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.     

Superior performance of high-velocity oxyfuel-sprayed nanostructured TiO<Subscript>2</Subscript> in comparison to air plasma-sprayed conventional Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-13TiO<Subscript>2</Subscript>

Air plasma-sprayed conventional alumina-titania (Al₂O₃-13wt.%TiO₂) coatings have been used for many years in the thermal spray industry for antiwear applications, mainly in the paper, printing, and textile industries. This work proposes an alternative to the traditional air plasma spraying of conventional aluminatitania by high-velocity oxyfuel (HVOF) spraying of nanostructured titania (TiO₂). The microstructure, porosity, hardness (HV 300 g), crack propagation resistance, abrasion behavior (ASTM G65), and wear scar characteristics of these two types of coatings were analyzed and compared. The HVOF-sprayed nanostructured titania coating is nearly pore-free and exhibits higher wear resistance when compared with the air plasma-sprayed conventional alumina-titania coating. The nanozones in the nanostructured coating act as crack arresters, enhancing its toughness. By comparing the wear scar of both coatings (via SEM, stereoscope microscopy, and roughness measurements), it is observed that the wear scar of the HVOF-sprayed nanostructured titania is very smooth, indicating plastic deformation characteristics, whereas the wear scar of the air plasma-sprayed alumina-titania coating is very rough and fractured. This is considered to be an indication of a superior machinability of the nanostructured coating.     

Preparation and characterization of nanostructured Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sn<Subscript>0.5</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Nanostructured Bi₂Se₃ and Sn_0.5-Bi₂Se₃ were successfully synthesized by hydrothermal coreduction from SnCl₂·H₂O and the oxides of Bi and Se. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM). Bi₂Se₃ powders obtained at 180°C and 150°C consist of hexagonal flakes of 50–150 nm in side length and nanorods of 30–100 nm in diameter and more than 1 μm in length. The product obtained at 120°C is composed of thin irregular nanosheets with a size of 100–200 nm and several nanometers in thickness. The major phase of Sn_0.5-Bi₂Se₃ synthesized at 180°C is similar to that of Bi₂Se₃. Sn_0.5-Bi₂Se₃ powders are primarily nanorod structures, but small amount of powders demonstrate irregular morphologies.     

HVOF thermal spray deposited Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-stabilized ZrO<Subscript>2</Subscript> coatings for thermal barrier applications

High velocity oxy-fuel (HVOF) thermal spray has been successfully used to deposit yttria-stabilized zirconia (YSZ) for thermal barrier coating (TBC) applications. Adherent coatings were obtained within a limited range of spray conditions using hydrogen as fuel gas. Spray parameters such as hydrogen-to-oxygen ratio, spray distance, and substrate cooling were investigated. Spray distance was found to have a pronounced effect on coating quality; adherent coatings were obtained for spray distances between 75 and 125 mm from the gun exit for the hydrogen-to-oxygen ratios explored. Compared to air plasma spray (APS) deposited YSZ coatings, the HVOF deposited coatings were more fully stabilized in the tetragonal phase, and of similar density, surface roughness, and cross-sectional microhardness. Notably, fracture surfaces of the HVOF coatings revealed a more homogeneous structure. Many theoretical models predict that it should not be possible to melt YSZ in an HVOF flame, and therefore it should not be possible to deposit viable YSZ coatings by this process. The experimental results in the present work clearly contradict those expectations. The present results can be explained by taking into account the effect of partial melting and sintering on particle cohesion, as follows. Combustion chamber pressures (P _o) of ∼3.9 bar (58.8 psi) realized during HVOF gun operation allows adiabatic flame temperature values that are above the zirconia melting temperature. Under these conditions, the Ranz-Marshall heat transfer model predicts HVOF sprayed particle surface temperatures T _p that are high enough for partial melting of small (∼10 μm) zirconia particles, T _p=(1.10−0.95)T _m. Further analysis shows that for larger particles (38 μm), adherent coatings are produced when the particle temperature, T _p=0.59−0.60 T _m, suggesting that sintering may have a role in zirconia particle deposition during HVOF spray. These results suggest two different bonding mechanisms for powders having a broad particle size distribution.     

Performance and capacity fading reason of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries after storing at high temperature

Spinel LiMn₂O₄ was synthesized by a solid-state method. A 204468-size battery was fabricated and stored at 55°C. The structure and morphology of the LiMn₂O₄ cathode were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) technique. Energy dispersive spectroscopy (EDS) was used to analyze the surface component of the carbon anode. The discharge capacities of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 106, 98, 96, and 92 mAh·g⁻¹, respectively. The cyclic performance is improved after storage. The capacity retentions of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 83.8%, 85.8%, 86.9%, and 88.6% after 180 cycles. The intensity of all the LiMn₂O₄ diffraction peaks is weakened. Mn is detected from the carbon electrode when the battery is stored for 96 h. Cyclic voltammograms and electrochemical impedance spectroscopy (EIS) were used to examine the surface state of the electrode after storage. The results show that the resistance and polarization of LiMn₂O₄/electrolyte is increased after storage, which is responsible for the fading of capacity.     

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.     

The corrosion inhibition of Ti-alloy (VT-9) in mixture of H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-NaF by organic compounds

This investigation deals with corrosion behavior of high strength titanium alloy in concentrated sulphuric acid solution containing different concentrations (500, 1000, 1500 ppm) of fluoride ion (F⁻) using various organic compounds (MPA, L-OH, NFP) as inhibitor, potentiodynamically. The open circuit potential values noted before and after each experiment, varied appreciably. These values were negative before polarization but after completion of the experiment turned positive and remained stable over long period of time. It is observed that cathodic current density values increase with increasing cathodic potential (more negative) and fluoride ion. The values of cathodic Tafel slopes derived from the curves (∼110 − 140 mV/dec I) indicate hydrogen evolution reaction (h.e.r). The corrosion potential (E _corr) varied slightly with addition of inhibitors. The corrosion current densities (I _corr) increased with increasing fluoride ion concentration, but these values decreased appreciably when inhibitor (MPA) was used. SEM micrograph reveals reduction of pits in the presence of inhibitor (MPA). So this concludes that organic compound was used in this case acts as a good inhibitor. The article is published in the original.     

Microstructure and Properties of HVOF-Sprayed WC-(W,Cr)<Subscript>2</Subscript>C-Ni Coatings

The composition WC-(W,Cr)₂C-Ni is one of the standard compositions used for the preparation of thermally sprayed coatings by high velocity oxy-fuel (HVOF) spraying. Surprisingly, this composition has been poorly investigated in the past. Frequent use of commercial designations WC-‘CrC’-Ni, WC-Cr₃C₂-Ni, and WC-NiCr indicates the insufficient knowledge about the phase compositions of these powders and coatings. The properties of these coatings differ significantly from those of WC-Co and WC-CoCr coatings. In this paper, the results of different series of experiments conducted on HVOF-sprayed WC-(W,Cr)₂C-Ni coatings are compiled and their specific benefits pointed out. The focus of this study is on the analysis of the microstructures and phase compositions of the feedstock powders and coatings. Unlike WC-Co and Cr₃C₂-NiCr, WC-(W,Cr)₂C-Ni is not a simple binary hard phase—binder metal composite. The phase (W,Cr)₂C with unknown physical and mechanical properties appears as a second hard phase, which is inhomogeneously distributed in the feedstock powders and coatings. As examples of coating properties, the oxidation resistance and dry sliding wear properties are compared with those of WC-10%Co-4%Cr coatings.     

Synthesis of nano-sized Co<Subscript>3</Subscript>O<Subscript>4</Subscript> powder by spray conversion method for anode material of lithium battery

A nano-sized Co₃O₄ powder was prepared using a spray conversion method that could be applied for mass production. The spray-conversion process consisted of spray drying of a metallic liquid solution, a calcination treatment, and a ball milling process. The calcined Co₃O₄ powder consisted of agglomerated spherical clusters with nano-sized particles. After milling for 24 h, agglomerated powders were fragmented into fine powders sized below 60 nm. The lithium/cobalt oxide cell was charge-discharged at a constant current density of 0.2 mAcm⁻² and showed a first discharge capacity of 1100 mAhg⁻¹. The discharge capacity of the Li/Co₃O₄ cell drastically decreased with cycle number. By increasing the carbon content of the anode, the cycle life was improved. For a Co₃O₄ electrode containing 40 wt.% carbon, the discharge capacity was over 400 mAhg⁻¹ after 50 cycles. The spray conversion method might be a useful method to prepare nano-sized Co₃O₄ powder for the anode material of lithium batteries.     

The effect of heat treatment on the corrosion resistance of 440C stainless steel in 20% HNO<Subscript>3</Subscript> + 2.5% Na<Subscript>2</Subscript>Cr<Subscript>2</Subscript>O<Subscript>7</Subscript> solution

The effect of heat treatment on the corrosion resistance of 440C stainless steel was investigated in a 20% HNO₃ + 2.5% Na₂Cr₂O₇ solution using electrochemical noise (ECN) measurements, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) examinations. The noise resistance (Rn), which has been found to be inversely related to the localized corrosion rate, was measured to be 5.7E + 08 Ω-cm², 4.2E + 08 Ω-cm², and 3.7E + 04 Ω-cm² for the oil-quenched, air-quenched, and vacuum furnace cooled (VFC) samples, respectively, after 1200 s exposures. The Rn for all heat treat conditions stabilized within a range of 1.0E + 07 Ω-cm² to 3.2E + 08 Ω-cm² after 2 h exposures. The EIS response showed a polarization resistance (R _p) on the order of 6.6E + 04 Ω-cm², 5.3E + 04 Ω-cm², and 1.1E + 04 Ω-cm² for the oil-quenched, air-quenched, and VFC samples, respectively, after 2 h exposures. The EIS data are in good agreement with ECN data and indicate that after longer exposures, general corrosion mechanisms dominate and the corrosion rates are comparable. SEM examinations of specimens subjected to 1200 s exposures revealed that severity of pitting and intergranular corrosion damage was consistent with trends in the Rn data. Specifically, the electrochemical noise data as well as SEM examinations of specimens revealed a higher localized corrosion resistance of the hardened specimens during the early stages of passivation. This greater resistance to localized corrosion can be attributed to an increased stability of the natural passive film resulting from a higher concentration of chromium atoms in solution for the martensite phase.     

Impact of Corrosion on Mass Loss,Fatigue and Hardness of BSt500<Subscript><Emphasis Type="Italic">s</Emphasis></Subscript> Steel

The impact of corrosion on the properties of steel reinforcement in concrete structures was examined. An experimental investigation was carried out in order to gain better insight of the effect of corrosion on the mass loss, fatigue and hardness, of BSt500 _s 12 and 8 mm diameter steel bars that were artificially corroded in a Sodium Chloride environment for different corrosion levels. The fatigue limit of the 12 mm steel was reduced by 20–40% and the mass loss was 1.5–2.9% for 15 and 30 days corrosion level, while the mass loss of the 8 mm steel was 1.2–32% for 10–90 days corrosion. The hardness of the 8 mm steel was reduced by 25–35% and 2–10% in the outer and inner layers of the specimens for 30 and 60 days corrosion respectively. Corrosion created considerable reduction in the fatigue strength and life of the steel bars due to drastic drop in the energy density, formation of pitting and notches along with destruction of the hardest outer layer of martensite.     

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.     

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.     

Synthesis and electrochemical performances of LiCoO<Subscript>2</Subscript> recycled from the incisors bound of Li-ion batteries

A new LiCoO₂ recovery technology for Li-ion batteries was studied in this paper. LiCoO₂ was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li₂CO₃, LiOH·H₂O and LiAc·2H₂O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO₂ was obtained by calcining the mixture at 850°C for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO₂ synthesized by adding Li₂CO₃ is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g⁻¹ between 3.0–4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g⁻¹.     

Development of plasma nitrocarburizing and post-oxidation technology for the replacement of Cr<Superscript>6+</Superscript> plating for application to vehicle engine shafts

Plasma nitrocarburizing and post-oxidation treatments were performed to improve the wear and corrosion resistance of S45C steel. Plasma nitrocarburizing was conducted for 3 h at 570°C in a nitrogen, hydrogen and methane atmosphere to produce the ε-Fe₂₋₃(N,C) phase. It was found that the compound layer produced by plasma nitrocarburising was predominantly composed of the ∈-phase with traces of the γ′-Fe₄(N,C) phase. The thickness of the compound layer was approximately 12 μm and the diffusion layer was approximately 300 μm in thickness. Plasma post oxidation was performed on nitrocarburized samples with various oxygen/hydrogen ratios at a constant temperature of 500°C for 1 h. The very thin magnetite (Fe₃O₄) layer 1 μm to 2 μm in thickness on top of the compound layer was obtained by plasma post oxidation. It was also confirmed that further improvement of the corrosion characteristics of the nitrocarburized compound layer was possible with an application of the superficial magnetite layer. Finally, throttle valve shafts of S45C steel were treated under optimum plasma processing conditions. Accelerated life time test results using a throttle body assembled with a shaft treated by plasma nitrocarburising and post oxidation showed that plasma nitrocarburizing and plasma post-oxidation processes could be a viable technology in the very near future in place of Cr⁶ plating.     

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.     

Thermodynamic optimization of the Na<Subscript>2</Subscript>O-B<Subscript>2</Subscript>O<Subscript>3</Subscript> pseudo-binary system

The Na₂O-B₂O₃ system is thermodynamically optimized by means of the CALPHAD method. A two-sublattice ionic solution model, (Na⁺¹)_P(O⁻²,BO₃ ⁻³,B₄O₇ ⁻²,B₃O_4.5)_Q, has been used to describe the liquid phase. All the solid phases were treated as stoichiometric compounds. A set of thermodynamic parameters, which can reproduce most experimental data of both phase diagram and thermodynamic properties, was obtained. Comparisons between the calculated results and experimental data are presented.     

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.     

RETRACTED ARTICLE: Dislocation-particle interaction in precipitation strengthened Ll<Subscript>2</Subscript>-ordered Ni<Subscript>3</Subscript>Al

Transmission electron microscope investigation has been performed on the particle-dislocation interactions in Ni₃Al-based intermetallics containing various types of fine precipitates. In an Ll₂-ordered Ni₃Al alloy with 4 mol.% of chromium and 0.2–0.5 mol.% of carbon, fine octahedral precipitates of M₂₃C₆ type carbide, which has a cube-cube orientation relationship with the matrix, appear during aging. Typical Orowan loops are formed in Ni₃Al containing fine dispersions of M₂₃C₆ particles. In the alloys with appropriate titanium content, fine precipitates of coherent disordered γ are formed during aging. The γ precipitates are initially spherical or rounded cubic in shape and grow into platelets as aging proceeds. Loss of coherency is initiated by the introduction of dislocations at the γ/γ′ interface and results in step formation at the dislocations. The γ precipitates become globular after the loss of coherency. In the γ′ phase hardened by the precipitation of the disordered γ phase, dislocations are attracted into the disordered γ phase and cut through the particles during deformation at any stage of aging. In Ni₃Al containing a fine dispersion of disordered γ, superdislocations are strongly attracted to the disordered particles and dissociate on the (111) plane in the γ particles, while they dissociate on the (010) plane in the matrix. It is shown by comparison that the strengthening due to attractive interaction is more effective than that due to repulsive interaction. The roles of the variation of the interaction modes and of the dissociation of superdislocations in the matrix and particles are discussed in connection with the optimum microstructures of Ll₂-ordered intermetallics as high temperature structural materials.     

Solvothermal synthesis and thermoelectric properties of skutterudite compound Fe（0.25）Ni（0.25）Co（0.5）Sb3

Nanostructured skutterudite-related compound Fe_0.25Ni_0.25Co_0.5Sb₃ was synthesized by a solvothermal method using FeCl₃, NiCl₂, CoCl₂, and SbCl₃ as the precursors and NaBH₄ as the reductant. The solvothermally synthesized powders consisted of fine granules with an average particle size of tens of nanometers. The bulk material was prepared by hot pressing the powders. Transport property measurements indicated a heavily doped semiconductor behavior with n-type conduction. The thermal conductivity is about 1.83 W·m⁻¹·K⁻¹ at room temperature and decreases to 1.57 W·m⁻¹·K⁻¹ at 673 K. The low thermal conductivity is attributed to small grain size and high porosity. A maximum dimensionless figure of merit of 0.15 is obtained at 673 K.