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.     

Effect of nanostructuring and Al alloying on friction and wear behaviour of thermal sprayed WC–Co coatings

Nanostructured WC–Co and WC–Co–Al coatings, with about 300-μm as-deposited coating thickness, were deposited by high velocity oxy-fuel (HVOF) spraying. Agglomerated nanostructured cermet powders produced by the Mechanomade® process was used for HVOF spraying. Dense and well-adherent coatings with crystal sizes below 30 nm were deposited on stainless steel 304 substrate. Porosity was less than 5% and the bond strength with the substrate was around 60 MPa. Experimental data on friction, wear, and abrasion resistance revealed that nanostructured WC–Co based coatings containing some Al as alloying element, exhibit improved tribological characteristics in comparison to nanostructured and micron-sized WC–Co coatings. This was attributed to a carbide particle distribution within the coating revealed by SEM, the absence of brittle W₂C-like phases revealed by XRD, and the presence of Al at particle/matrix boundaries revealed by TEM.     

Effect of Feedstock Size and its Distribution on the Properties of Detonation Sprayed Coatings

The detonation spraying is one of the most promising thermal spray variants for depositing wear and corrosion resistant coatings. The ceramic (Al₂O₃), metallic (Ni-20 wt%Cr) , and cermets (WC-12 wt%Co) powders that are commercially available were separated into coarser and finer size ranges with relatively narrow size distribution by employing centrifugal air classifier. The coatings were deposited using detonation spray technique. The effect of particle size and its distribution on the coating properties were examined. The surface roughness and porosity increased with increasing powder particle size for all the coatings consistently. The feedstock size was also found to influence the phase composition of Al₂O₃ and WC-Co coatings; however does not influence the phase composition of Ni-Cr coatings. The associated phase change and %porosity of the coatings imparted considerable variation in the coating hardness, fracture toughness, and wear properties. The fine and narrow size range WC-Co coating exhibited superior wear resistance. The coarse and narrow size distribution Al₂O₃ coating exhibited better performance under abrasion and sliding wear modes however under erosion wear mode the as-received Al₂O₃ coating exhibited better performance. In the case of metallic (Ni-Cr) coatings, the coatings deposited using coarser powder exhibited marginally lower-wear rate under abrasion and sliding wear modes. However, under erosion wear mode, the coating deposited using finer particle size exhibited considerably lower-wear rate.     

Study of plasma- and detonation gun-sprayed alumina coatings using taguchi experimental design

Atmospheric plasma spraying (APS) is a most versatile thermal spray method for depositing alumina (Al₂O₃) coatings, and detonation gun (D-gun) spraying is an alternative thermal spray technology for depositing such coatings with extremely good wear characteristics. The present study is aimed at comparing the characteristics of Al₂O₃ coatings deposited using the above techniques by using Taguchi experimental design. Alumina coating experiments were conducted using a Taguchi fractional-factorial (L₈) design parametric study to optimize the spray process parameters for both APS and D-gun. The Taguchi design evaluated the effect of four APS and D-gun spray variables on the measured coating attributes. The coating qualities evaluated were surface roughness, porosity, microhardness, abrasion, and sliding wear. The results show that the coating quality is directly related to the corresponding coating microstructure, which is significantly influenced by the spray parameters employed. Though it is evident that the D-gun-sprayed coatings consistently exhibit dense and uniform microstructure, higher hardness, and superior tribological performance, the attainment of suitable plasma-sprayed coatings can be improved by employing the Taguchi analysis.     

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.     

Properties of alumina-based coatings deposited by plasma spray and detonation gun spray processes

Alumina, Al₂O₃ + 3 to 40 wt% TiO₂, and Al₂O₃ + 40 wt% ZrO₂ coatings were deposited by atmospheric plasma spraying (APS) and detonation gun spraying (DGS). The coatings were evaluated by optical microscopy, microhardness measurements, and X- ray diffraction. Wear resistance of the coatings was evaluated by rubber wheel sand abrasion and particle erosion test methods. Detonation gun- sprayed coatings exhibited more homogeneous microstructures and somewhat higher microhardness than corresponding plasma- sprayed coatings. Small additions of TiO₂ (3 wt%) improved both the abrasion and erosion wear resistance, whereas 40 wt% TiO₂ significantly decreased the erosion wear resistance of both APS and DGS coatings. Alumina + 40% ZrO₂ coatings exhibited the best abrasion wear resistance of both APS and DGS coatings, but the erosion wear resistance of these coatings was lower than that of the Al₂O₃ and Al₂O₃ + 3 wt% TiO₂ coatings. The best abrasion wear resistance of the coatings studied was obtained with DGS Al₂O₃ + 40 wt% ZrO₂ and Al₂O₃ + 3 to 40 wt% TiCh coatings. These coatings exhibited lower wear rates than bulk Al₂O₃. The best erosion wear resistance was obtained with the DGS Al₂O₃ + 3 wt% TiO₂ coating; however, it exhibited a higher wear rate than bulk Al₂O₃. In general, detonation gun- sprayed coatings showed significantly enhanced abrasion and erosion wear resistance than the corresponding plasma- sprayed coatings.     

In-situ TiB2 and Al2O3 formation by DC plasma spraying

In-situ plasma spraying (IPS) is a promising process to fabricate composite coatings with in-situ formed thermodynamically stable phases. In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). It has been observed that, during the coating process, TiB₂ and Al₂O₃ are in-situ formed through the reaction between starting powders and finely dispersed in hypereutectic Al-Si matrix alloy. Also, obtained results demonstrate that in-situ reaction intensity strongly depends on spray conditions.     

Structural and Tribological Properties of Nanostructured Supersonic Cold Sprayed Ni-20 wt.% Sn Coatings

80-μm-thick nanostructured coatings consisting of a Ni solid solution, Ni₃Sn, Ni₃Sn₂, and metastable NiSn intermetallic phases were deposited via supersonic cold spraying onto inconel 718 alloy substrates. These coatings have complex nanostructured metallurgical phases as revealed by transition electron microscopy, scanning electron microscopy, and x-ray diffraction techniques. Their mechanical properties were determined by nanoindentation measurements. Furthermore, the wear behavior of these nanostructured sprayed coatings was compared to the one of the industrial bulk or sprayed coated benchmark materials. It was found that the nanostructured coatings exhibit higher wear resistance than the industrial benchmarks, thanks to an appropriate balance of hard intermetallic phases and soft Ni matrix, as well as to their nanostructuring. Their frictional characteristics under reciprocating sliding are mainly determined by the formation of an oxide-based tribo-layer, which was analyzed by x-ray photoelectron spectroscopy. The role of intermetallic phases in these coatings on the friction and wear is also discussed.     

Mechanical and tribological performance of Al2O3-TiO2 coatings elaborated by flame and plasma spraying

Mechanical properties and wear rates of Al₂O₃-13 wt.% TiO₂ (AT-13) and Al₂O₃-43 wt.% TiO₂ (AT-43) coatings obtained by flame and atmospheric plasma spraying were studied. The feed stock was either ceramic cords or powders. Results show that the wear resistance of AT-13 coatings is higher than that of AT-43 and it seems that the effect of hardness on wear resistance is more important than that of toughness. Additionally, it was established that, according to conditions used to elaborate coatings and the sliding tribological test chosen, spray processes do not seem to have an important effect on the wear resistance of these coatings.     

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.     

Effects of critical plasma spray parameter and spray distance on wear resistance of Al2O3-8 wt.%TiO2 coatings plasma-sprayed with nanopowders

Effects of plasma spraying conditions on wear resistance of nanostructured Al₂O₃-8 wt.%TiO₂ coatings plasma-sprayed with nanopowders were investigated in this study. Five kinds of nanostructured coatings were plasma-sprayed on a low-carbon steel substrate by varying critical plasma spray parameter (CPSP) and spray distance. The coatings consisted of fully melted region of γ-Al₂O₃ and partially melted region, and the fraction of the partially melted regions and pores decreased with increasing CPSP or decreasing spray distance. The hardness and wear test results revealed that the hardness of the coatings increased with increasing CPSP or decreasing spray distance, and that the hardness increase generally led to the increase in wear resistance, although the hardness and wear resistance were not correlated in the coating fabricated with the low CPSP. The main wear mechanism was a delamination one in the coatings, but an abrasive wear mode also appeared in the coating fabricated with the low CPSP. According to these wear mechanisms, the improvement of wear resistance in the coating fabricated with the low CPSP could be explained because the improved resistance to fracture due to the presence of partially melted regions might compensate a deleterious effect of the hardness decrease.     

Study of Al2O3 coatings on AISI 316 stainless steel obtained by controlled atmosphere plasma spraying (CAPS)

The tribological behaviour of Al₂O₃ coatings on AISI 316 stainless steel, obtained by the process of controlled atmosphere plasma spraying (CAPS), is studied in this work. Atmospheric plasma spraying (APS) and high pressure plasma spraying (HPPS) were applied in order to produce these coatings. The APS coatings exhibited lower microhardness values compared to the values of HPPS coatings. Regarding the HPPS coatings it was found that plasma composition, through its heat capacity, does influence the heat transfer to particles, and, consequently, their flattening and densification process, which govern coating properties. It was revealed that tribological behaviour of coatings was influenced by the applied spraying method too. Coatings from HPPS under high-enthalpy conditions led to worst wear behaviour. In general, properties, such as microstructure, microhardness, coefficient of friction and wear resistance depended on the processing conditions such as pressure and composition of the spraying chamber atmosphere.     

Microhardness as a simple means of estimating relative wear resistance of carbide thermal spray coatings: Part 1. characterization of cemented carbide coatings

A selection of WC-Co and Cr₃C₂-25%NiCr coatings deposited by plasma spraying and high velocity oxygen fuel (HVOF) were tested. The microstructures of the coatings were characterized, and their mechanical properties were assessed using Knoop microindentation procedures. The coatings were also subjected to various wear tests. All of the coatings were at least 200 μm thick and were deposited onto stainless steel substrates. The wear tests simulated abrasion, cavitation wear, sliding wear, and particle erosion wear. In this first part of a two-part contribution, the microstructures of the coatings are characterized and a discussion on the evaluation of mechanical properties from the microindentation response is presented. The nature of microhardness testing as applied to thermal spray coatings is evaluated as a means of assessing resistance to plastic flow, elasticity, and brittleness. In Part 2, the results of the various wear simulations are reported, and the utility of microhardness as an indicator of wear resistance is examined.     

Microstructure and Thermal Properties of Nanostructured 4?wt.%Al2O3-YSZ Coatings Produced by Atmospheric Plasma Spraying

Microstructure and phase composition of the nanostructured Al₂O₃ doped YSZ coatings by atmospheric plasma spraying method have been characterized with XRD, TEM and SEM. The nanostructured 4AlYSZ coatings consist mainly of t-ZrO₂, crystalline Al₂O₃ phase is absent in the coatings and the grain size of the 4AlYSZ coating is about 65 nm. The APS 4AlYSZ coating is characterized by nanozones, dense area and voids. After doping, the coefficient of thermal expansion of YSZ is decreased to 10.928 × 10⁻⁶/K. The addition of Al₂O₃ has a great influence on decreasing the thermal conductivity of nano-YSZ, which is mainly caused by the point defect scattering and grain-boundary scattering. The lifetime of nanostructured 4AlYSZ coating is about 1000 cycles at 1100 °C.     

等离子喷涂Cu-Al2O3梯度涂层的组织与耐磨性分析

针对纯陶瓷涂层由于结合强度低、孔隙率高、影响涂层耐磨性的实际,用等离子喷涂法制备了Cu-Al2O3梯度涂层,用电子扫描显微镜(SEM)、金相显微镜等手段对涂层进行微观组织和成分分析,用自制销盘式固定磨料磨损试验机,检测了Cu-Al2O3梯度涂层的耐磨料磨损性能.结果表明,采用等离子喷涂法制备的Cu-Al2O3梯度涂层无明显的组织突变和宏观层间界面,涂层的组织表现出宏观不均匀性和微观连续性分布特征;梯度涂层中当Al2O3含量(质量分数,%)达到80%时(GC6),涂层的耐磨性最高,约为基体的3倍,随着Al2O3含量继续增大,纯陶瓷涂层(GC7)的耐磨性有所下降.     

Carbon doped α-Al2O3 coatings grown by chemical vapor deposition

Alumina (Al₂O₃) coatings deposited by chemical vapor deposition (CVD) with different modifications and dopants are widely applied as wear resistant coatings on cemented carbide cutting tools. The aim of this work was to investigate the influence of CH₄ addition on the deposition of α-Al₂O₃ by low-pressure chemical vapor deposition (LPCVD). The coatings were deposited at 1005 °C on a TiN–TiCN base layer using a precursor gas mixture of AlCl₃, CH₄, CO₂, HCl, H₂S, and H₂. Coating characterization was conducted by scanning electron microscopy (SEM), glow discharge optical emission spectroscopy (GDOES), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), glancing angle X-ray diffraction (GAXRD), nanoindentation and tribological ball-on-disk tests against Al₂O₃ balls. Additionally, the ball-on-disk wear tracks were investigated by Raman spectroscopy.     

Preparation and characterization of nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-13wt.%TiO<Subscript>2</Subscript> ceramic coatings by plasma spraying

Nanostructured and conventional Al₂O₃-13wt.%TiO₂ ceramic coatings were prepared by plasma spraying with nanostructured agglomerated and conventional powders, respectively. The microstructure and microhardness of the coatings were investigated using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and microhardness measurement. Meanwhile, the friction and wear behaviors were analyzed and compared using a ball-on-disk tribometer. The results show that the conventional coating has lamellar stacking characteristic and has some pores. However, the nanostructured coating shows a bimodal microstructure, which is composed of both fully melted regions and partially melted regions. According to the microstructural difference, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The microstructural characteristics of the liquid-phase sintered region are formed due to the selective melting of TiO₂ nanoparticles during plasma spraying. On the other hand, the TiO₂ and Al₂O₃ nanoparticles of the solid-phase sintered regions are all unmelted during plasma spraying. Due to the existence of nanostructured microstructures, the nanostructured coating has a higher microhardness, a lower friction coefficient, and a better wear resistance than the conventional coating.     

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.     

自反应电弧喷涂原位合成Ti(C,N)-TiB2-Al2O3复相陶瓷涂层

以Ti+B4C为反应药芯、Al为外皮材料制备反应型喷涂丝材,探讨利用自反应电弧喷涂技术在45钢基体表面制备复相陶瓷涂层的可行性。以X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)等方法分析、观察了涂层的组织与结构,测试了涂层的主要力学性能。结果表明:利用制备的药芯丝材进行喷涂试验,可获得由TiB2、TiB、TiC0.3N0.7、TiN、Al2O3、AlN等多相组成的复相陶瓷涂层。涂层呈典型的层状结构,其连续的基体相内弥散分布着离散的第二、第三相。涂层与基体间的结合强度为18.9MPa,涂层的平均显微硬度与弹性模量分别为735.4HV0.2和461.4GPa,摩擦因数在0.45～0.50之间,耐磨性能较基体材料提高3倍以上。     

A comparative study of tribological behavior of plasma and D-gun sprayed coatings under different wear modes

In recent years, thermal sprayed protective coatings have gained widespread acceptance for a variety of industrial applications. A vast majority of these applications involve the use of thermal sprayed coatings to combat wear. While plasma spraying is the most versatile variant of all the thermal spray processes, the detonation gun (D-gun) coatings have been a novelty until recently because of their proprietary nature. The present study is aimed at comparing the tribological behavior of coatings deposited using the two above techniques by focusing on some popular coating materials that are widely adopted for wear resistant applications, namely, WC-12% Co, A1₂O₃, and Cr₃C₂-MCr. To enable a comprehensive comparison of the above indicated thermal spray techniques as well as coating materials, the deposited coatings were extensively characterized employing microstructural evaluation, microhardness measurements, and XRD analysis for phase constitution. The behavior of these coatings under different wear modes was also evaluated by determining their tribological performance when subjected to solid particle erosion tests, rubber wheel sand abrasion tests, and pin-on-disk sliding wear tests. The results from the above tests are discussed here. It is evident that the D-gun sprayed coatings consistently exhibit denser microstructures and higher hardness values than their plasma sprayed counterparts. The D-gun coatings are also found to unfailingly exhibit superior tribological performance superior to the corresponding plasma sprayed coatings in all wear tests. Among all the coating materials studied, D-gun sprayed WC-12%Co, in general, yields the best performance under different modes of wear, whereas plasma sprayed Al₂O₃ shows least wear resistance to every wear mode.