Effect of 2D WS<Subscript>2</Subscript> Addition on Cold-Sprayed Aluminum Coating

Tungsten disulfide (WS₂) has excellent solid lubrication properties due to its 2D layered structure. This study focuses on depositing Al-2 wt.% WS₂ composite coating by cold spray technique. The effect of WS₂ addition on the microstructure, mechanical and tribological properties of the composite coatings is examined in the as-deposited and heat-treated conditions. After heat treatment, the coating density increased to 99% with improved intersplat bonding. The microhardness of the heat-treated Al-2 wt.% WS₂ coating increased by 56% as compared to the as-sprayed coating. The wear resistance of heat-treated Al-2 wt.% WS₂ coating improved by 75% with a synergistic reduction in the coefficient of friction (COF) by 51%. Transmission electron microscopy investigation reveals the presence of layered WS₂ within aluminum splats with a strong interface. This study shows that cold spraying can be effectively used to integrate 2D layered WS₂ as a solid lubricant in the metallic coatings.     

Formation of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Diffusion Barrier Between Cr-Contained Stainless Steel and Cold-Sprayed Ni Coatings at High Temperature

A novel approach to prepare a coating system containing an in situ grown Cr₂O₃ diffusion barrier between a nickel top layer and 310SS was reported. Cold spraying was employed to deposit Ni(O) interlayer and top nickel coating on the Cr-contained stainless steel substrate. Ni(O) feedstock was prepared by mechanical alloying of pure nickel powders in ambient atmosphere, acting as an oxygen provider. The post-spray annealing was adopted to grow in situ Cr₂O₃ layer between the substrate and nickel coating. The results revealed that the diffusible oxygen can be introduced into nickel powders by mechanical alloying. The oxygen content increases to 3.25 wt.% with the increase of the ball milling duration to 8 h, while Ni(O) powders maintain a single phase of Ni. By annealing the sample in Ar atmosphere at 900 °C, a continuous Cr₂O₃ layer of 1-2 μm thick at the interface between 310SS and cold-sprayed Ni coating is formed. The diffusion barrier effect evaluation by thermal exposure at 750 °C shows that the Cr₂O₃ oxide layer effectively suppresses the outward diffusion of Fe and Cr in the substrate effectively.     

Corrosion Behavior and Microhardness of Ni-P-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nano-composite Coatings on Magnesium Alloy

In the present work, nano-composites of Ni-P-SiO₂-Al₂O₃ were coated on AZ91HP magnesium alloy. The surface morphology of the nano-composite coating was studied by field emission scanning electron microscopy (FESEM). The amount of SiO₂ in the coating was determined by energy-dispersive analysis of x-ray (EDX), and the crystalline structure of the coating was examined by x-ray diffractometer (XRD). All the experiments concerning the corrosion behavior of the coating carried out in 3.5 wt.% NaCl solution and evaluated by electrochemical impedance spectroscopy (EIS) and polarization technique. The results showed that an incorporation of SiO₂ and Al₂O₃ in Ni-P coating at the SiO₂ concentration of 10 g/Land 14 g/LAl₂O₃ led to the lowest corrosion rate (i _corr = 1.3 µA/cm²), the most positive E _corr and maximum microhardness (496 VH). Furthermore, Ni-P-SiO₂-Al₂O₃ nano-composite coating possesses less porosity than that in Ni-P coating, resulting in improving corrosion resistance.     

Effect of Nano-Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Additives and Plasma Treatment on the Dry Sliding Wear Behavior of Plasma Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-8YSZ Ceramic Coatings

In this paper, the effect of nano-Si₃N₄ additives and plasma treatment on the wear behavior of Al₂O₃-8YSZ ceramic coatings was studied. Nano-Al₂O₃, nano-8YSZ (8 wt.% Y₂O₃-stabilized ZrO₂) and nano-Si₃N₄ powders were used as raw materials to fabricate four types of sprayable feedstocks. Plasma treatment was used to improve the properties of the feedstocks. The surface morphologies of the ceramic coatings were observed. The mechanical properties of the ceramic coatings were measured. The dry sliding wear behavior of the Al₂O₃-8YSZ coatings with and without Si₃N₄ additives was studied. Nano-Si₃N₄ additives and plasma treatment can improve the morphologies of the coatings by prohibiting the initiation of micro-cracks and reducing the unmelted particles. The hardness and bonding strength of AZSP (Al₂O₃-18 wt.% 8YSZ-10 wt.% Si₃N₄-plasma treatment) coating increased by 79.2 and 44% compared to those of AZ (Al₂O₃-20 wt.% 8YSZ) coating. The porosity of AZSP coating decreased by 85.4% compared to that of AZ coating. The wear test results showed that the addition of nano-Si₃N₄ and plasma treatment could improve the wear resistance of Al₂O₃-8YSZ coatings.     

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.     

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.     

Influence of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Particle Size on Microstructure,Mechanical Properties and Abrasive Wear Behavior of Flame-Sprayed and Remelted NiCrBSi Coatings

The influence of micrometric alumina (low surface area-to-volume ratio) and nanometric alumina (high surface area-to-volume ratio) on microstructure, hardness and abrasive wear of a NiCrBSi hardfacing alloy coating applied to an AISI 304 substrate using flame spraying (FS) combined with surface flame melting (SFM) is studied. Remelting after spraying improved the mechanical and tribological properties of the coatings. Microstructural characterization using XRD, SEM and EDS indicated that alumina additions produced similar phases (NiSi, Ni₃B, CrC and Ni₃₁Si₁₂) regardless of the alumina size, but the phases differed in morphology, size distribution and relative proportions from one coating to another. The addition of 12 wt.% nanometric Al₂O₃ increased the phases concentration more than five- to sixfold and reduced the hard phases size about four-to threefold compared with NiCrBSi + 12 wt.% micrometric Al₂O₃. Nanoalumina led to reduced mass loss during abrasive wear compared to micrometric alumina and greater improvement in hardness.     

Thermodynamic Assessment of PrCl<Subscript>3</Subscript>-CaCl<Subscript>2</Subscript> and NdCl<Subscript>3</Subscript>-CaCl<Subscript>2</Subscript> Systems

By using the CALPHAD technique, an assessment of the binary PrCl₃-CaCl₂ and NdCl₃-CaCl₂ systems have been carried out. From measured phase equilibrium data and experimental integral properties, the PrCl₃-CaCl₂ and NdCl₃-CaCl₂ phase diagrams were optimized and calculated. A set of thermodynamic functions has been optimized based on an interactive computer-assisted analysis. The calculated results by present method agree well with the experimental data.     

Up-Date of a Thermodynamic Database of the ZrO<Subscript>2</Subscript>-Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System for TBC Applications

The thermodynamic database of the ZrO₂-Gd₂O₃-Y₂O₃-Al₂O₃ system is up-dated taking into account new data on lattice stabilities of ZrO₂, Gd₂O₃ and Y₂O₃ and heat capacity measurements for the monoclinic phase Gd₄Al₂O₉ and phase with garnet structure Gd₃Al₅O₁₂. New data for the heat capacities of Gd₂Zr₂O₇ (pyrochlore) and GdAlO₃ (perovskite) as well as on the enthalpy of formation of fluorite solid solutions (Zr_1−x Gd _x )O_2−x/2 were found to be in good agreement with calculated results. In comparison with the previous assessment, taking into account new experimental data resulted in a change of the melting character of the Gd₄Al₂O₉ phase from a peritectic one to a congruent one in the Gd₂O₃-Al₂O₃ system. Correspondently, in the ternary system ZrO₂-Gd₂O₃-Al₂O₃, the melting character of the three-phase assemblage Gd₂O₃ (B), Gd₄Al₂O₉ and GdAlO₃ changed from eutectic to transition type U. The T ₀-lines for T/M and F/T diffusionless transformations and driving force of partitioning to equilibrium assemblage T + F were calculated in the ZrO₂-Gd₂O₃-Y₂O₃ system.     

Preparation and optical properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> powder

Y(NO3)3 and NH3·H2O were used as a raw materials,and nano-Y2O3 powder was successfully synthesized by a precipitation method.Employing TEOS as a raw material,SiO2 powder was successfully prepared by a alkoxide-hydrolysis method,and a Y2O3/SiO2 composite powder was obtained by coating.The Y2O3,SiO2,and Y2O3/SiO2 powders were characterized using X-ray diffraction(XRD),scanning electron microscopy(SEM),and Fourier transform infrared spectrophotometer(FT-IR);the Y2O3 and Y2O3/SiO2 powders were further examined ...     

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.     

Microstructure and High-Temperature Oxidation Behavior of Cold Gas-sprayed Ni-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Coatings

Cermet coatings are widely used for high-temperature industrial applications. This study investigates the effect of high-temperature oxidation on cold gas dynamic-sprayed Ni-Al₂O₃ coatings. For this purpose, high-temperature oxidation tests were performed at 520 and 640 °C. The selected exposure times were 24, 48, 72, 168, and 336 h. The microstructural evolution during exposure at high temperature was analyzed by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), and x-ray diffraction (XRD). The oxidation kinetics was estimated by thickness measurements. The results show that the coatings protect the substrates against oxidation. In order to study possible changes in the mechanical properties of the system, Vickers microhardness experiments on the coatings and on the 10CrMo9-10 steel substrates were conducted. It was observed that hardness decreased by exposing the specimens to high temperature.     

Oxidation Behavior of NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Spinel-Coated Interconnects in Wet Air

Corrosion of boilers and heat exchangers is accelerated in the presence of vanadium, sodium, and sulfur from low-grade fuels. Several iron- and nickel-based alloys were immersed in 60 mol% V₂O₅–40Na₂SO₄ salt for 1000 h in order to investigate their degradation behavior at 600 °C in air. Materials performance was analyzed by means of substrate recession rate and metallographic characterization. Their corrosion mechanism is characterized by the formation of a sulfide/oxide layer adjacent to the metal, the dissolution of scale oxides in the molten deposit, and their precipitation near the outer surface of the deposit. High Ni- and Cr-containing alloys show the lowest metal loss rates. Al addition was detrimental due to low-melting eutectic AlVO₄–V₂O₅ formation. Fe–Cr-based alloys showed the highest metal loss rates. In such alloys, high Cr additions (above 20%) did not improve the performance due to the negative synergetic effect by simultaneous dissolution of Fe₂O₃ and Cr₂O₃. The predominant salt composition at the corrosion front varied from vanadate rich to sulfate rich during the exposure. This change in the attacking salt makes it difficult to find a protective material for mixed sulfate–vanadate-induced corrosion.     

PbO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> composite electrodes

Electrodeposition of composite PbO₂-based materials containing titanium dioxide particles was studied. The TiO₂ content of the composite depends on the bath composition and the deposition conditions. Inclusion of TiO₂ particles in PbO₂ substantially changes the morphology and structure of the deposit. The oxygen overpotential at composite materials increased but the rate of the conversion of 4-chlorophenol into nontoxic compounds remained virtually unchanged. The lifetime of the electrodes containing the inert TiO₂ phase was found to be twice as long as that of traditional PbO₂ anodes.     

Phase Diagram of the Quaternary Al(NO<Subscript>3</Subscript>)<Subscript>3</Subscript>-Cu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-Zn(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O System

The phase diagram of the H₂O-Zn(NO₃)₂-Al(NO₃)₃-Cu(NO₃)₂ quaternary system at 30 °C has been established by using the conductivity measurements. The solid-liquid equilibria of the H₂O-Zn(NO₃)₂-Al(NO₃)₃, H₂O-Zn(NO₃)₂-Cu(NO₃)₂, H₂O-Al(NO₃)₃-Cu(NO₃)₂ ternary systems and two isoplethic sections were determined experimentally. The solid phases in equilibrium with the saturated solution are the tri- and hemipentahydrate of copper nitrate, the hexahydrate α and β of the zinc nitrate and the nonahydrate of aluminum nitrate. The copper and zinc nitrates are relatively soluble in opposition to the aluminum nitrate which presents some important precipitation domains.     

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.     

Fabrication and Properties of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> Composite Coatings

Al₂O₃ /xZrO₂ (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al₂O₃ and nano-sized monoclinic-ZrO₂ powders. Microstructural investigation showed that the coatings comprised well-separated Al₂O₃ and ZrO₂ lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al₂O₃ and tetragonal-ZrO₂ with trace of original α-Al₂O₃ and monoclinic-ZrO₂ phases. The effect of ZrO₂ addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO₂ improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.     

Swelling Behavior of High-Chromium,Vanadium-Bearing Titanomagnetite Pellets in H<Subscript>2</Subscript>-CO-CO<Subscript>2</Subscript> Gas Mixtures

In this study, the effects of temperature, gas composition and reduction degree on the reduction swelling index (RSI) of high-chromium vanadium-bearing titanomagnetite (HCVT) pellets during reduction with H₂-CO-CO₂ gas mixtures are investigated. The results show that the formation of massive wüstite causes most of the volume expansion of the pellets. The swelling of HCVT pellets is intensified with the temperature and content of CO, and the RSI reaches a maximum at the reduction degree of 35–50%. In H₂/CO = 5/2 (volume ratio) with a temperature range from 1223 K to 1373 K, the maximum RSI increases from 14.68% to 22.54%. Nevertheless, when the ratio of H₂/CO increases from 2/5 to 5/2 at 1223 K, the maximum RSI of the pellets decreases from 21.25% to 19.55%. Meanwhile, the shrinking rate of the pellets also decreases from 33.20% to 27.26%.     

Viscosity and Structure of CaO-SiO<Subscript>2</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-Fe<Subscript>t</Subscript>O System with Varying P<Subscript>2</Subscript>O<Subscript>5</Subscript> and FeO Content

A rotary viscosimeter and Raman spectrum were employed to measure the viscosity and structural information of the CaO-SiO₂-P₂O₅-Fe_tO system at 1673 K. The experimental data have been compared with the calculated results using different viscosity models. It shows that the National Physical Laboratory (NPL) and Pal models fit the CaO-SiO₂-P₂O₅-FeO_t system better. With the P₂O₅ content increasing from 5% to 14%, the viscosity increases from 0.12 Pa s to 0.27 Pa s. With the FeO content increasing from 30% to 40%, the viscosity decreases from 0.21 Pa s to 0.12 Pa s. Increasing FeO content makes the complicated molten melts become simple, and increasing P₂O₅ content will complicate the molten melts. The linear relation between viscosity and structure parameter Q(Si + P) was obtained by regression analysis. The calculated viscosity by using the optimized NPL and Pal model are almost identical with the fitted values.     

Development and Application of Binary Suspensions in the Ternary System Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for S-HVOF Spraying

Compositions in the system Cr₂O₃-TiO₂-Al₂O₃ are among the most used ceramic materials for thermally sprayed coating solutions. Cr₂O₃ coatings present good sliding wear resistance; Al₂O₃ coatings show excellent insulation behavior and TiO₂ striking corrosion properties. In order to combine these properties, coatings containing more than one oxide are highly interesting. The conventional spraying process is limited to the availability of binary feedstock powders with defined compositions. The use of suspensions offers the opportunity for tailor-made chemical compositions: within the triangle of Cr₂O₃-TiO₂-Al₂O₃, each mixture of oxides can be created. Criteria for the selection of raw materials as well as the relevant aspects for the development of binary suspensions in the Cr₂O₃-TiO₂-Al₂O₃ system to be used as feedstock for thermal spraying are presented. This formulation of binary suspensions required the development of water-based single-oxide suspensions with suitable behavior; otherwise, the interaction between the particles while mixing could lead up to a formation of agglomerates, which affect both the stability of the spray process and the coating properties. For the validation of this formulation procedure, binary Cr₂O₃-TiO₂ and Al₂O₃-TiO₂ suspensions were developed and sprayed using the S-HVOF process. The binary coatings were characterized and discussed in terms of microstructure and microhardness.