Effect of Feedstock Powders on the Microstructural and Electrical Characteristics of 8 mol% Yttria-Stabilized Zirconia Plasma-Sprayed Coatings

Plasma-sprayed coatings of 8 mol% yttria-stabilized zirconia (YSZ) were fabricated using the feedstock powders obtained from co-precipitation (PPT) and spray-drying (SD) processes. Particle size and the specific mass (SM) of the feedstock powder were found to be the critical parameters that influence the microstructural and electrical properties of the coatings. While dense and larger particle-sized PPT powder resulted in a porous microstructure, dense coatings were obtained for SD powders with relatively lower SM. Electrical conductivity values of SD-coatings were found to be 30% higher than that of PPT-coatings. Electrical conductivity values of plasma-sprayed PPT-coatings improved significantly on decreasing the particles size. However, the size effect was only subtle in the case of SD coatings. PPT-coatings fabricated from smaller particle-sized powders had the necessary electrical conductivities appropriate for solid oxide fuel cell electrolyte applications.     

Tribological properties of TiC-Fe coatings obtained by plasma spraying reactive powders

Titanium carbide-based coatings have been considered for use in sliding wear resistance applications. Carbides embedded in a metal matrix would improve wear properties, providing a noncontinuous ceramic surface. TiC-Fe coatings obtained by plasma spraying of spray-dried TiC-Fe composite powders containing large and angular TiC particles are not expected to be as resistant as those containing TiC particles formed upon spraying. Coatings containing 60 vol% TiC dispersed in a steel matrix deposited by plasma spraying reactive micropellets, sintered reactive micropellets, and spray-dried TiC-Fe composite powders are compared. The sliding wear resistance of these coatings against steel was measured following the test procedure recommended by the Versailles Advanced Materials and Standards (VAMAS) program, and the inherent surface porosity was evaluated by image analysis. Results show that, after a 1-km sliding distance, TiC-Fe coatings obtained after spraying sintered reactive powders exhibit scar ring three times less deep than sprayed coatings using spray-dried TiC-Fe composite powders. For all coatings considered, porosity is detrimental to wear performance, because it generally lowers the coating strength and provides cavities that favor the adhesion of metal. However, porosity can have a beneficial effect by entrapping debris, thus reducing friction. The good wear behavior of TiC-Fe coatings manufactured by plasma spraying of sintered reactive powders is related to their low coefficient of friction against steel. This is due to the microstructure of these coatings, which consists of 0.3 to 1 μm TiC rounded particles embedded in a steel matrix. Presented at the International Conference on Metallurgical Coatings and Thin Films, ICMCTF-92, Apr 6–10, 1992, San Diego.     

Manufacturing of high performance solid oxide fuel cells (SOFCs) with atmospheric plasma spraying (APS)

The potential of atmospheric plasma spraying (APS) technology has been investigated for the manufacture of anode, electrolyte and cathode of a solid oxide fuel cell. As the substrate a tape-casted FeCr alloy was used. It turned out that all layers can be applied by this technique, however, the APS cathode layer, although applied by suspension plasma spraying led to cells with rather low performance. Much better cell characteristics could be obtained by using screen-printed LSCF cathodes, which do not need any additional thermal treatment.Anode layers with high electrochemical activity were produced by separate injection of NiO and YSZ powders. The manufacturing of gastight electrolyte layers was a key-issue of the present development. As APS ceramic coatings typically contain microcracks and pores their leakage rate is not sufficiently low for SOFC applications.Based on the understanding of the formation of defects during spraying an optimized spraying process was developed which led to highly dense coatings with the appearance of a bulk, sintered ceramic. Open cell voltages above 1 V proofed the low leakage rates of the rather thin (< 50 μm) coatings. With these cells having a screen-printed cathode an output power of 500 mW/cm² could be achieved at 800 °C.It turned out that the long-term stability of the metal substrate based APS SOFCs was rather poor. The aging of the cells was probably due to interdiffusion of anode and substrate material. Hence, diffusion barrier was applied by APS between substrate and anode. These layers were very effective in reducing the degradation rate. For these cells the output power reached 800 mW/cm².     

Hot isostatic pressing of plasma sprayed Ni-base alloys

This article reports the effects of hot isostatic pressing (HIPing) on the microstructure and properties of plasma sprayed Ni-based alloy coatings. Hot isostatic pressing was used as a post- spray treatment on plasma sprayed Ni-5Al, Ni-20Al, and NiCrAl coatings. The aim was to densify the coatings and modify physical properties such as strength, amount of porosity, and hardness. The coatings were HIPed at 750 to 950 ‡C at pressures of 50 to 200 MPa and held for 1 h. The treated coatings were examined by optical microscopy and scanning electron microscopy (SEM). Coating porosity was determined using a combination of an image analyzer and SEM. Near- zero porosity levels could be obtained, and HIP treatment at increasing temperatures and pressures changed the microstructure and increased the microhardness of the coatings. Mechanical testing of the coatings was performed on a Dynamic Mechanical Analyzer (DMA) from ambient to — 1000 ‡C. The results showed that the elastic modulus of HIPed coatings was greater than as-sprayed coatings up to — 750 ‡C. These changes can be related to plastic flow, interlamellar diffusion, and creep that occur at increased temperatures and pressures.     

Copper-titanium diboride coatings obtained by plasma spraying reactive micropellets

Electrotribological applications require materials with both high electrical conductivity and wear resisance. For this purpose, a copper- base plasma sprayed coating containing titanium diboride particles was developed. The process for fabricating this CU- TiB₂ coating consists of plasma spraying reactive powders that contain a Cu- Ti alloy and boron. The reaction between the copper alloy and boron proceeds in different steps going from solid- state diffusion of titanium and copper to the synthesis of TiB₂ in a liquid below 1083 ‡C. Plasma sprayed copper coatings contain finer TiB₂ crystals than Cu- TiB₂ materials synthesized in a furnace at 1200 ‡C. Coatings with 25 vol% TiB2 have hardnesses that are comparable to Cu- Co- Be and Cu- Ni- Be alloys and to Cu- W and Cu- Mo alloys used in spot welding. Their low electrical resistivity of 52 ΜΩ cm could be increased by lowering the oxygen content with coatings and controlling the formation of TiB₂ clusters, the titanium content in solution in copper remaining low after the synthesis reaction.     

Dry sliding wear behavior of ceramic-metal composite coatings prepared by plasma spraying of self-reacting powders

Ceramic-metal composite (CMC) coatings were deposited on the surface of Fe-0.14–0.22 wt.% C steel by plasma spraying of self-reacting Fe₂O₃−Al composite powders. The dry sliding friction and wear character of the CMC coatings are investigated in this paper. The wear resistance of the CMC coatings was significantly better than that of Al₂O₃ coatings under the same sliding wear conditions. The tough metal, which is dispersed in the ceramic matrix, obviously improved the toughness of the CMC coatings. Wear mechanisms of the CMC coatings were identified as a combination of abrasive and adhesive wear.     

Improved Protection Properties by Using Nanostructured Ceramic Powders for HVOF Coatings

The potential of the high-velocity oxy-fuel (HVOF) thermal spray process for reduced porosity in coatings compared to those produced by other ambient thermal spray processes is well known. The ability to produce high-density ceramic coatings offers potential in high-performance applications in the field of wear, corrosion resistance, and dielectric coatings. However, due to operational limit of the HVOF process to effectively melt the ceramic particles, the process—structure relationship must be well optimized. It has been also demonstrated that benefits from HVOF ceramic coatings can be obtained only if particles are melted enough and good lamella adhesion is produced. One strategy to improve melting of ceramic particles in relative low-flame temperatures of HVOF process is to modify particle crystal structure and composition. In this paper the effect of the powder manufacturing method and the composition on deposition efficiency of spray process as well as on the mechanical properties of the HVOF sprayed are studied. Effect of fuel gas, hydrogen vs. propane, was also demonstrated. Studied materials were alumina-, chromia-, and titania-based agglomerated powders. Coating properties such as microstructure, hardness, abrasive wear resistance, and relative fracture toughness were compared to the coating manufactured by using conventional fused and crushed powders. It can be concluded that powder size distribution and microstructure should be optimized to fulfill process requirements very carefully to produce coatings with high deposition efficiency, dense structure, improved fracture toughness, and adhesion.     

The effects of artificial aging on the microstructure and fracture toughness of Al-Cu-Li alloy 2195

Aluminum-lithium alloys have shown promise for aerospace applications, and National Aeronautics and Space Administration (NASA) has selected the aluminum-lithium Alloy 2195 for the main structural alloy of the super light weight tank (SLWT) for the space shuttle. This alloy has significantly higher strength than conventional2xxx alloys (such as 2219) at both ambient and cryogenic temperatures. If properly processed and heat treated, this alloy can display higher fracture toughness at cryogenic temperature than at ambient temperature. However, the properties of production materials have shown greater variation than those of other established alloys, as is the case with any new alloy that is being transitioned to a demanding application. Recently, some commercial 2195 plates for the SLWT program were rejected, mostly due to low CFT or FTR at ambient and cryogenic temperatures. Investigation of the microstructure property relationships of Al-Cu-Li based alloys indicates that the poor fracture toughness properties can be attributed to excessive T₁ precipitation at subgrain boundaries. Lowering the aging temperature is one way to avoid excessive T₁ precipitation at subgrain boundaries. However, this approach results in a significant drop in yield strength. In addition, low-temperature aging is associated with sluggish aging kinetics, which are not desirable for industrial mass production. Therefore, the present study was undertaken to develop an aging process that can improve fracture toughness without sacrificing yield and tensile strength. A multistep heating-rate controlled (MSRC) aging treatment has been developed that can improve the cryogenic fracture toughness of aluminum-lithium Alloy 2195. At the same levels of yield strength (YS), this treatment results in considerably higher fracture toughness than that found in Alloy 2195, which has received conventional (isothermal) aging. Transmission electron microscopy revealed that the new treatment greatly reduces the size and density of subgrain-boundary T₁ precipitates. In addition, it promotes T₁ and θ" nucleation, resulting in a fine and dense distribution of precipitate particles in the matrix. The MSRC aging treatment consists of (a) aging at 127‡C (260‡F) for 5 h, (b) heating continuously from 127‡C (260‡F) to 135‡C (275‡F) at a rate of 0.556‡C/h (1‡F/h), (c) holding at 135‡C (275‡F) for 5 h, (d) heating continuously from 135 to 143‡C (275 to 290‡F) at a rate of 0.556‡C/h (1‡F/h), and (e) holding at 143‡C (290‡F) for 25 h to obtain a near peak-aged condition.     

Influence of Ceramic Powder Size on Process of Cermet Coating Formation by Cold Spray

Influence of the ceramic particle size on the process of formation of cermet coatings by cold spray is experimentally studied. A specially developed nozzle with separate injection of ceramic and metal powders into the gas stream is used in the experiments. The results obtained demonstrate that fine ceramic powders (Al₂O₃, SiC) produce a strong activation effect on the process of spraying soft metal (Al, Cu) and increase deposition efficiency of the metal component of the mixture compared to the pure metal spraying. At the same time, coarse ceramic powder produces a strong erosion effect that considerably reduces coating mass growth and deposition efficiency of the metal component. It is experimentally shown that the addition of fine hard powder to soft metals as Al and Cu allows to significantly reduce the “critical” temperature (the minimum gas stagnation temperature at which a nonzero particle deposition is observed) for spraying these metals.     

Plasma Sprayed Coating Using Mullite and Mixed Alumina/Silica Powders

Plasma sprayed ceramic coatings are widely used for thermal barrier coating applications. Commercially available mullite powder particles and a mixture of mechanically alloyed alumina and silica powder particles were used to deposit mullite ceramic coatings by plasma spraying. The coatings were deposited at three different substrate temperatures (room temperature, 300?°C, and 600?°C) on stainless steel substrates. Microstructure and morphology of both powder particles as well as coatings were investigated by using scanning electron microscopy. Phase formation and degree of crystallization of coatings were analyzed by x-ray diffraction. Differential thermal analysis (DTA) was used to study phase transformations in the coatings. Results indicated that the porosity level in the coatings deposited using mullite initial powder particles were lower than those deposited using the mixed initial powder particles. The degree of crystallization of the coatings deposited using the mixed powder particles was higher than that deposited using mullite powder particles at substrate temperatures of 25 and 300?°C. DTA curves of the coatings deposited using the mixed powders showed some transformation of the retained amorphous phase into mullite and alumina. The degree of crystallization of the as sprayed coatings using the mixed powder particles was significantly increased after post deposition heat treatments. The results indicated that the mechanically alloyed mixed powder can be used as initial powder particles for deposition of mullite coatings instead of using mullite powders.     

Electrophoretic co-deposition of diamond/borosilicate glass composite coatings

Composite coatings made of diamond powders and borosilicate glass have been deposited on stainless steel substrates by electrophoretic co-deposition. Ethanol and acetone suspensions containing diamond powders of particle size 1-2 μm and borosilicate glass powders of size 0.1-0.5 μm were used. Electrophoretic deposition (EPD) parameters were optimized by a trial-and-error-approach. Microstructures of deposited and sintered coatings were investigated by XRD and SEM analysis. The results show that applied voltages up to 10 V led to thin and incomplete coatings. Voltages higher than 50 V resulted in uneven coatings with uncontrolled thickness and poor uniformity. The best results were achieved using ethanol suspensions. Smooth, uniform and dense coatings with diamond and glass particles distributed uniformly were obtained under applied voltages in the range of 30-50 V and a deposition time of 4 min. The concentration ratio of diamond to borosilicate glass in the composite coatings was in good correlation with the original ratio in suspension, thus control of the coating microstructure and composition is possible. During sintering at 900 °C, the glass particles softened; sintered by viscous flow and spread over the diamond particles surface. Thus a glass layer forms protecting the diamond from oxidization or graphitization and bonding the diamond particles together.     

Reactive plasma spraying of wear-resistant coatings

A method for producing wear-resistant, carbide-reinforced coatings has been investigated. A conventional low-pressure plasma gun has been modified with a downstream reactor into which carbon-containing gases are mixed, heated, and disassociated. The disassociated gas ions—H* and C* —are subsequently brought into contact with heated, molten metal matrix powders. Experiments with NiCr/Ti blends and W powders have shown that uniformly dispersed carbides such as, TiC, Cr^Cy, WC, and W2C were formed in situ on the metal precursor powders during deposition. The in situ formed particles, being formed directly from the matrices, show excellent matrix cohesion and lead to high and uniform deposit microhardnesses. The process is described and several evaluations of materials, reactive gases, and spray conditions are reported. Microanalysis of the coatings are presented, microhardness values are reported, and XRD identifies the in situ formed phases.     

Application of Suspension Plasma Spraying (SPS) for Manufacture of Ceramic Coatings

Conventional thermal spray processes as atmospheric plasma spraying (APS) have to use easily flowable powders with a size up to 100 μm. This leads to certain limitations in the achievable microstructural features. Suspension plasma spraying (SPS) is a new promising processing method which employs suspensions of sub-micrometer particles as feedstock. Therefore much finer grain and pore sizes as well as dense and also thin ceramic coatings can be achieved. Highly porous coatings with fine pore sizes are needed as electrodes in solid-oxide fuel cells. Cathodes made of LaSrMn perovskites have been produced by the SPS process. Their microstructural and electrochemical properties will be presented. Another interesting application is thermal barrier coating (TBC). SPS allows the manufacture of high-segmented TBCs with still relatively high porosity levels. In addition to these specific applications also the manufactures of new microstructures like nano-multilayers and columnar structures are presented.     

Formation and behavior of thermal barrier coatings on nickel-base superalloys

Plasma-sprayed thermal barrier coatings (TBCs) have been used to extend the life of combustors. Electron beam physical vapor deposited (EB-PVD) ceramic coating has been developed for more demanding rotating as well as stationary turbine components. Here 3 kW RF magnetron sputtering equipment was used to gain zirconia ceramic coatings on hollow turbine blades and vanes, which had been deposited NiCrAIY by cathodic arc deposition. NiCrAlY coating surface was treated by shot peening; the effects of shot peening on the residual stress are presented. The results show that RF sputtered TBCs are columnar ceramics, strongly bonded to metal substrates. NiCrAlY bond coat is made of β, γ‘ and Cr phases, ZrO2 ceramic layer consists of t‘ and c phases. No degradation occurs to RF ceramic coatings after 100 h high temperature oxidation at 1150℃ and 500 thermal cycles at 1150℃ for 2 min, air-cooling.     

Modeling of plasma spraying of two powders

The behavior of metal and ceramic powders co-sprayed through a plasma jet was simulated using a commercial fluid dynamics model in which the particles are considered as discrete Langrangian entities. Computations were carried out for the plasma jet and the injected particles using (a) a steady-state three-dimensional (3-D) jet and (b) a simplified two-dimensional (2-D) model. An analytical method was used to estimate the appropriate injection velocities for the metal and ceramic particles, injected through opposing nozzles perpendicular to the plasma flow, so that their “mean” trajectories would impinge on the same area on the target surface. Comparison of the model projections with experimental measurements showed that this method of computation can be used to predict and control the behavior of particles of widely different properties.     

Effect of reinforcement size on the scratch resistance and crystallinity of HVOF sprayed nylon-11/ceramic composite coatings

The high-velocity oxyfuel (HVOF) combustion spraying of dry ball-milled nylon-11/ceramic composite powders is an effective, economical, and environmentally sound method for producing semicrystalline micron and nanoscale reinforced polymer coatings. Composite coatings reinforced with multiple scales of ceramic particulate material are expected to exhibit improved load transfer between the reinforcing phase and the matrix due to interactions between large and small ceramic particles. An important step in developing multiscale composite coatings and load transfer theory is determining the effect of reinforcement size on the distribution of the reinforcement and the properties of the composite coating. Composite feedstock powders were produced by dry ball-milling nylon-11 together with 7, 20, and 40 nm fumed silica particles, 50 and 150 nm fumed alumina particles, and 350 nm, 1, 2, 5, 10, 20, 25, and 50 μm white calcined alumina at 10 vol.% overall ceramic phase loadings. The effectiveness of the ball-milling process as a function of reinforcement size was qualitatively evaluated by scanning electron microscopy+energy dispersive x-ray spectroscopy (SEM+EDS) microanalysis and by characterizing the behavior of the powder during HVOF spraying. The microstructures of the sprayed coatings were characterized by optical microscopy, SEM, EDS, and x-ray diffraction (XRD). The reinforcement particles were found to be concentrated at the splat boundaries in the coatings, forming a series of interconnected lamellar sheets with good three-dimensional distribution. The scratch resistance of the coatings improved consistently and logarithmically as a function of decreasing reinforcement size and compared with those of HVOF sprayed pure nylon-11. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Effect of SiC particle size on flexural strength of porous self-bonded SiC ceramics

Porous self-bonded silicon carbide (SBSC) ceramics were fabricated from SiC powders with various particle sizes (0.7 μm, 25 μm, 50 μm, 65 μm), plus Si, C and boron (as a sintering additive). The effects of submicron (0.7 μm) SiC particle incorporation into the SBSC and the SiC particle size (25 μm, 50 μm, 65 μm) on the flexural strength and porosity of the ceramics were investigated as a function of sintering temperature. Incorporating 0.7 μm SiC particles into the ceramic material containing 25 μm SiC particles increased the flexural strength by 3 times, from 11.7 MPa up to 35.5 MPa after sintering at 1800 °C. Simultaneously, the porosity was reduced by ∼5 %. Furthermore, the flexural strength of ceramic with 25 μm SiC particles was superior to that with 65 μm SiC particles. Generally, the flexural strength of the SBSC increased as, both, a function of submicron SiC particle incorporation along with relatively small micron-sized particles (25 μm) in the microstructure of the ceramic plus increased sintering temperature.     

A high Cr-Mo alloy iron

The structure, hardness, abrasion, and erosion wear of Cr-Mo white iron (containing approximately 28 % Cr and 1 % Mo) heat treated at certain temperatures were studied. Results show that the heat treatment of white iron changes the structures and properties; that is morphology, amount, size, and distribution of secondary phases are affected. When white iron was heated at 800 to 850 ‡C the secondary phase precipitated at the phase boundary, making the abrasion and erosion wear worse. When the iron was heated at 900 to 950 ‡C, the secondary phase precipitated dispersively at the matrix, and the corrosion wear was optimum. If the iron is heated at 1000 to 1050 ‡C, the resistance of abrasion is inhibited, as the secondary phases precipitate in large amounts, and the hardness is increased. When the white iron is tempered at 500 to 600 ‡C, the resistance of abrasion is better.     

Structure and properties of precipitation-hardening ceramic Ti-Zr-C and Ti-Ta-C materials

Precipitation hardening alloys of the Ti-Ta-C and Ti-Zr-C systems produced by self-propagating high-temperature synthesis (SHS) have been studied. Optimum compositions of the alloys and heat-treatment conditions, under which the decomposition of supersaturated solid solution accompanied by the precipitation of fine particles both inside carbide grains and at their boundaries occurs, have been determined. The precipitation hardening ceramic materials exhibit high hardness (∼15–23 GPa) and heat resistance (the mass increase of the Ti-9.4% Ta-10.5% C alloy is less than 8 g/m² during a 50-h exposure in air at 800°C) and can be recommended for the application as materials for deposited multifunctional coatings, high-temperature contacts, evaporation crucibles, and abrasion-resistive tools.     

Characteristics of Fe powders prepared by spray pyrolysis from various types of Fe precursors as a heat pellet material

Aggregated Fe powders comprising elongated and aggregated particles used in the production of heat pellets for application in thermal batteries were prepared by spray pyrolysis. Iron oxide powders comprising dense and hollow particles were prepared by spray pyrolysis from spray solutions containing various types of Fe precursors. Iron oxide powders prepared from iron chloride and iron nitrate precursors were comprised of spherical and micron-sized particles. On the other hand, iron oxide powders prepared from iron oxalate were comprised of large, hollow, and thin-walled particles. The Brunauer-Emmett-Teller (BET) surface areas of iron oxide powders prepared from iron chloride, iron nitrate, and iron oxalate precursors were 17.5, 71.9, and 78.5 m² g⁻¹, respectively. At a low reduction temperature of 550 °C, iron oxide powders prepared from iron oxalate afforded loosely aggregated Fe powders comprised of elongated and loosely aggregated particles, with a BET surface area of 5.9 m² g⁻¹. The heat pellets prepared from Fe powders reduced at 550 °C and composed of fine primary powders had an ignition sensitivity of 0.9 W and a burn rate of 10 cm s⁻¹.