The effect of solids and dispersant loadings on the suspension viscosities and deposition rates of suspension plasma sprayed YSZ coatings

Suspension plasma spraying (SPS) is a promising modification of traditional plasma spraying techniques that uses small (≤ 2 μm) particles suspended in a liquid to fabricate coatings with fine microstructures and controlled porosity rapidly and without the need for post-deposition heat treatments. These qualities make SPS an interesting new technique to manufacture solid oxide fuel cell (SOFC) active layers. However, in order to be able to manufacture layers with good microstructures, the properties of the feedstock suspension must be optimized to enhance particle dispersion and improve feedability. This study uses a pressurized gas delivery system to feed aqueous YSZ suspensions containing an organic dispersant to a Northwest Mettech Axial III axial injection suspension plasma spray system. Three different dispersant types (polyacrylic acid (PAA), polyethylene imine (PEI) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA)) were characterized and the effects of solid loadings, dispersant type, and dispersant concentration on suspension properties such as viscosity and feedability, and layer characteristics such as microstructure and deposited thickness were examined.     

等离子体喷涂纳米结构热障涂层微观组织及性能

以纳米结构氧化钇部分稳定的氧化锆热喷涂粉末为原料,采用大气热等离子体喷涂法制备了纳米结构热障涂层。利用扫描电子显微镜和X射线衍射仪对粉末原料及涂层的微观组织和结构进行分析,并对涂层的结合强度及热导率进行测定。结果表明,纳米结构热障涂层具有优异的性能,热导率为1.1 W/(m.K),界面结合强度为47 MPa。并分析了涂层纳米结构组织对涂层性能的影响,明确了优化涂层微观组织结构和提高涂层性能的具体方法。     

Process diagnostics in suspension plasma spraying

Benefits and limitations of process diagnostics are investigated for the suspension plasma spraying of yttria-stabilized zirconia thermal barrier coatings. The methods applied were enthalpy probe measurements, optical emission spectroscopy, and in-flight particle diagnostic.It was proved that the plasma characteristics are not affected negatively by the injection of the ethanol based suspension since the combustion of species resulting from ethanol decomposition achieves a gain of plasma enthalpy. Furthermore, the conditions of the suspension injection into the plasma were found to be optimum as a significant content of evaporated powder material could be detected. Regarding the void content and segmentation crack density of the coatings, the in-flight particle diagnostic showed that the spray distance should be dimensioned in a way that the molten particles reach the substrates just before solidification starts.     

等离子喷涂纳米氧化锆涂层摩擦性能研究

利用大气等离子喷涂技术,在不锈钢基体上用不同颗粒尺寸的纳米粉末制备了两种纳米氧化锆涂层S1(平均粒度较小颗粒的喷雾造粒粉末所得)和B1(平均粒度较大颗粒的喷雾造粒粉末所得).运用XRD、SEM、TEM、拉曼光谱和金相技术等分析手段对喷涂用的粉末原料和涂层的显微结构、物相组成进行了观察与确定;利用环-块摩擦试验在干摩擦条件下对涂层的摩擦磨损性能进行了测试.结果表明,两种氧化锆涂层的摩擦系数均随载荷增大而减小.在较低载荷(100 N)条件下,S1涂层与不锈钢的摩擦系数低于B1涂层与不锈钢的摩擦系数;而在较高(400 N)载荷下,两种氧化锆涂层的摩擦系数开始趋于一致.其原因在于:较低的载荷下两种涂层与不锈钢摩擦副的摩擦磨损机制不同,S1涂层的磨损属于粘着磨损,B1涂层的磨损属于磨粒磨损;而在较高载荷下,两种涂层的磨损机制趋于一致,均为粘着磨损.     

Temperature behaviour of titania field emitters realized by suspension plasma spraying

Titania field electron cathodes made with solution precursor plasma spraying (SPS) were investigated. The emission characteristics were measured using a self-made installation. Microstructure analysis was carried out using scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The electron emission was found to decrease with increasing temperature of tested samples. This was explained in terms of the coating microstructure and, in particular, the phase content and change in dielectric properties of coating components.     

Preparation of perovskite powders and coatings by radio frequency suspension plasma spraying

Perovskite-type LaMnO₃ powders and coatings have been prepared by a novel technique: reactive suspension plasma spraying (SPS) using an inductively coupled plasma of approximately 40 kW plate power and an oxygen plasma sheath gas. Suitable precursor mixtures were found on the basis of solid state reactions, solubility, and the phases obtained during the spray process. Best results were achieved by spraying a suspension of fine MnO₂ powder in a saturated ethanol solution of LaCl₃ with a 1 to 1 molar ratio of lanthanum and manganese. A low reactor pressure was helpful in diminishing the amount of corrosive chlorine compounds in the reactor. As-sprayed coatings and collected powders showed perovskite contents of 70 to 90%. After a posttreatment with an 80% oxygen plasma, an almost pure LaMnO₃ deposit was achieved in the center of the incident plasma jet. This paper originally appeared in Thermal Spray: Meeting the Challenges of the 21st Century; Proceedings of the 15th International Thermal Spray Conference, C. Coddet, Ed., ASM International, Materials Park, OH, 1998. This proceedings paper has been extensively reviewed according to the editorial policy of the Journal of Thermal Spray Technology.     

The evaluation of powder processing on microstructure and mechanical properties of hydroxyapatite (HA)/yttria stabilized zirconia (YSZ) composite coatings

In clinical applications, the mechanical failure of HA-coated titanium alloy implants suffered at the interface of the HA coating and titanium alloy substrate will be a potential weakness in prosthesis. Yttria stabilized zirconia (YSZ) reinforced HA coatings have been proven to enhance the mechanical properties of the HA coating significantly and reduce the formation of calcium oxide (CaO). In this paper, HA/YSZ (30 wt.% YSZ) composite coatings were sprayed by the plasma technique. The effects of the powder processing–mechanical ball milling method and spheroidization method on the microstructure and mechanical properties of the HA/YSZ composite coatings were evaluated. The experimental results showed that the spheroidized powders melted better than the ball milled powders during plasma spraying and formed higher mechanical property coatings (1.6326±0.08 MPa m^−0.5 of fracture toughness, 58.59±2.91 GPa of elastic modulus and 43.42±2.53 MPa of tensile bond strength). HA/YSZ solid solution formed during deposition on the substrate, which played a very important role in the mechanical properties of the HA/YSZ composite coatings. Tensile bond strength tests showed that the fracture mode was cohesive and that failure occurred at the interface of HA and unmelted YSZ particles. The molten state of YSZ had a great influence on the properties of the HA/YSZ composite coatings.     

Design of the synthesis of fine HA powder for suspension plasma spraying

Hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) is a bioactive material being frequently used as a coating onto implants. The typical coating technology is air plasma spraying with the use of coarse powder. The resulting coatings are relatively thick (about 200-400 µm) and porous. Much thinner coatings being 5-40 µm thick, can be obtained by emerging technology of suspension plasma spraying with the use of powder particles having the diameters ranging from a few submicrometers to a few micrometers. The paper describes the way of synthesizing and preparing such fine powder starting from an aqueous solution of ammonium phosphate (H₂(PO₄)NH₄) and calcium nitrate (Ca(NO₃)·4H₂O) using statistical design of experiments (DOE). The design was made using composite matrix including a full factorial plan, star points and 3 experiments in the centre. The crystal phases purity and the mass of powder batch were the optimized responses of the powder synthesis and the concentration of calcium ions and volume of ammonium hydroxide were the experimental variables. The synthesized material was characterized by X-ray diffraction (XRD). The powder was calcined and crushed using a milling machine with zirconia balls and resulting morphology and size of fine particles was characterized using scanning electron microscope (SEM) and laser sizer correspondingly. The powder was then formulated into water and alcohol based suspension and the zeta potential was determined to understand its capacity of agglomeration. It was found out that the formulation of the suspension with the use of ethanol slightly favours dispersion of solid particles in the suspension. The initial tests of water based suspension plasma spraying onto titanium substrate were also carried out and the XRD phase analysis of obtained coatings was carried out the presence of HA and its phases of decomposition.     

Nanostructured photocatalytic titania coatings formed by suspension plasma spraying

This paper describes formation of titanium dioxide coatings designed for photocatalytic applications, obtained by suspension plasma spraying (SPS), an alternative of the atmospheric plasma spraying (APS) technique in which the material feedstock is a suspension of the material to be sprayed. Two different TiO₂ powders were dispersed in distilled water and ethanol and injected in Ar-H₂ or Ar-H₂-He plasma under atmospheric conditions. Scanning electron microscopy (SEM) and x-ray diffraction (XRD) analyses were performed to study the microstructure of the titania coatings. Photocatalytic efficiency of the elaborated samples was evaluated from the conversion ratio of different air pollutants: nitrogen oxides (NOx) and sulfur dioxide (SO₂). The morphology and crystalline structure of the deposits depended mainly on the nature of the solvent (water or alcohol) used in the preparation of the slurries. Dense coatings were obtained starting from aqueous suspensions and porous deposits were elaborated by plasma spraying of a PC105 alcoholic suspension. A significant phase transformation from anatase to rutile occurred when ethanol was used as a solvent. Different photocatalytic performances were observed as a function of the nature of the liquid material feed-stock, the spraying parameters, and the nature of the pollutant. 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.     

Nanostructured yttria stabilized zirconia coatings deposited by air plasma spraying

Nanostructured yttria partially stabilized zirconia coatings were deposited by air plasma spraying with reconstituted nanosized powder. The microstructures and phase compositions of the powder and the as-sprayed nanostructured coatings were characterized by transmission electron microscopy（TEM）, scanning electron microscopy（SEM） and X-ray diffxaction（XRD）. The results demonstrate that the microstructure of as-sprayed nanostructured zirconia coating exhibits a unique tri-modal distribution including the initial nanostructure of the powder, equiaxed grains and columnar grains. Air plasma sprayed nanostructured zirconia coatings consist of only the nontransformable tetragonal phase, though the reconstituted nanostructured powder shows the presence of the monoclinic, the tetragonal and the cubic phases. The mean grain size of the coating is about 42 nm.     

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.     

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.     

Microstructures of nanostructured ceramic coatings obtained by suspension thermal spraying

In the present work, the elaboration of nanostructured alumina and titania coatings by thermal spraying with liquid precursors is described. Nano- and submicrometer-sized powders were used to prepare aqueous or alcoholic suspensions. The suspensions were sprayed using APS and HVOF processes in order to obtain thin and thick deposits. The paper discusses the coating microstructures as a function of suspension characteristics and spray parameters in both APS and HVOF processes.     

Formation of high hardness zirconia coatings by gas tunnel type plasma spraying

The high hardness zirconia (ZrO₂) coatings could be obtained at an atmospheric pressure by using a gas tunnel type plasma spraying. The characteristics of these high hardness ZrO₂ coatings were investigated. The Vickers hardness of the ZrO₂ coating at a short spraying distance was very high; a high hardness of more than H_v=1200 was achieved at the surface side of the coating. The microstructure of the obtained high hardness ZrO₂ coating was also investigated by the microscopic method. And the characteristics of the high hardness ZrO₂ coating was discussed in comparison with that of the coating formed by the conventional type plasma spraying. It was clarified that the ZrO₂ coating of the gas tunnel type was not only much harder but also less porous than that of the conventional type.     

The role of torch instabilities in the suspension plasma spraying process

In spite of the fact that plasma spraying is a commonly used technique for coating elaboration, it remains important to follow in time the characteristics of the arc jet delivered by the plasma torch. Arc voltage and heat loss measurement could be used, together with the control parameters such as arc current and plasma gas flow rate, to investigate the global behavior of the torch in association with a simple analytical model. It is shown that the specific enthalpy and the isentropic coefficient of the plasma gas have a strong influence on the jet velocity, this latter being also significantly modified by the drift of the torch performance. This work is completed by the analysis of the plasma jet instabilities that are responsible for the discrepancy in particle thermal histories. The rear part of the torch is involved in self sustained oscillations, so that the torch shows the characteristics of a Helmholtz resonator, giving rise to periodic variations of the torch voltage, higher in amplitude than the commonly admitted restrike mode. It is also evoked, that the generated acoustic waves are interacting with the solvent vaporization.     

Study on instant droplet and particle stages during suspension plasma spraying (SPS)

Suspension plasma spraying (SPS) is a new process in the field of the atmospheric plasma spraying (APS). The SPS process uses a heterogeneous mixture of liquids and particles. Thus it is possible to process particles with a size between ten to a few hundred nanometres. This leads to completely new or at least improved material features and structures. Notwithstanding the process and the involved mechanisms that lead from a suspension droplet to a molten ceramic droplet and its influence on the generated coating are not yet completely understood. Because of the liquid in the suspension and much smaller particles the process in the plasma is much more complex compared to the APS process. Based on empiric studies including in-flight monitoring of the particles as well as splat and coating analyses a new schematic of the single stages during suspension plasma spraying and their influence on the coating structure will be introduced.     

Advanced microstructural study of suspension plasma sprayed titanium oxide coatings

Suspension plasma sprayed titanium oxide coatings were analyzed using transmission electron microscope (TEM) and using Raman spectroscopy. The suspensions used to spray were formulated using fine rutile pigment, water, alcohol or their mixtures, and a small quantity of dispersant. TEM study realized using a “face-to-face” preparation technique enabled to visualize a lamellar shape of grains and their columnar growth. The Raman spectroscopy was made for the samples prepared using different operational spray parameters. The investigations showed the presence of rutile and anatase phase in coatings sprayed using rutile fine powder.     

等离子喷涂氧化锆涂层及激光重熔涂层的摩擦磨损性能

采用等离子喷涂制备了常规氧化锆涂层和纳米氧化锆涂层,并对制备的纳米氧化锆涂层进行了激光重熔处理,系统地研究了3种氧化锆涂层(常规、纳米和激光重熔涂层)在常温和高温下的摩擦磨损性能.结果表明,纳米氧化锆涂层耐磨性能明显优于常规氧化锆涂层,而激光重熔处理后的纳米氧化锆涂层在常温和高温下,都表现出最低的摩擦系数和最好的耐磨性能.这3种涂层的表面粗糙程度、涂层孔隙率和裂纹状况明显不同,从而表现出不同的摩擦磨损特性;说明纳米粉末等离子喷涂结合激光重熔技术是提高氧化锆涂层性能的有效方法.     

Life cycle assessment of using powder and liquid precursors in plasma spraying: The case of yttria-stabilized zirconia

Plasma spraying using liquid precursors makes possible the production of finely-structured coatings and thin coatings. This technology has been investigated for nearly ten years in many laboratories and applications are now emerging, using conventional plasma equipment except for the feedstock injection system. While superior quality is expected from the nano-structured coatings, the question remains as to the impacts of using liquid precursors on the environment. In this study, we used the life cycle assessment (LCA) methodology to compare the conventional plasma spray process using powder feedstock, with injection of the precursor in the form of a liquid solution or suspension. The LCA methodology consists of identifying and comparing the environmental impacts of feedstock, energy inputs, products and emissions (solid, liquid and gaseous) of these two alternatives. The LCA study was carried out using the SimaPro program developed in the Netherlands and a peer-reviewed database of upstream materials and energy (EcoInvent v.2). The specific application studied was the plasma spraying of yttria-stabilized zirconia.     

Developments in direct current plasma spraying

Thermal spray processing is used to confer specific in-service properties to components via the production of a coating between 50 μm (minimum value) to a few millimeters thick. Thermal spray represents a global market of about 4.8 Billion Euros (i.e., ∼ US$5 billion) in 2004; 30% of which is European based. 50% of this activity is devoted to plasma spray processing with about 90% dedicated to direct current (DC) plasma torches. Several developments of new torch architectures, among which three-cathode torches, have evolved recently. However, most of the recent progress has been applied to conventional DC torches. The advances were related to two prime factors: (i) the development of industrial sensors permitting to diagnose the processes during spray operation (especially in-flight particle characteristics in terms of their surface temperature and velocity) and additionally the monitoring of the substrate and coating temperatures with the objective of controlling the operating parameters via a close-loop controller; (ii) the adaptation of plasma spray systems to manufacture nano-structured coatings via the development of suspension plasma spray and solution plasma spray. As well, there has been an enhanced understanding of the mechanisms controlling the coating formation and of the effects of the arc root fluctuations; thereby permitting a more robust process. This paper develops the above points by presenting focused examples.