The β to α phase transition of tantalum coatings deposited by modulated pulsed power magnetron sputtering

Tantalum coatings are of particular interest today as promising candidates to replace potentially hazardous electrodeposited chromium coatings for tribological and corrosion resistant applications, such as the internal lining on large-caliber gun barrels. Tantalum coatings have two crystalline phases, α-Ta (body-centered-cubic) and β-Ta (metastable tetragonal) that exhibit relatively different properties. Alpha-Ta is typically preferred for wear and corrosion resistant applications and unfortunately, is very difficult to deposit without the assistance of substrate heating or post-annealing treatments. Furthermore, there is no general consensus on the mechanism which causes α or β to form or if there is a phase transition or transformation from β → α during coating deposition. In this study, modulated pulsed power (MPP) magnetron sputtering was used to deposit tantalum coatings with thicknesses between 2 and 20 μm without external substrate heating. The MPP Ta coatings showed good adhesion and low residual stress. This study shows there is an abrupt β → α phase transition when the coating is 5–7 μm thick and not a total phase transformation. Thermocouple measurements reveal substrate temperature increases as a function of deposition time until reaching a saturation temperature of ~ 388 °C. The importance of substrate temperature evolution on the β → α phase transition is also explained.

Raman and XRD study on brookite-anatase coexistence in cathodic electrosynthesized titania

Among the many methods developed for the synthesis of titanium dioxide, cathodic electrosynthesis has not received much attention because the resulting amorphous oxy-hydroxide matrix demands a further thermal annealing step to be transformed into crystalline titania. However, the possibility of filling deep recessed templates by the control of the solidliquid interface makes it a potentially suitable technique for the fabrication of porous scaffolds for photovoltaics and photocatalysis. Furthermore, a careful control of the crystallization process enables the growth of larger grains with lower density of grain boundaries, which act as electron traps that slow down electronic transport and promote charge recombination. In this report, well crystallized titania deposits were obtained by thermal annealing of amorphous deposits fabricated by cathodically assisted electrosynthesis on indium-tin oxide (ITO)substrates. The combined use of Raman spectroscopy and X-ray diffraction showed that the crystallization process is more intricate than previously assumed. It is shown that the amorphous matrix evolves into a rutile-free mixture of brookite and anatase at temperatures as low as 200 degrees C that persists up to 800 degrees C, when pure anatase dominates. The amount of brookite in the brookiteanatase mixture reaches a maximum at 400 degrees C. This very simple method for obtaining a brookiteanatase mixture and the ability to tune their proportions by thermal annealing is a promising alternative whose potential for solar cells and photocatalysis deserves a careful evaluation. Copyright (C) 2011 John Wiley & Sons, Ltd.

Highly stabilized alpha-NiCo(OH)(2) nanomaterials for high performance device application

Improving the charge capacity, electrochemical reversibility and stability of anode materials are main challenges for the development of Ni-based rechargeable batteries and devices. The combination of cobalt, as additive, and electrode material nanostructuration revealed a very promising approach for this purpose. The new alpha-NiCo mixed hydroxide based electrodes exhibited high specific charge/discharge capacity (355-714 C g(-1)) and outstanding structural stability, withstanding up to 700 redox cycles without any significant phase transformation, as confirmed by cyclic voltammetry, electrochemical quartz crystal microbalance and X-ray diffractometry. In short, the nanostructured alpha-NiCo mixed hydroxide materials possess superior electrochemical properties and stability, being strong candidates for application in high performance batteries and devices. (C) 2012 Elsevier B.V. All rights reserved.

Predicting Delta Ferrite Content in Stainless Steel Castings

The distribution of delta ferrite fraction was measured with the magnetic method in specimens of different stainless steel compositions cast by the investment casting (lost wax) process. Ferrite fraction measurements published in the literature for stainless steel cast samples were added to the present work data, enabling an extensive analysis about practical methods to calculate delta ferrite fractions in stainless steel castings. Nineteen different versions of practical methods were formed using Schaeffler, DeLong, and Siewert diagrams and the nickel and chromium equivalent indexes suggested by several authors. These methods were evaluated by a detailed statistical analysis, showing that the Siewert diagram, including its equivalent indexes and iso-ferrite lines, gives the lowest relative errors between calculated and measured delta ferrite fractions. Although originally created for stainless steel welds, this diagram gives relative errors lower than those for the current ASTM standard method (800/A 800M-01), developed to predict ferrite fractions in stainless steel castings. Practical methods originated from a combination of different chromium/nickel equivalent indexes and the iso-ferrite lines from Schaeffler diagram give the lowest relative errors when compared with combinations using other iso-ferrite line diagrams. For the samples cast in the present work, an increase in cooling rate from 0.78 to 2.7 K/s caused a decrease in the delta ferrite fraction, but a statistical hypothesis test revealed that this effect is significant in only 50% of the samples that have ferrite in their microstructures.

Vanadium and Titanium Mixed Oxide Films: Synthesis, Characterization and Application as Ion Sensor

Vanadium/titanium mixed oxide films were produced using the sol-gel route. The structural investigation revealed that increased TiO2 molar ratio in the mixed oxide disturbs the V2O5 crystalline structure and makes it amorphous. This blocks the TiO2 phase transformation, so TiO2 stabilizes in the anatase phase. In addition the surface of the sample always presents larger amounts of TiO2 than expected, revealing a concentration gradient along the growth direction. For increased TiO2 molar ratios the roughness of the surface is reduced. Ion sensors were fabricated using the extended gate field effect transistor configuration. The obtained sensitivities varied in the range of 58 mV/pH down to 15 mV/pH according to the composition and morphology of the surface of the samples. Low TiO2 amounts presented better sensing properties that might be related to the cracked and inhomogeneous surfaces. Rising the TiO2 quantity in the films produces homogeneous surfaces but diminishes their sensitivities. Thus, the present paper reveals that the compositional and structural aspects change the surface morphology and electrical properties accounting for the final ion sensing properties of the V2O5/TiO2 films. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.053206jes] All rights reserved.

Dependence of brittle-to-ductile transition on crystallographic direction in diamond turning of single-crystal silicon

The objective of this paper is to show the dependence relationship between the crystallographic orientations upon brittle-to-ductile transition during diamond turning of monocrystalline silicon. Cutting tests were performed using a -5 degrees rake angle round nose diamond tool at different machining scales. At the micrometre level, the feedrate was kept constant at 2.5 micrometres per revolution (mu m/r), and the depth of cut was varied from 1 to 5 mu m. At the submicrometre level, the depth of cut was kept constant at 500 nm and the feedrate varied from 5 to 10 mu m/r. At the micrometre level, the uncut shoulder generated with an interrupted cutting test procedure provided a quantitative measurement of the ductile-to-brittle transition. Results show that the critical chip thickness in silicon for ductile material removal reaches a maximum of 285 nm in the [100] direction and a minimum of 115 nm in the [110] direction, when the depth of cut was 5 mu m. It was found that when a submicrometre depth of cut was applied, microcracks were revealed in the [110] direction, which is the softer direction in silicon. Micro Raman spectroscopy was used to estimate surface residual stress after machining. Compressive residual stress in the range 142 MPa and smooth damage free surface finish was probed in the [100] direction for a depth of cut of 5 mu m, whereas residual stresses in the range 350 MPa and brittle damage was probed in the [110] direction for a depth of cut of 500 nm.

CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

Ceria (CeO2) plays a vital role in emerging technologies for environmental and energy-related applications. The catalytic efficiency of ceria nanoparticles depends on its morphology. In this study, CeO2 nanoparticles were synthesized by a microwave-assisted hydrothermal method under different synthesis temperatures. The samples were characterized by X-ray diffraction, transmission electron microscopy, Raman scattering spectroscopy, electron paramagnetic resonance spectroscopy and by the Brunauer-Emmett-Teller method. The X-ray diffraction and Raman scattering results indicated that all the synthesized samples had a pure cubic CeO2 structure. Rietveld analysis and Raman scattering also revealed the presence of structural defects due to an associated reduction in the valence of the Ce4+ ions to Ce3+ ions caused by an increasing molar fraction of oxygen vacancies. The morphology of the samples was controlled by varying the synthesis temperature. The TEM images show that samples synthesized at 80 degrees C consisted of spherical particles of about 5 nm, while those synthesized at 120 degrees C presented a mix of spherical and rod-like nanoparticles and the sample synthesized at 160 degrees C consisted of nanorods with 10 nm average diameter and 70 nm length. The microwave-assisted method proved to be highly efficient for the synthesis of CeO2 nanoparticles with different morphologies.

Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions

The dependences of phase stability and solid state phase transitions on the crystallite size in ZrO2-10, 12 and 14 mol% Sc2O3 nanopowders are investigated by X-ray powder diffraction using a synchrotron source (S-XPD). The average crystallite sizes lie within the range of 35 to 100 nm, approximately. At room temperature these solid solutions were previously characterised as mixtures of a cubic phase and one or two rhombohedral phases, beta and gamma, with their fractions depending on composition and average crystallite sizes. In this study, it is shown that at high temperatures these solid solutions become cubic single-phased. The size-dependent temperatures of the transitions from the rhombohedral phases to the cubic phase at high temperature are determined through the analyses of a number of S-XPD patterns. These transitions were studied on cooling and on heating, exhibiting hysteresis effects whose relevant features are size and composition dependent.