peaks for AA at 0.01 and 0.35 V in alkaline, neutral, and acidic pHs. The cause for the observed two oxidation peaks for AA was due to the presence of both nanorods and spherical nanoparticles on the electrode surface. The presence of spherical AuNPs on the MPTS sol gel film oxidized AA at more positive potential, whereas the GNRs oxidized AA at less positive potential. The observed 340 mV less positive potential shift in the oxidation of AA suggested that GNRs are better electrocatalysts for the oxidation of AA than the spherical AuNPs.

On the evaluation of stability of rare earth oxides as face coats for investment casting of titanium

Attempts have been made to evaluate the thermal stability of rare earth oxide face coats against liquid titanium. Determination of microhardness profiles and concentration profiles of oxygen and metallic constituents of oxide in investment cast titanium rods has allowed grActation of relative stability of rare earth oxides. The relative stability of evaluated oxides in the order of increasing stability follows the sequence CeO2 — ZrO2 — Gd2O3 — didymium oxide — Sm2O3 —Nd2O3 — Y2O3. The grading does not follow the free energy data of the formation of these oxides. A better correlation with the experimental observations is obtained when the solubility of the metallic species in titanium is also taken into consideration.

Synthesis of Novel Oxide Pyrochlores, A2BB?O7 (A = La, Nd; BB? = Pb, Sn, Bi), by Alkali Melt Route

Oxide pyrochlores of the formula A2BB? O7 (A = La, Nd; BB? = Pb, Sn, Bi) have been synthesized by a low-temperature ambient-pressure route employing KOH melts. All the compositions, including La2Bi2O7 and its strontium-substituted derivatives, La2-xSrxBi2O7-?, are deeply colored insulators, confirming that a metallic ground state is not achieved for Pb(IV) and Bi(IV/V) oxides with the pyrochlore structure.

X-ray diffraction line profile analysis of deformation microstructure in boron modified Ti-6Al-4V alloy

X-ray diffraction line profile analysis (XRDLPA) techniques have been applied to investigate the deformed microstructure of a recently developed boron modified two-phase titanium alloy Ti-6Al-4V. The alloy was hot compressed at 750 degrees C up to 50% height reduction at two different strain rates (10(-3) S-1 and 1 S-1). Microstructural parameters like average domain size, average microstrain within the domain and dislocation density of the two phases were determined using X-ray diffraction line profile analysis. The results indicate an increase in the microstrain and dislocation density for the alpha-phase and decrease for the beta-phase in the case of boron modified alloys as compared to the normal material. Microstructural modifications viz, the grain refinement and the presence of hard, brittle TiB particles in the case of boron modified alloy are held responsible for the observed difference in the dislocation density. (C) 2010 Elsevier Inc. All rights reserved.