Controlling graphite content in plasma sprayed cast iron coatings via in-flight particle diagnostic

Graphite formation and degradation in thermally sprayed cast iron coatings is a technological barrier for achieving superior wear resistant coatings. Therefore, there is a need to understand the in-flight particle behavior of cast iron powder and introduce new approaches to control the graphite content. In this study, it has been demonstrated that the graphite content can be controlled by means of in-flight particle diagnostic. For this purpose, cast iron coatings were plasma sprayed under a variety of spray conditions and characterized by using an optical microscope, X-ray diffractometer and electron probe micro-analyzer. As a result, a significant amount of graphite with respect to a wide range of in-flight particle temperature and velocity was preserved in cast iron coatings.     

Preparation and cell-materials interactions of plasma sprayed strontium-containing hydroxyapatite coating

The use of strontium-containing hydroxyapatite (Sr-HA) as a biomaterial has been reported recently. In vitro and in vivo studies have shown that Sr-HA promotes osteoblast response and stimulates new bone formation. In order to extend its usage to major load-bearing applications, such as artificial hip replacement, it has been proposed that the material could be used in the form of a coating on implant surfaces. This paper reports a preliminary study of biocompatibility of plasma sprayed Sr-HA coatings on a metallic substrate. Coatings of Sr-HA containing 10 mol% Sr²⁺ was produced on titanium alloy substrates. The coating exhibited good bonding with the substrate. The bioactivity of Sr-HA coating was evaluated in vitro by immersion in simulated body fluid (SBF). After immersion in SBF, Sr-HA coating exhibited great ability to induce apatite precipitation on its surface. The possible effects of cell-materials interactions of Sr-HA coating were examined by culturing osteoprecursor cells (OPC1) on coating surfaces. The effect of Sr-HA was also compared to a hydroxyapatite (HA) coating, which is widely used in orthopedics and dentistry. The results indicated that Sr-HA coating had good biocompatibility with human osteoblasts. OPC1 cells survived and proliferated well on the surface of coating. Sr-HA coating promoted OPC1 cells attachment, and more local contacts were produced on the surface. The presence of Sr stimulated OPC1 cell differentiation and ALP expression. No deleterious effect on ECM formation and mineralization was found with Sr-HA coating. The results indicated that Sr-HA coating had good mechanical properties and bioactivity in vitro.     

Hydroxyapatite coatings prepared by a high power laminar plasma jet

For two hydroxyapatite (HA) powders, containing particles differing in mass by a factor of 20, a set of optimum deposition parameters was defined, leading to the coatings with high crystallinity (80-90%), high adhesion strength (60 and 40 MPa for the coating thicknesses of 120 μm and 350 μm, respectively) and excellent microstructure (coatings were without micro- or macro-cracks, without delaminating on substrate-coating surface contact, and possess low porosity, 1-2%). It was shown that higher plasma power (52 kW) did not necessarily lead to a higher HA decomposition.     

微束等离子喷涂氧化锆增韧羟基磷灰石复合涂层

采用微束等离子喷涂方法,在Ti-6Al-4V基体上制备了羟基磷灰石 氧化锆(70HA-30ZrO2,质量分数,%)复合涂层.将复合涂层置于模拟体液中分别浸泡了3,7,14,28 d并观察表面磷灰石的生长情况以评价涂层生物活性.采用扫描电镜(SEM)和X射线衍射(XRD)分析技术对涂层浸泡前后的表面形貌和相组成进行了研究.结果表明,涂层中ZrO2主要以立方相存在;喷涂过程中羟基磷灰石(HA)出现了一定的分解,产生大量的α-Ca3(PO4)2杂质相.HA涂层熔化效果很好,但涂层中有未熔化的ZrO2颗粒.涂层在模拟体液中浸泡28 d后表面可以形成磷灰石,说明涂层具有很好的生物活性.     

Nanostructured zirconia coatings processed by PROSOL deposition

The development of nanostructured coatings is a new field of interest in the world of thermal spraying. Novel techniques, such as HVOF or plasma spraying have been developed with respect to thermally activated processes, in order to reach the nanometric scale (10-20 nm). Frequently, the evolution consists in using agglomerated nanoparticles or suspension feedings. The CEA has patented a process called PROSOL [K. Wittmann-Ténèze, K. Vallé, L. Bianchi, F. Blein, P. Belleville, CEA Le Ripault, France, “Revêtement nanostructuré et procédé de revêtement”, Fr patent n°04 52390, (2004).], which is based on the injection of a sol-gel colloidal solution in a plasma source. Studies on the resulting coatings have principally shown that a nanostructured material could be prepared all the while preserving the intrinsic properties of the nanoparticle sol, the nanoparticle size and the crystalline phase distribution.The present investigation illustrates the PROSOL process through an example of spraying of a zirconia (ZrO₂) sol, prepared under hydrothermal conditions, in an atmospheric plasma jet. A time-stabilized sol of zirconia nanoparticles (10 nm) crystallized in both monoclinic and tetragonal phases was obtained. The injection of such a sol in the plasma plume was performed through a liquid injector that dispensed a sol jet under pressure without any pulverization gas. Because of the high temperature and the high velocity medium, the sol was fragmented into droplets and the liquid phase was vaporized. The resulting nanoparticle agglomerates embedded in droplets were accelerated and collected on a substrate without melting. By adjusting the plasma spraying parameters, more or less dense coatings could be obtained. Various characterization techniques were performed on the as-sprayed layers, including SEM, XRD and TEM. Results showed that the coatings were constituted of 10 nm-sized grains in the monoclinic and tetragonal phases. The flexibility of the process was also highlighted, i.e., the possibility to obtain coatings with thicknesses between one and several microns, produced without any physical change at a given deposition rate, on a variety of geometries and on a vast range of substrates.     

Effect of Ti-OH formation on bioactivity of vacuum plasma sprayed titanium coating after chemical treatment

The effect of Ti-OH groups on bioactivity of NaOH treated titanium coating was investigated in this paper. The NaOH-heat treatment was also applied to modify the titanium coating for comparison. The results show that the amount of Ti-OH groups was important to induce apatite formation on the treated titanium coating. When the NaOH treated titanium coating was exposed to SBF, it released Na⁺ ions from the sodium titanate layer on its surface into the SBF via exchanging with H₃O⁺ ions in the fluid and Ti-OH groups were rapidly formed on the surface. So the NaOH treated titanium coating has good bioactivity in simulated body fluid (SBF). The amount of Ti-OH groups on the titanium coating was reduced after heat treatment, so the bioactivity of NaOH-heat treated titanium coating was obviously affected.     

Microstructure and thermal cycle resistance of plasma sprayed mullite coatings made from secondary mullitized natural andalusite powder

Natural andalusite powder was calcinated at a high temperature in air to realize secondary mullitization. The resultant secondary mullitized powder was spray-dried and heat-treated to improve sprayable capability. The heat-treated spherical powder was then plasma sprayed onto Ni-based high-temperature alloy (Hastelloy C-276) to form mullite coatings. The chemical composition and phase structure of the as-sprayed and thermally cycled mullite coatings were determined by means of energy dispersive X-ray fluorescence (ED-XRF) and X-ray diffraction. The microstructure of the as-sprayed coatings was analyzed by using a scanning electron microscope; and their porosity, microhardness and bonding strength were measured. Moreover, the phase transition temperature and enthalpy of the coatings were determined by means of differential scanning calorimetry; and their thermal shock resistance was evaluated as well. Results show that the spray-dried and heat-treated powder consists of mullite and a small amount of Al₂O₃; while the as-sprayed mullite coatings are composed of crystalline mullite as the major phase and a small amount of amorphous glass phase. During thermal cycle test, the amorphous glass phase is partially transformed to crystalline mullite, finally leading to failure of the coatings. Whether before or after thermal cycle, the mullite coatings experience phase transition around 980 °C, and the enthalpy of crystallization is determined to be − 141.9 × 10^− 3 J/kg and − 95.48 × 10^− 3 J/kg, respectively. The as-sprayed mullite coatings have a porosity of about 6.0 ± 0.2% and possess good thermal cycle resistance, showing promising prospect in a high-temperature application.     

On-line temperature monitoring and process diagnosis of plasma sprayed coatings

On-line temperature monitoring of plasma sprayed coating is presented, which is based on IR pyrometery combined to robot trajectories. Temperature fields of the substrate before spraying and the deposited coating when the damage happens are taken to investigate the temperature fluctuation information. Experimental results demonstrate that coating damage always occurs in the temperature transition area of the substrate from the higher to the lower, as well as the higher temperature area. The temperature difference between the peak and the mean of the relevant regions is beyond 30-50 ℃ or even higher. This case provides the omen of coating damage and the focusing scopes for the process control of coating temperature in plasma spraying.     

Sintering characteristics of plasma sprayed zirconia coatings containing different stabilisers

Zirconia powders with different types of stabiliser (Y₂O₃, Dy₂O₃ and Yb₂O₃) have been air plasma sprayed onto metallic substrates. The coatings were detached and dimensional changes during heat treatment were measured by dilatometry. Ytterbia-stabilised specimens exhibited the highest rates of shrinkage, in both in-plane and through-thickness directions. However, it was noted that these specimens had higher initial porosity levels, and a finer microstructure, than coatings containing the other stabilisers. In-plane stiffness and through-thickness thermal conductivity were also measured after different heat treatments. These increased at greater rates for specimens with higher porosity levels (ie the Yb-stabilised coatings). Changes in pore architecture during heat treatments were also studied. Fine scale porosity is rapidly reduced during heat treatment. This correlates with enhanced inter-splat bonding and healing of intra-splat microcracks. In general, the sintering behaviour, and consequent changes in microstructure and properties, appear to be more sensitive to the pore architecture than to stabiliser type. This is correlated with theoretical expectations that it is grain boundary and surface diffusion which will dominate the sintering behaviour, rather than lattice diffusion, and these are more likely to be affected by pore structure, and possibly by the presence of certain types of impurity, than by stabiliser content. It is also noted that thermal cycling appears to retard sintering, at least in terms of the rate of shrinkage. This effect, which could be of practical significance, is briefly discussed.     

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.     

喷涂工艺参数对硅灰石涂层结构的影响

采用等离子喷涂方法,在不同喷涂距离、主气流量和喷涂功率下制备硅灰石涂层.使用扫描电镜观察了涂层的微观形貌,研究了喷涂工艺参数对涂层结构的影响.结果表明,在较大主气流量下,随着喷涂距离增加,涂层粒子扁平化程度降低,涂层内孔隙逐渐增多;在较小主气流量下,涂层粒子扁平化程度随喷涂距离增加呈现先增加后减小的趋势.主气流量增加,涂层致密,粒子扁平充分.喷涂功率增加,粒子熔化好,涂层致密;但随喷涂功率进一步增加,涂层中出现较多的圆形孔隙.喷涂工艺参数对涂层结构的影响主要通过影响熔融粒子的温度和速度所致.     

Atmospheric plasma spraying of yttria-stabilized zirconia coatings with specific porosity

The interdependence between plasma spray process parameters and porosity of YSZ coating microstructures was investigated with simultaneous consideration of the deposition efficiency. Based on a factorial experimental plan, the argon plasma gas flow, the current, the interaction of argon flow and current, and the spray distance for the Triplex II plasma gun were found to yield the main contributions to porosity as well as to deposition efficiency.Each of these three process parameters has a significant individual effect on the in-flight particle velocities and temperatures. The contribution to the effects on porosity arises almost exclusively from the particle temperature. Regarding the deposition efficiency, the larger contribution originates from the particle velocity.To achieve a targeted high porosity at reasonable deposition efficiency a simple linear regression model was applied yielding an argon flow of 50 slpm and a current of 470 A at a spray distance of 200 mm as the optimum parameter set. The average particle temperature estimated for this optimum is just above the melting temperature. At this setting, a porosity of 17.7% and a deposition efficiency of 32.5% may be expected.At a greater spray distance and lower power density (lower current and/or higher argon plasma gas flow) the deposition efficiency was observed to drop considerably. The cooling of the particles here becomes critical, i.e. the particles are only partly molten. This was verified by an analysis of the density distributions of measured in-flight particle temperatures.     

Formation and structure of plasma sprayed manganese-cobalt spinel coatings on preheated metallic interconnector plates

Manganese-cobalt spinels are promising materials for protective coatings on metallic interconnector plates in solid oxide fuel cells. These protective coatings are used to prevent growth and evaporation of chromium oxide, chromium poisoning and ageing phenomena of the cathode side of the fuel cell. It is well known that chromium trioxide and chromium hydroxide on interconnector plate may easily evaporate at high temperatures and transform back to chromium oxide at the cathodes active area and cause degradation of the solid oxide fuel cell performance.In the present study, plasma spraying together with a substrate pre- and simultaneous heating was found to be an appropriate technique to control the formation and densification of the coating. When plasma spraying Mn-Co spinel powder for cold substrate, high cracking effect inside the splats and in the formed coating was noticed. When applying the molten drops to the substrate heated up to 450 °C amount of cracks in single splats and coatings could be mostly eliminated. The splats stayed in the liquid state longer, which effected for spreading properties and spinel structure could be better preserved by longer crystallize time.     

Antibacterial properties of vacuum plasma sprayed titanium coatings after chemical treatment

Implant-related infection is one of the common clinical complications that cause high rates of mortality and morbidity in orthopedic surgery. Endowing implant antibacterial properties is a useful method to reduce such infection. In this paper, vacuum plasma sprayed titanium coatings were treated by NaOH solution firstly, and then antimicrobial silver was introduced into the coatings by immersing in 0.02 mM (denoted as CA1), 0.06 mM (denoted as CA2) and 0.1 mM (denoted as CA3) Ag⁺ containing calcification solution. Antibacterial property of the treated titanium coatings was examined by employing three types of bacteria stains, Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. X-Ray diffraction and scanning electron microscopy were used to observe the phase composition and surface morphology of the modified titanium coatings. Results showed that all of the three kinds of coatings exhibited more than 90.00% antibacterial ratio except CA1 to Staphylococcus aureus which is 63.30%. The release of silver in physiological environment was monitored and it was found that the excellent antibacterial property of the treated coatings was attributed to the release of silver.     

Erosion-resistance of plasma sprayed coatings

Cr₃C₂/NiCr, ZrO₂/NiCr, WTiC₂/NiCr, and X40 were plasma sprayed on the substrate 1Cr18Ni9Ti in order to solve the erosion wear at high temperature encountered in the oil-refining industry. A series of properties of the coatings, including their microstructure, hardness, and erosion-behavior, have been tested. The test results show that the properties of the coatings have a significant effect on their erosionresistant performance. Good erosion-resistant materials need to be hard and tough. Both Cr₃C₂/NiCr and X40 have good erosion resistance at elevated temperature.     

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.     

晶须增韧等离子喷涂陶瓷涂层的可控制备与力学性能研究

针对新一代航空发动机和重型燃气轮机对长寿命、高韧性热障涂层的迫切需求,本文通过喷雾造粒法制备了长径比为10的ZrO2晶须复合YSZ喷涂粉末,采用SAPS技术制备了YSZ/ZrO2晶须増韧陶瓷复合涂层,对复合涂层的工艺参数进行优化,研究了熔融指数对陶瓷复合涂层微观结构的影响规律;通过狭缝法收集单个摊片的实验,阐明了ZrO2晶须增韧YSZ陶瓷涂层的形成机理,建立了晶须増韧陶瓷涂层的微观结构与热力学性能的内在关系。基于晶须弥散分布于复合涂层未熔颗粒区的特征,相比纳米结构YSZ涂层,YSZ/ZrO2晶须増韧陶瓷复合涂层的断裂韧性与热循环寿命均提高一倍。     

Process map for plasma sprayed aluminum oxide-carbon nanotube nanocomposite coatings

Process map has been developed for plasma sprayed aluminum oxide (Al₂O₃) ceramic nanocomposite coatings with carbon nanotube (CNT) reinforcement in varying content and spatial distribution. The process map was constructed using the temperature and velocity data of the in-flight powder particles exiting from the plasma plume. Process map elucidates the interdependence of powder feedstock pre-treatment, CNT content and dispersion behavior on the in-flight particle thermal history and subsequently evolving microstructure and coating properties. High thermal conductivity of CNTs alters the heat transfer characteristic during the splat formation. Microstructure of the coatings consists of fully melted zone (FM), partially melted or solid-state sintered zone (PM) and porosity. Process map provides a processing control tool for plasma spraying of Al₂O₃-CNT nanocomposite coatings.     

Non-destructive evaluation of plasma sprayed functionally graded thermal barrier coatings

Acoustic emission (AE) as a non-destructive evaluation technique has recently been used in a number of studies to investigate the performance and failure behavior of plasma sprayed thermal barrier coatings. The mechanism of coating failure is complex, especially when considering the composite nature of the coating. In the present paper, the thermal shock tests with in situ acoustic emission are used to study the cracking behavior of plasma sprayed functionally graded thermal barrier coatings. Each thermal cycle consists of 8 min heating in the furnace at 1000°C and 8 min cooling from 1000°C to the room temperature by a compressed air jet. The AE signals are recorded during the quench stage. Three, four and five layer functionally graded coatings have been tested. The results show that the five layer functionally graded coatings appear to have the best thermal shock resistance in the specimens tested, because of the gradual changes in material properties. Higher AE energy counts and cumulative counts recorded by the tests are associated with the macro-crack initiation and growth. On the other hand, micro cracking and phase transformation only give rise to lower AE signals.