Deposition of Al2O3-TiO2 Nanostructured Powders by Atmospheric Plasma Spraying

Al₂O₃-13%TiO₂ coatings were deposited on stainless steel substrates from conventional and nanostructured powders using atmospheric plasma spraying (APS). A complete characterization of the feedstock confirmed its nanostructured nature. Coating microstructures and phase compositions were characterized using SEM, TEM, and XRD techniques. The microstructure comprised two clearly differentiated regions. One region, completely fused, consisted mainly of nanometer-sized grains of γ-Al₂O₃ with dissolved Ti⁺⁴. The other region, partly fused, retained the microstructure of the starting powder and was principally made up of submicrometer-sized grains of α-Al₂O₃, as confirmed by TEM. Coating microhardness as well as tribological behavior were determined. Vickers microhardness values of conventional coatings were in average slightly lower than the values for nanostructured coating. The wear resistance of conventional coatings was shown to be lower than that of nanostructured coatings as a consequence of Ti segregation. A correlation between the final properties, the coating microstructure, and the feedstock characteristics is given.     

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.     

The Effect of Heat Treatment on the Oxidation Behavior of HVOF and VPS CoNiCrAlY Coatings

Free-standing VPS and HVOF CoNiCrAlY coatings were produced. The as-sprayed HVOF coating retained the γ/β microstructure of the feedstock powder, and the VPS coating consisted of a single (γ) phase. A 3-h, 1100 °C heat treatment in vacuum converted the single-phase VPS coating to a two-phase γ/β microstructure and coarsened the γ/β microstructure of the HVOF coating. Oxidation of free-standing as-sprayed and heat-treated coatings of each type was carried out in air at 1100 °C for a duration of 100 h. Parabolic rate constant(s), K _p, were determined for free-standing, as-sprayed VPS and HVOF coatings as well as for free-standing coatings that were heat treated prior to oxidation. The observed increase in K _p following heat treatment is attributed to a sintering effect eliminating porosity from the coating during heat treatment. The lower K _p values determined for both HVOF coatings compared to the VPS coatings is attributed to the presence of oxides in the HVOF coatings, which act as the barrier to diffusion. Oxidation of the as-sprayed coatings produced a dual-layer oxide consisting of an inner α-Al₂O₃ layer and outer spinel layer. Oxidation of the heat-treated samples resulted in a single-layer oxide, α-Al₂O₃. The formation of a thin α-Al₂O₃ layer during heat treatment appeared to prevent nucleation and growth of spinel oxides during subsequent oxidation.     

Microstructural characterization of radio frequency and direct current plasma-sprayed Al2O3 coatings

Microstructures of radio frequency (RF) and direct current (DC) plasma-sprayed Al₂O₃ coatings deposited onto steel substrates were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), electron microprobe analysis (EMPA), polarizing optical microscopy (OM), and transmission electron microscopy (TEM). Because RF and DC plasmas produce different particle heating and acceleration, the morphology, phase structure, and fracture modes of the coatings vary substantially. In the case of RF coatings, a clear lamellar microstructure with relatively thick lamellae was observed, which is due to the large particles and the low particle velocities, with α-Al₂O₃ as the predominant phase and with delamination type of fracture detected on the fracture surface. In contrast, the DC coatings consisted of predominantly metastable γ-Al₂O₃ as well as amorphous phases, with a mixed fracture mode of the coating observed. In spite of limited interfacial interdiffusion detected by EMPA, TEM showed an interfacial layer existing at the interface between the coating and the substrate for both cases. For RF coatings, the interfacial layer on the order of 1 μm was composed of three sublayers, each of which was different in composition and morphology. However, the interfacial layer for the DC coating consisted primarily of an amorphous phase, containing both coating and substrate materials with or without platelike microcrystals; although in some regions a thick amorphous Al₂O₃ layer was in direct contact with the substrate.     

Characterization of plasma sprayed Fe-17Cr-38Mo-4C amorphous coatings crystallizing at extremely high temperature

A Fe-17Cr-38Mo-4C alloy powder was plasma sprayed by three processes: an 80 kW low-pressure plasma spray (LPPS), a 250 kW high-energy plasma spray (HPS), and a 40 kW conventional plasma spray (APS). The as-sprayed coating obtained by the LPPS process is composed of only amorphous phase. As-sprayed coatings obtained by the HPS and APS processes are a mixture of amorphous and crystalline phases. The three as-sprayed coatings exhibit a high hardness of 1000 to 1100 DPN. The amorphous phase in these coatings crystallizes at a high temperature of about 920 K. A very fine structure composed of hard ϰ-phase and carbides is formed after crystallization. The hardness of the coating obtained by LPPS reaches a maximum of 1450 DPN just after crystallization on tempering and retains a high hardness more than 1300 DPN after tempering at high temperatures of 1173 or 1273 K. The corrosion potential of the amorphous coating is the highest among the three coatings and higher than that of a SUS316L stainless steel coating. The anodic polarization measurements infer that the corrosion resistance of the amorphous coating is superior or comparable to SUS316L stainless steel coating in H₂SO₄ solution.     

Plasma Spray Coatings of Ni-Al-SiC Composite

Ni-Al-SiC powder mixture containing 12 wt.% SiC was prepared by conventional ball milling. Morphological and microstructural investigations showed that powder particles after 15 h of milling time had the optimum characteristics with respect to their size and microstructure. X-ray diffraction patterns of powder particles included only the elemental Ni, Al, and SiC peaks without any traces of oxides or intermetallic phases. The powder mixture was then deposited onto a steel substrate by atmospheric plasma spray (APS) process under different conditions. The results showed that under APS conditions used here, the coatings were composed of various intermetallics including Ni-Al and Ni₂Al₃. The mean hardness of coating was found to be about 567 HV. It was also found that by increasing current density of APS, the coating/substrate adhesive strength was increased.     

Yb<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>7</Subscript> Environmental Barrier Coatings Deposited by Various Thermal Spray Techniques: A Preliminary Comparative Study

Dense, crack-free, uniform, and well-adhered environmental barrier coatings (EBCs) are required to enhance the environmental durability of silicon (Si)-based ceramic matrix composites in high pressure, high gas velocity combustion atmospheres. This paper represents an assessment of different thermal spray techniques for the deposition of Yb₂Si₂O₇ EBCs. The Yb₂Si₂O₇ coatings were deposited by means of atmospheric plasma spraying (APS), high-velocity oxygen fuel spraying (HVOF), suspension plasma spraying (SPS), and very low-pressure plasma spraying (VLPPS) techniques. The initial feedstock, as well as the deposited coatings, were characterized and compared in terms of their phase composition. The as-sprayed amorphous content, microstructure, and porosity of the coatings were further analyzed. Based on this preliminary investigation, the HVOF process stood out from the other techniques as it enabled the production of vertical crack-free coatings with higher crystallinity in comparison with the APS and SPS techniques in atmospheric conditions. Nevertheless, VLPPS was found to be the preferred process for the deposition of Yb₂Si₂O₇ coatings with desired characteristics in a controlled-atmosphere chamber.     

Plasma-sprayed nanostructured Al2O3/TiO2 powders and coatings

Air plasma spray has been used to produce metastable oxide-ceramic powders and coatings, starting with commercially available Al₂O₃/13TiO₂ powder feed. The feed material undergoes rapid melting and homogenization in the high-temperature zone of the plasma jet. A metastablex-Al₂O₃·TiO₂ phase is formed when the molten droplets are quenched on a chilled substrate. The metastable phase has a defect spinel structure and a nanocrystalline grain size. When heated, it decomposes into an equilibrium two-phase structure, consisting ofα-Al₂O₃ andβ-Al₂O₃·TiO₂. Both types of ceramic materials have potential as hard, wear-resistant coatings.     

Structure and Tribological Performance of Nanostructured ZrO<Subscript>2</Subscript>-3 mol% Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Coatings Deposited by Air Plasma Spraying

In this study, nanostructured ZrO₂-3 mol% Y₂O₃ coatings were deposited by air plasma spray using reconstituted feedstock. The coating structures were characterized by x-ray diffractometer, micro-Raman spectrometer, field emission scanning electron microscope, and transmission electron microscope. It is revealed that the as-sprayed coating is mainly composed of columnar grains with diameters <100 nm and demonstrates the better toughness, higher microhardness, and lower porosity. It consists only of nontransformable tetragonal ZrO₂ phase. The tribological performance of the coating was examined with a ball-on-disk apparatus under dry sliding conditions. The results show that the friction coefficient of as-sprayed coating was approximately one-fifth of the conventional zirconia coating and wear rate was lower one order of magnitude than the conventional zirconia coating. The dominant wear mechanism is abrasive wear. The improved wear resistance can be attributed to the increased mechanical properties of as-sprayed coating.     

Effect of Microstructure on the Thermal Conductivity of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-YSZ Coatings

The microstructures of three atmospheric plasma-sprayed (APS) Al₂O₃-ZrO₂ coatings were investigated using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The differences in the microstructures of the three Al₂O₃-ZrO₂ coatings, including their phase compositions, cracks, pores, grain sizes, and solid solutions, were analyzed in detail. A close relationship was observed between the thermal conductivities of the coatings and the microstructures, and the Al₂O₃-YSZ coatings with more spherical pores, fewer vertical cracks, and finer grains exhibited the lowest thermal conductivity of 0.91 W/m·K. Compared with YSZ coatings, Al₂O₃-YSZ coatings can exhibit lower thermal conductivity, which may be attributed to the formation of an amorphous phase, smaller grains, and Al₂O₃-YSZ solid solution.     

Comparison of ZrB<Subscript>2</Subscript>-MoSi<Subscript>2</Subscript> Composite Coatings Fabricated by Atmospheric and Vacuum Plasma Spray Processes

In this work, ZrB₂-20 vol.% MoSi₂ (denoted as ZM) composite coatings were fabricated by atmospheric plasma spray (APS) and vacuum plasma spray (VPS) techniques, respectively. Phase composition and microstructure of the composite coatings were characterized. Their oxidation behaviors and microstructure changes at 1500 °C were comparatively investigated. The results showed that VPS-ZM coating was composed of hexagonal ZrB₂, tetragonal and hexagonal MoSi₂, while certain amount of ZrO₂ existed in APS-ZM coating. The oxide content, surface roughness and porosity of VPS-ZM coating were apparently lower than those of APS-ZM coating. The mass gain of APS-ZM coating was maximum at the beginning (1500 °C, 0 h) and then decreased with the oxidation time extending, while the mass of VPS-ZM coating gradually increased with increasing the oxidation time. The possible reasons for the different oxidation behaviors of the two kinds of coatings were analyzed.     

Mechanical and Thermal Transport Properties of Suspension Thermal-Sprayed Alumina-Zirconia Composite Coatings

Micro-laminates and nanocomposites of Al₂O₃ and ZrO₂ can potentially exhibit higher hardness and fracture toughness and lower thermal conductivity than alumina or zirconia alone. The potential of these improvements for abrasion protection and thermal barrier coatings is generating considerable interest in developing techniques for producing these functional coatings with optimized microstructures. Al₂O₃-ZrO₂ composite coatings were deposited by suspension thermal spraying (APS and HVOF) of submicron feedstock powders. The liquid carrier employed in this approach allows for controlled injection of much finer particles than in conventional thermal spraying, leading to unique and novel fine-scaled microstructures. The suspensions were injected internally using a Mettech Axial III plasma torch and a Sulzer-Metco DJ-2700 HVOF gun. The different spray processes induced a variety of structures ranging from finely segregated ceramic laminates to highly alloyed amorphous composites. Mechanisms leading to these structures are related to the feedstock size and in-flight particle states upon their impact. Mechanical and thermal transport properties of the coatings were compared. Compositionally segregated crystalline coatings, obtained by plasma spraying, showed the highest hardness of up to 1125 VHN_{3 N}, as well as the highest abrasion wear resistance (following ASTM G65). The HVOF coating exhibited the highest erosion wear resistance (following ASTM G75), which was related to the toughening effect of small dispersed zirconia particles in the alumina-zirconia-alloyed matrix. This microstructure also exhibited the lowest thermal diffusivity, which is explained by the amorphous phase content and limited particle bonding, generating local thermal resistances within the structure.     

Phase Relations in Si-Al-M-O-C (M = Zr,Mg) Systems

The present work determined the phase relations in Si-Al-M-O-C (M = Zr, Mg) systems, involving SiC-Al₂O₃-ZrO₂, SiC-Al₂O₃-MgO, SiC-SiO₂-Al₂O₃-ZrO₂ and SiC-SiO₂-Al₂O₃-MgO systems by XRD phase analyses of the solid-state reacted samples from powder mixtures of SiC, Al₂O₃, ZrO₂, MgO and SiO₂. Within these systems, SiC was respectively compatible with other neighboring phases, forming a set of four-phase compatibility tetrahedrons. The subsolidus phase diagrams of the SiC-SiO₂-Al₂O₃-ZrO₂ and SiC-SiO₂-Al₂O₃-MgO quaternary systems were presented.     

Consolidation of Al2O3/Al Nanocomposite Powder by Cold Spray

While the improvement in mechanical properties of nanocomposites makes them attractive materials for structural applications, their processing still presents significant challenges. In this article, cold spray was used to consolidate milled Al and Al₂O₃/Al nanocomposite powders as well as the initial unmilled and unreinforced Al powder. The microstructure and nanohardness of the feedstock powders as well as those of the resulting coatings were compared. The results show that the large increase in hardness of the Al powder after mechanical milling is preserved after cold spraying. Good quality coating with low porosity is obtained from milled Al. However, the addition of Al₂O₃ to the Al powder during milling decreases the powder and coating nanohardness. This lower hardness is attributed to non-optimized milling parameters leading to cracked particles with insufficient Al₂O₃ embedding in Al. The coating produced from the milled Al₂O₃/Al mixture also showed lower particle cohesion and higher amount of porosity.     

Reactive Plasma Spraying of Fine Al2O3/AlN Feedstock Powder

Reactive plasma spraying (RPS) is a promising technology for in situ formation of aluminum nitride (AlN) coatings. Recently, AlN-based coatings were fabricated by RPS of alumina (Al₂O₃) powder in N₂/H₂ thermal plasma. This study investigated the feasibility of RPS of a fine Al₂O₃/AlN mixture and the influence of the plasma gases (N₂, H₂) on the nitriding conversion, and coating microstructure and properties. Thick AlN/Al₂O₃ coatings with high nitride content were successfully fabricated. The coatings consist of h-AlN, c-AlN, Al₅O₆N, γ-Al₂O₃, and a small amount of α-Al₂O₃. Use of fine particles enhanced the nitriding conversion and the melting tendency by increasing the surface area. Furthermore, the AlN additive improved the AlN content in the coatings. Increasing the N₂ gas flow rate improved the nitride content and complete crystal growth to the h-AlN phase, and enhanced the coating thickness. On the other hand, though the H₂ gas is required for plasma nitriding of the Al₂O₃ particles, increasing its flow rate decreased the nitride content and the coating thickness. Remarkable influence of the plasma gases on the coating composition, microstructure, and properties was observed during RPS of the fine particles.     

Al2O3-ZrO2 mixed oxide composite incorporated aluminium rich zinc coatings for high wear resistance

Corrosion resistance and wear resistance are the two important parameters for high performance of zinc galvanic coating. In the present work, the improvement of these two characteristics was achieved by the incorporation of Al₂O₃-ZrO₂ mixed oxide composite in the coating. Al₂O₃-ZrO₂ mixed oxide composite was synthesized from ZrOCl₂·8H₂O. Aluminium rich zinc coatings with high sliding wear resistance was developed from a galvanic bath containing the mixed oxide. Based on the performance of the coating during physicochemical and electrochemical characterization, the concentration of mixed oxide composite in the bath was optimized as 0.50 wt% Al₂O₃-0.50 wt% ZrO₂. While rich in Al-metal content in the coating caused high corrosion resistance, the incorporation of the mixed oxide improved structural characteristics of the coating resulting in high wear resistance also. The coating was nonporous in nature and even the interior layers had high stability. The coatings have potential scope for high industrial utility.     

In-situ formed γ-Al2O3 nanocrystals repaired and toughened Al2O3 coating prepared by plasma spraying

During process of plasma spraying of alumina with the stable α phase in the as-received powder, metastable γ phase tends to form in the as-deposited coating. In this paper, plasma-sprayed Al₂O₃ coating was investigated using transmission electron microscopy. In situ formation of γ-Al₂O₃ nanocrystals was observed in the pre-existing cracks of the as-sprayed Al₂O₃ coating, which contributes to self-repairing and self-toughening of the Al₂O₃ coating. Except for the predominant intergranular fracture, the pre-formed γ-Al₂O₃ nanocrystals would effectively obstruct the crack development in the coating and then the coating fracture toughness is enhanced.     

Column Formation in Suspension Plasma-Sprayed Coatings and Resultant Thermal Properties

The suspension plasma spray (SPS) process was used to produce coatings from yttria-stabilized zirconia (YSZ) powders with median diameters of 15 μm and 80 nm. The powder-ethanol suspensions made with 15-μm diameter YSZ particles formed coatings with microstructures typical of the air plasma spray (APS) process, while suspensions made with 80-nm diameter YSZ powder yielded a coarse columnar microstructure not observed in APS coatings. To explain the formation mechanisms of these different microstructures, a hypothesis is presented which relates the dependence of YSZ droplet flight paths on droplet diameter to variations in deposition behavior. The thermal conductivity (k _th) of columnar SPS coatings was measured as a function of temperature in the as-sprayed condition and after a 50 h, 1200 °C heat treatment. Coatings produced from suspensions containing 80 nm YSZ particles at powder concentrations of 2, 8, and 11 wt.% exhibited significantly different k _th values. These differences are connected to microstructural variations between the SPS coatings produced by the three suspension formulations. Heat treatment increased the k _th of the coatings generated from suspensions containing 2 and 11 wt.% of 80 nm YSZ powder, but this k _th increase was less than has been observed in APS coatings.     

In situ Formed α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Repaired the Preexisting Microcracks in Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating via Stress-Induced Phase Transformation

In the present study, the phase composition and generation mechanism of the nanocrystals located in the microcracks of plasma-sprayed Al₂O₃ coating were reevaluated. The Al₂O₃ coatings were investigated using transmission electron microscopy and x-ray diffraction. We supply the detailed explanations to support the new viewpoint that in situ formation of α-Al₂O₃ nanocrystals in the preexisting microcracks of the as-sprayed Al₂O₃ coating may be due to the stress-induced phase transformation. Owing to the partially coherent relationship, the phase interfaces between the α-Al₂O₃ nanocrystals with the preferred orientation and the γ-Al₂O₃ matrix may possess better bonding strength. The α-Al₂O₃ nanocrystals could repair the microcracks in the coating, which further strengthens grain boundaries. Grain boundary strengthening is beneficial to the coating fracture toughness enhancement.     

Wear Resistance Improvement of Small Dimension Invar Massive Molds for CFRP Components

Invar alloy (Fe-36%Ni) is used in industrial applications that require high dimensional stability because of its exceptionally low thermal expansion coefficient. The purpose of this work is to improve the wear resistance of the molds in the production of carbon-fiber reinforced plastic (CFRP) components applying thermal spray coatings. Four different kinds of commercial powders were coated on an Invar substrate: ZrO₂-8Y₂O₃, Al₂O₃-13TiO₂, and Cr₂O₃ by air plasma spray (APS) and WC-CoCr by high-velocity oxygen fuel (HVOF). Metallographic microscopy observation and scanning electron microscopic analysis were carried out, microhardness and fracture toughness were evaluated using the microindentation method. Friction behavior and wear resistance were evaluated with pin-on-disk apparatus. Tungsten carbide coating had the lowest average coefficient of friction. Cermet and alumina-titania coatings showed the lowest wear mass loss. Among the APS ceramic coatings, alumina-titania exhibited the best wear behavior and the HVOF cermet coating exhibited the best behavior among all the coatings.