Interdiffusion in <Emphasis Type="Italic">L</Emphasis>1<Subscript>2</Subscript>-Ni<Subscript>3</Subscript>Al Alloyed with Re

Ternary interdiffusion in L1₂-Ni₃Al with ternary alloying addition of Re was investigated at 1473 K using solid-to-solid diffusion couples. Interdiffusion flux of Ni, Al, and Re were directly calculated from experimental concentration profiles and integrated for the determination of average ternary interdiffusion coefficients. The magnitude of main interdiffusion coefficients and was determined to be much larger than that of the main interdiffusion coefficient A moderate tendency for Re to substitute for Al sites was reflected by its influence on interdiffusion of Al, quantified by large and positive coefficients. Similar trends were observed from ternary interdiffusion coefficients determined by Boltzmann-Matano analysis. Profiles of concentrations and interdiffusion fluxes were also examined to estimate binary interdiffusion coefficients in Ni₃Al, and tracer diffusion coefficients of Re (5.4 × 10⁻¹⁶ ± 2.3 × 10⁻¹⁶ m²/s) in Ni₃Al.     

Studies on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> high K gate dielectrics applied in a fully depleted SOI MOSFET

Al₂O₃/ZrO₂/Al₂O₃ gate stacks were prepared on ultrathin SOI (Silicon on insulator) substrates by ultrahigh vacuum electron beam evaporation and post-annealed in N₂ at 450°C for 30 min. Three clear nanolaminate layered structure of Al₂O₃(2.1 nm)/ZrO₂(3.5 nm)/Al₂O₃(2.3 nm) was observed with a high-resolution cross-sectional transmission electron microscope (HR-XTEM). High frequency capacitance voltage (C-V) characteristics of a fully depleted (FD) SOI MOS capacitor at 1 and 5 MHz were studied. The minority carriers determine the high frequency C-V properties, which is opposite to the case of bulk MOS capacitors. The series resistance of the SOI substrate is found to be the determinant factor of the high frequency characteristics of FD SOI MOS capacitors. This article is based on a presentation in “The 7th Korea-China Workshop on Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24≈27, 2003.     

Structure and electric property comparison between Ge nanoclusters embedded in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>

Metal-insulator-semiconductor (MIS) structures containing Ge nanocrystals embedded in both Al₂O₃ and ZrO₂/Al₂O₃ are fabricated by an ultra-high vacuum electron-beam evaporation method. Secondary ion mass spectroscopy (SIMS) results indicate that Ge embedded in Al₂O₃ diffuses towards the surface of the Al₂O₃ layer after annealing at 800°C in N₂ ambient for 30 min. Ge embedded in ZrO₂/Al₂O₃ is stable, thus inducing less leakage current. Capacitance voltage studies indicate that annealing can effectively passivate the negatively charged trapping centers. Memory effect of the Ge nanoclusters is verified by hysteresis in the C-V curves in the Al₂O₃/Ge+Al₂O₃/Al₂O₃ and ZrO₂/Ge+Al₂O₃/Al₂O₃ samples. This article is based on a presentation in “The 7th Korea-China Workshop On Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24–27, 2003.     

Photoresponse and donor concentration of plasma-sprayed TiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript>-ZnO electrodes

The photoelectrochemical characteristics of plasma-sprayed porous TiO₂, TiO₂-5%ZnO, and TiO₂-10%ZnO electrodes in 0.1 N NaOH solution were studied through a three-electrode cell system. The microstructure, morphology, and composition of the electrodes were analyzed using an electron probe surface roughness analyzer (ERA-8800FE), scanning electron microscopy, and x-ray diffraction. The results indicate that the sprayed electrodes have a porous microstructure, which is affected by the plasma spray parameters and composition of the powders. The TiO₂-ZnO electrodes consist of anatase TiO₂, rutile TiO₂, and Zn₂Ti₃O₈ phase. The photoresponse characteristics of the plasma-sprayed electrodes are comparable to those of single-crystal TiO₂, but the breakdown voltage is close to 0.5 V (versus that of a saturated calomel electrode). The short-circuit photocurrent density (J _SC) increases with a decrease of donor concentration, which was calculated according to the Gartner-Butler model. For the lowest donor concentration of a TiO₂-5%ZnO electrode sprayed under an arc current of 600 A, the short-circuit J _SC is approximately 0.4 mA/cm² higher than that of the TiO₂ electrodes under 30 mW/cm² xenon light irradiation. The J _SC increases linearly with light intensity. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Application,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

Tunneling magnetoresistance in sintered Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> samples diluted with Fe and α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Electric transport and magnetoresistance characteristics were investigated for Fe₃O₄-x Fe(x=0, 10, 20 wt.%) samples and Fe₃O₄-α-Fe₂O₃ samples sintered at 500°C. For composition dependence of Fe₃O₄-x Fe samples, the largest room temperature MR, 3.3% at 10 kOe, was obtained from a Fe₃O₄-10 Fe sample. For the surface heat treatment dependence of Fe₃O₄ powders, the largest room temperature MR, 4% at 10 kOe, was obtained from a Fe₃O₄-α-Fe₂O₃ sample sintered with Fe₃O₄ powders heated at 200°C in air. It was found that these enhanced MR ratios always appear together with the appropriate excess resistance which is regarded as the tunneling barrier. These enhanced MR ratios of Fe₃O₄-10 Fe and Fe₃O₄-α-Fe₂O₃ samples can be explained by the increased interparticle contact sites and the appropriate thickness of α-Fe₂O₃, respectively.     

Effect of a surface treatment for LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> cathode material in lithium secondary batteries

LiNi_1/3Co_1/3Mn_1/3O₂ cathode material was surface-treated to improve its electrochemical performance. Al₂O₃ nanoparticles were coated onto the surface of LiNi_1/3Co_1/3Mn_1/3O₂ powder using a sol-gel method. The as-prepared Al₂O₃ nano-particle was identified as the cubic structure of Al₂O₃. XRD showed that the LiNi_1/3Co_1/3Mn_1/3O₂ structure was not affected by the Al₂O₃ coating. With a coating of 3 wt.% Al₂O₃ on LiNi_1/3Co_1/3Mn_1/3O₂, the cyclic-life performance and rate capability were improved. However, heavier coatings (5 wt.%) on LiNi_1/3Co_1/3Mn_1/3O₂ resulted in a considerable decrease of the discharge capacity and rate capability. The thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂ materials was greatly improved by the 3 wt.% Al₂O₃ coating.     

Effect of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> content on the oxidation behavior of Fe-Cr-Al-based ODS alloys

A study was conducted to investigate the cyclic oxidation behavior of two oxide dispersion strengthened (ODS) Fe-Cr-Al based alloys containing 0.17 wt.% and 0.7 wt.% Y₂O₃. The alloys were oxidized in air for 100 h at 1200°C based on a 24 h cycle period. X-ray diffraction (XRD) and analytical transmission electron microscopy (TEM) were used to characterize the structure, morphology, and composition of the oxide scales. Both alloys formed highly adherent and continuous layers of α-Al₂O₃ exhibiting a morphology indicative of inward scale growth. The role of Y₂O₃ was to promote adherence by segregating to the grain boundaries within the oxide. Concurrently, Y₂O₃ generated micro-porosity resulting in a scale of comparatively higher thickness in the alloy with 0.7 wt.% Y₂O₃.     

Effects of defects generated in ALD TiO<Subscript>2</Subscript> films on electrical properties and interfacial reaction in TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>/Si system upon annealing in vacuum

Thin TiO₂ layers grown at 130°C on SiO₂-coated Si substrates by atomic layer deposition (ALD) using TTIP and H₂O as precursors were annealed, and the effects of the annealing temperature on the resulting electrical properties of TiO₂ and the interface properties between a Pt electrode and TiO₂ were examined using transmission line model (TLM) structures. The as-deposited TiO₂ thin film had an amorphous structure with OH groups and a high resistivity of 6×10³Ω-cm. Vacuum annealing at 700 °C transformed the amorphous film into an anatase structure and reduced its resistivity to 0.04Ω-cm. In addition, the vacuum-annealing of the TiO₂/SiO₂ structure at 700°C produced free silicon at the TiO₂-SiO₂ interface as a result of the reaction between the Ti interstitials and SiO₂. The SiO₂ formed on the TiO₂ surface caused a Schottky contact, which was characterized by the TLM method. The use of the TLM method enabled the accurate measurement of the resistivity of the vacuum-annealed TiO₂ films and the characterization of the Schottky contacts of the metal electrode to the TiO₂.     

Corrosive wear behavior of 7075 aluminum alloy and its composite containing Al<Subscript>2</Subscript>O<Subscript>3</Subscript> particles

Corrosive wear behavior of 7075 aluminum alloy and a composite containing 0.10 volume fraction of alumina particles (VFAP) has been evaluated. Transient current (TC) generated as a result of impacting a rotating cylindrical electrode immersed in a 0.1M NaCl solution with a Vickers diamond hardness indenter has been used to measure the corrosive wear response. Age hardenable 7075 alloy shows TC values that are sensitive to prior solutionizing time. The effect of alumina particles in a 7075 aluminum alloy matrix has been studied by comparing the TC values of a monolith along with composites under almost identical experimental conditions. The role of microstructural features associated with composites, such as dislocations generated after solutionizing treatment and during the corrosive wear process, has been observed with the help of near surface microstructures through transmission electron microscopy (TEM). Deformation induced dislocations, as well as those that are due to differences in the coefficient of thermal expansion (CTE) values between the particles and the matrix during solutionizing, have been attributed to the experimentally observed TC values. They may also be affected by the aging response of the monolith and composites, depending on solutionizing time.     

Simulation of hydrogen diffusion in TiH<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> structures

Quantum-mechanical calculations of the energies of the formation of Frenkel pairs and barriers for hydrogen migration via different mechanisms in the titanium hydride δ-TiH _x and in the α phase of titanium have been carried out. Using the potential of interaction developed for the molecular-dynamic simulation, diffusion coefficients of hydrogen in fcc and hcp lattices of TiH _x were calculated depending on the temperature. The opportunity to approximate the coefficients of hydrogen self-diffusion has been analyzed in terms of the model of non-interacting point defects. For δ-TiH _x , the range of concentrations and temperatures was separated where the self-diffusion of hydrogen becomes liquid-like (ceases be dependent on the hydrogen concentration), upon the transition into which there takes place a sharp increase in the isochoric heat capacity. The effect of defects in the Ti sublattice on the coefficient of self-diffusion of H has been investigated.     

Preparation of TiO<Subscript>2</Subscript> Nanopowders by Plasma Spray and Characterizations

TiO₂ powders with the range of 10-60 nm were prepared successfully by plasma spray in the self-developed plasma spray equipment. The prepared nanopowders were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results showed that the prepared TiO₂ nanopowders were the mixture of anatase phase and rutile phase, the main phase was anatase. There were O, Ti, and C elements in powders; Ti element still existed in tetravalent. The photocatalytic degradation of methyl orange indicated that all methyl orange (20 mg/L) can be degraded fully when the addition of prepared TiO₂ nanopowders and illumination time were 1 g/L and 150 min, respectively.     

Chemical observation of anodic TiO<Subscript>2</Subscript> for biomaterial application

Anodic TiO₂ film on Ti a substrate was fabricated at 170 V in sulfuric acid solutions containing phosphoric acid and hydrogen peroxide. The pores in the oxide layer were not uniform in size, shape, or direction of growth, particularly near the interface between the substrate and the oxide layer, compared with those of the surface layer. The formation of an irregular type of pores seemed to be caused by the spark discharge phenomena, which occurred extensively when the anodic voltage was increased. The pore diameter and the cell size increased and the number of cells per unit area decreased over time. From the analysis of chemical states in the XPS spectrum, the incorporated phosphate species were found mostly in the forms of HPO₄, PO₄, and PO₃. In addition, Ti, O, and P were well dispersed in TiO₂ oxide film, as shown in the results of element mapping analyses by an energy dispersive X-ray spectrometer. An SEM observation of osteoblast-likes cells grown on treated TiO₂ oxide film samples for 24h showed clear differences in cell density and spreading pattern. MC3T3 osteoblast-like cells were flat with a polygonal configuration and were attached to the substrate by cellular extensions.     

HVOF-Sprayed Coatings Engineered from Mixtures of Nanostructured and Submicron Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> Powders: An Enhanced Wear Performance

In previous studies, it has been demonstrated that nanostructured Al₂O₃-13 wt.%TiO₂ coatings deposited via air plasma spray (APS) exhibit higher wear resistance when compared to that of conventional coatings. This study aimed to verify if high-velocity oxy-fuel (HVOF)-sprayed Al₂O₃-13 wt.%TiO₂ coatings produced using hybrid (nano + submicron) powders could improve even further the already recognized good wear properties of the APS nanostructured coatings. According to the abrasion test results (ASTM G 64), there was an improvement in wear performance by a factor of 8 for the HVOF-sprayed hybrid coating as compared to the best performing APS conventional coating. When comparing both hybrid and conventional HVOF-sprayed coatings, there was an improvement in wear performance by a factor of 4 when using the hybrid material. The results show a significant antiwear improvement provided by the hybrid material. Scanning electron microscopy (SEM) at low/high magnifications showed the distinctive microstructure of the HVOF-sprayed hybrid coating, which helps to explain its excellent wear performance. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Dependency of fracture toughness of plasma sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coatings on lamellar structure

The fracture toughness of plasma-sprayed Al₂O₃ coatings in terms of critical strain energy release rate G _Ic was investigated using a tapered double cantilever beam (TDCB) approach. This approach makes the fracture toughness be measured only using the critical fracture load disregarding crack length during test. The Al₂O₃ coatings were deposited under different spray distances and plasma powers to clarify the effect of spray parameters on the G _Ic of the coatings. The fracture surfaces were examined using scanning electron microscope. On the basis of an idealized layer microstructure model for thermal sprayed coatings, the theoretical relationship between the cohesive fracture toughness and microstructure is proposed. The correlation between the calculated fracture toughness and observed value is examined. It was found that the fracture toughness of plasma sprayed Al₂O₃ coatings is not significantly influenced by spray distance up to 110 mm, and further increase in spray distance to 130 mm resulted in large decrease in the fracture toughness of the coatings. The G _Ic value predicted based on the proposed model using lamellar interface mean bonding ratio and the effective surface energy of bulk ceramics agreed well with the observed G _Ic data. Such agreement evidently shows that the fracture toughness of thermally sprayed ceramic coatings at the direction along coating surface is determined by lamellar interface bonding.     

Electrochemical characteristics of amorphous MgTixNi （x = 0,0.1, and 0.2） hydrogen storage alloys

MgTi _x Ni (x = 0, 0.1, and 0.2) alloys were successfully prepared by mechanical alloying (MA), and the influence of milling time on the electrochemical characteristics of the electrodes was discussed. MgTi _x Ni alloys after 90 h milling displayed the best electrochemical performance. The X-ray diffraction patterns showed that the alloy ball-milled for 90 h was amorphous with a widened diffraction peak. The charge-discharge tests indicated that these alloys had good electrochemical activation properties, and the MgTi_0.2Ni alloy electrode exhibited the best cycle performance. The initial discharge capacity of the MgTi_0.2Ni alloy reached up to 401.1 mAh·g⁻¹, and the retention rate of capacity was 31.0% after 30 cycles, much higher than that of MgNi (17.3%). The Tafel polarization curves revealed that Ti addition could enhance the anticorrosion performance of these alloys in alkali solution, which was responsible for the ameliorated cyclic stability of these alloy electrodes.     

Microstructure and Properties of FeAlCrNiMo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> High-Entropy Alloys

FeAlCrNiMo _x high-entropy alloys were prepared. The effect of Mo content on the microstructure and the properties of the alloys were investigated. When the Mo content was 0.1, the alloys were composed of single BCC solid solution; when Mo content reaches 0.25, the alloys were composed of BCC solid solution and ordered B2 solid solution. When Mo content is more than 0.75, some σ phases emerged. The volume fraction of the second phase increases with the increasing Mo content, and the crystal grains became coarsening. The yield strength, fracture strength, and hardness increase with the increasing Mo content and reach 2252, 2612 MPa, and 1006 Hv, respectively. The magnetic transformation undergoes from the ferromagnetism to paramagnetism with the increasing Mo content. The saturation intensity and remnant magnetism are decreased with the increasing Mo content.     

Effect of the addition of Sm<Subscript>2</Subscript>O<Subscript>3</Subscript> on the microstructure of laser cladding alloy coating layers

The effects on the microstructures and phases of coating layers by the addition of micron-sized (m) and nano-sized (n) (m&n) Sm₂O₃ powders were investigated. The coating materials, which were prepared by means of 2.0 kW CO₂ laser cladding, consist of a powder mixture of m Ni-based alloy (NBA) powders comprising 1.5 wt.% m Sm₂O₃ and 3.0% n Sm₂O₃ powders. The results indicate that γ-Ni, Cr₂₃C₆ and Ni₃B are the primary phases of the NBA coatings. The Fe₇Sm and Ni₃Si phases are highlighted by the addition of m&n Sm₂O₃ powders. From the substrate, planar crystal layers are first grown in all NBA and m&n Sm₂O₃/NBA coatings. The dendrite growth then occurs as a result of the addition of the m Sm₂O₃ powder, and the equiaxed dendrite growth occurs as a result of the addition of the n Sm₂O₃. With the addition of a rare earth oxide such as Sm₂O₃ powder, the width of the planar crystal becomes smaller than that of the NBA coating.     

Tensile and wear properties of rolled Al5Mg-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> or C particulate composites

Al5Mg alloy matrix composites reinforced with different percentages of Al₂O₃ (60 μm) or C (90 μm) particulates were prepared by the vortex method. The composites were then subjected to hot or cold rolling with different reduction ratios. The microstructures of the rolled composites revealed that the matrix grains moved around the particulate causing deformation. By continuing deformation, the particulates rearranged themselves in the matrix, leading to lensoid distortion. It was found that the addition of Al₂O₃ or C particulates increased the 0.2% proof stress and reduced both the tensile strength and ductility, compared with the monolithic alloy. Scanning electron microscopy (SEM) fractographic examinations showed that the composites reinforced with Al₂O₃ particulates failed through particulate fracture and matrix ligament rupture. However, the failure of the composites reinforced with C particulates was through particulate decohesion, followed by ductile failure of the matrix. Abrasive wear results showed that the wear rate of the Al5Mg alloy decreased with the addition of C particulates. However, increasing the volume fraction of C particulates did not have a prominent effect on the wear rate. The composites reinforced with Al₂O₃ particulates exhibited a higher wear rate than that of the unreinforced alloy. Furthermore, addition of both C and Al₂O₃ particulates into the Al5Mg matrix alloy did not significantly improve the wear resistance. For all composites studied in this work, hot or cold rolling had a marginal effect on the wear results.     

Capacitance performance enhancement of TiO<Subscript>2</Subscript> doped with Ni and graphite

Nano-amorphous TiO₂ was prepared by a sol-gel method. The results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the composite electrode material (TiO₂-NiO-C) is made of powder with a grain size of 36.2 nm. Doping of nickel and graphite can increase the electrical conductivity and the specific surface area of nano-amorphous TiO₂. The electrochemical properties of TiO₂-NiO-C, such as self-discharge, leakage current, and cycle life, were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. With a charge-discharge current density of 500 mA/g, the specific capacity of the TiO₂-NiO-C composite material reaches 12.88 mAh/g. Also, the expense of capacity is only 3.88% after 500 cycles. The electrochemical capacitor with the electrode material of TiO₂-NiO-C shows excellent capacity and cycling performance.