Influence of powder characteristics on plasma sprayed hydroxyapatite coatings

Phase transformations, particle breakdown, and partial decomposition occur in hydroxyapatite (HA) powder feedstock during plasma spraying. The biological responses of the coatings consequently change from the bioactive nature of the starting material to a less biocompatible one. This paper investigates the influence of powder characteristics on the phase composition and microstructure of plasma sprayed HA coatings. The raw HA was prepared by chemically reacting calcium hydroxide with orthophosphoric acid. Subsequently, HA was either calcined and crushed, flame spheroidized, or spray dried. These three types of HA powders were plasma sprayed on steel substrates to form coatings. A previous study showed that the calcined HA powder suffered from particle breakdown in the plasma. The plasma sprayed HA powders contained other calcium phosphate phases (amorphous and crystalline) apart from hydroxyapatite. The flow properties and stability of spheroidized HA were better than calcined HA and spraydried HA. Standard metallographic preparation of the cross sections of the coatings revealed different microstructural features among the coatings. The HA coatings prepared from calcined HA were highly porous and lacking in intimate lamellar contact. The spheroidized HA powders produced the coating with the lowest porosity. Characterization of the powders and coatings was carried out using x-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy.     

Characterization of thermal sprayed hydroxyapatite powders and coatings

Calcium phosphate materials such as hydroxyapatite (HA) have biocompatible properties that can promote osteogenesis or new bone formation. Thermal spraying is an economical and effective process for coating the hydroxyapatite onto metal. It has been reported that plasma spraying changes the degree of crystallinity as well as the phase composition of the HA. This article reports the preparation and characterization of HA powders and coatings by two thermal spray processes (plasma and combustion flame) and suggests that the state of the starting powder adversely affects the coating characteristics. The raw HA powders are synthesized through a chemical reaction involving calcium hydroxide and orthophosphoric acid. Phase analysis using an X- ray diffractometer revealed that the synthesized powder consists of predominantly the HA phase. Calcined and crushed HA powders of various size ranges were fed into the plasma jet to produce HA coatings on metallic substrates. In addition, some HA powders were sprayed into distilled water by plasma spraying and combustion flame spraying to study powder melting characteristics. Other samples were plasma sprayed onto a solid rotating target to study atomization and impact behavior. The morphology of the rapidly solidified powders and thermal sprayed coatings were examined by scanning electron microscopy (SEM). An X- ray sedimentation particle size analyzer, laser diffraction particle size analyzer, and image analyzer performed the particle size analysis. Preliminary results indicate that particle cohesion, size range, and thermal treatment in the plasma affect the phase and structure of the as- sprayed coating, and some post- spray treatment may be necessary to produce a dense and adherent coating with the desired biocompatible properties.     

Reactive Atmospheric Plasma Spraying of AlN Coatings: Influence of Aluminum Feedstock Particle Size

Feedstock powder characteristics (size distribution, morphology, shape, specific mass, and injection rate) are considered to be one of the key factors in controlling plasma-sprayed coatings microstructure and properties. The influence of feedstock powder characteristics to control the reaction and coatings microstructure in reactive plasma spraying process (RPS) is still unclear. This study, investigated the influence of feedstock particle size in RPS of aluminum nitride (AlN) coatings, through plasma nitriding of aluminum (Al) feedstock powders. It was possible to fabricate AlN-based coatings through plasma nitriding of all kinds of Al powders in atmospheric plasma spray (APS) process. The nitriding ratio was improved with decreasing the particle size of feedstock powder, due to improving the nitriding reaction during flight. However, decreasing the particle size of feedstock powder suppressed the coatings thickness. Due to the loss of the powder during the injection, the excessive vaporization of fine Al particles and the completing nitriding reaction of some fine Al particles during flight. The feedstock particle size directly affects on the nitriding, melting, flowability, and the vaporization behaviors of Al powders during spraying. It concluded that using smaller particle size powders is useful for improving the nitriding ratio and not suitable for fabrication thick AlN coatings in reactive plasma spray process. To fabricate thick AlN coatings through RPS, enhancing the nitriding reaction of Al powders with large particle size during spraying is required.     

Plasma spray forming of tungsten coatings on copper electrodes

Both direct current dc plasma and radio frequency induction plasma were used to deposit tungsten coatings on copper electrodes. Fine tungsten powder with mean particle size of 5 um and coarse tungsten powder with particle size in the range from 45 um to 75 um were used as plasma spray feedstock. It is found that dc plasma is only applicable to spray the fine tungsten powder and induction plasma can be used to spray both the coarse powder and the fine powder. The tungsten coating deposited by the induction plasma spraying of the coarse powder is extremely dense. Such a coating with an interlocking structure and an integral interface with the copper substrate demonstrates high cohesion strength and adhesion strength.     

Particle melting behavior during high-velocity oxygen fuel thermal spraying

Particle melting behavior during high-velocity oxygen fuel (HVOF) thermal spraying was investigated using Inconel 625 powders. The powder characteristics and coating properties were investigated using scanning electron microscopy (SEM), x-ray, and microhardness studies. Results indicated that the volume fraction of unmelted particles in the coatings was dependent on the proportion of powder within a specified size range, in these experiments, 30 to 50 μm. This particle size range was primarily determined by the particle temperature, which was measured during spraying. Particle temperature significantly decreased as particle size increased. The microhardness values for the coatings containing unmelted particles were predicted by a simple rule-of-mixtures equation for the case of a low volume fraction of unmelted particles. However, for the condition of high volume fraction of unmelted particles, the measured microhardness values did not compare favorably with the calculated values, probably due to the presence of porosity, which occurred in the form of voids found among unmelted particles. The microstructure and characteristics of the feedstock powder were retained in the corresponding coating under certain spray conditions.     

Effect of Particle Morphology and Size Distribution on Cold-Sprayed Pure Titanium Coatings

The effects of commercially pure titanium particle morphology (spherical, sponge, and irregular) and size distributions (mean particle sizes of 20-49 μm) on the cold spray process and resulting coating properties were investigated. Numerous powder and coating characterizations were performed including: powder oxygen and nitrogen contents, powder flowability, powder compressibility, coating microhardness, coating porosity, LOM/SEM analyses, and XRD. Compared to spherical powders, the sponge and irregular CP-Ti powders had higher oxygen content, poorer powder flowability, higher compression ratio, lower powder packing factor, and higher average particle impact velocities. XRD results showed no new phases present when comparing the various feedstock powders to corresponding coatings. A higher particle temperature was also obtained with larger particle size for all feedstock powder morphologies processed with the same set of spray parameters. A spherical powder with 29 μm mean particle size was found to have the lowest porosity coating and best cold sprayability. The relationships of several as-cold sprayed coating characteristics to the ratio of particle impact and critical velocities were also discussed.     

Influence of NH4Cl Powder Addition for Fabrication of Aluminum Nitride Coating in Reactive Atmospheric Plasma Spray Process

Reactive plasma spray is the key to fabricating aluminum nitride (AlN) thermally sprayed coatings. It was possible to fabricate AlN/Al composite coatings using atmospheric plasma spray process through plasma nitriding of Al powders (Al 30 ??m). The nitriding reaction and the AlN content could be improved by controlling the spray distance and the feedstock powder particle size. Increasing the spray distance and/or using smaller particle size of Al powders improved the in-flight nitriding reaction. However, it was difficult to fabricate thick and dense AlN coatings with an increase in the spray distance and/or when using fine particles. Thus, the coatings thickness was suppressed because of the complete nitriding of some particles (formation of AlN particles) during flight, which prevents the particle deposition. Furthermore, the excessive vaporization of Al fine particles (due to increased particle temperature) decreased the deposition efficiency. To fabricate thick AlN coatings in the reactive plasma spray process, improving the nitriding reaction of the large Al particles at short spray distance is required to decrease the vaporization of Al particles during flight. This study investigated the influence of adding ammonium chloride (NH₄Cl) powders on the nitriding process of large Al powders and on the microstructure of the fabricated coatings. It was possible to fabricate thick AlN coatings at 100 mm spray distance with small addition of NH₄Cl powders to the Al feedstock powders (30 ??m). Addition of NH₄Cl to the starting Al powders promoted the formation of AlN through changing the reaction path to vapor-phase nitridation chlorination-nitridation sequences as confirmed by the thermodynamic analysis of possible intermediate reactions. This changes the nitriding reaction to a mild way, so it is more controlled with no explosive mode and with relatively low heating rates. Thus, NH₄Cl acts as a catalyst, nitrogen source, and diluent agent. Furthermore, the evolved gases from the sublimation or decomposition of NH₄Cl can prevent the Al particles coalescing after melting.     

粉末原料粒径对WC-17Co涂层性能的影响

本文利用超音速火焰喷涂技术喷涂四种不同粒径的WC-17Co粉末,评价粉末粒径对涂层机械性能和抗磨粒磨损性能的影响。结果表明,粉末的粒径越小,在超音速焰流作用下获得的速度和温度越高,形成的涂层越致密,颗粒间的粘接强度越高,同时涂层的显微硬度也越高。WC-17Co粉末的粒径越小,获得涂层的孔隙直径越小,颗粒间的粘接缺陷越少,因此涂层的抗磨粒磨损性能越好。但是当WC-17Co粉末的粒径过于微小时,涂层的断裂韧性将受到影响。在本文研究的四种粒径分布的WC-17Co粉末中,中间粒径且分布范围集中的粉末制得的涂层兼具良好的机械性能和抗磨粒磨损性能。     

Induction plasma spheroidization of tungsten and molybdenum powders

The melting, evaporation and oxidation behaviors as well as the solidification phenomena of tungsten and molybdenum in induction plasma were studied. Scanning electron microscopy was used to examine the morphology and the cross section of plasma-processed powders. X-ray diffraction was used to analyze the oxides formed on the particle surface of these two metals. The influence of spray chamber pressure on the spheroidization and oxidation phenomena was discussed. The results show that fewer Mo particles than W particles are spheroidized at the same powder feed rate under the same plasma spray condition although molybdenum has a lower melting point. A small fraction of tungsten is evaporized and condensed either on the surface of tungsten particles nearby or on the wall of spray chamber. Tungsten oxides were found in tungsten powder processed under soft vacuum condition. Extremely large grains form inside some spheroidized particles of tungsten powder.     

Characterization and processing of spray-dried zirconia powders for plasma spray application

The correlation between the performance of plasma spray coatings and feedstock powder properties is not fully understood. To demonstrate this correlation, eight spray-dried zirconia powders containing a mass fraction of 20% Y₂O₃ (yttria) were characterized with respect to their physical, bulk chemical, and surface chemical properties. The same powders were plasma spray deposited as coatings, and their relative performance was evaluated using a thermal rupture test developed by Pratt and Whitney. The specific powder properties studied were chemical composition, binder content, particle size distribution, powder morphology, interface chemistry, thermogravimetry, phase composition, and specific surface area. Among the characterization data, the binder-related properties of the powder correlated most strongly with the thermal rupture test data. Specifically, higher binder contents were associated with poor thermal rupture test performance.     

HVOF thermal spray deposited Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-stabilized ZrO<Subscript>2</Subscript> coatings for thermal barrier applications

High velocity oxy-fuel (HVOF) thermal spray has been successfully used to deposit yttria-stabilized zirconia (YSZ) for thermal barrier coating (TBC) applications. Adherent coatings were obtained within a limited range of spray conditions using hydrogen as fuel gas. Spray parameters such as hydrogen-to-oxygen ratio, spray distance, and substrate cooling were investigated. Spray distance was found to have a pronounced effect on coating quality; adherent coatings were obtained for spray distances between 75 and 125 mm from the gun exit for the hydrogen-to-oxygen ratios explored. Compared to air plasma spray (APS) deposited YSZ coatings, the HVOF deposited coatings were more fully stabilized in the tetragonal phase, and of similar density, surface roughness, and cross-sectional microhardness. Notably, fracture surfaces of the HVOF coatings revealed a more homogeneous structure. Many theoretical models predict that it should not be possible to melt YSZ in an HVOF flame, and therefore it should not be possible to deposit viable YSZ coatings by this process. The experimental results in the present work clearly contradict those expectations. The present results can be explained by taking into account the effect of partial melting and sintering on particle cohesion, as follows. Combustion chamber pressures (P _o) of ∼3.9 bar (58.8 psi) realized during HVOF gun operation allows adiabatic flame temperature values that are above the zirconia melting temperature. Under these conditions, the Ranz-Marshall heat transfer model predicts HVOF sprayed particle surface temperatures T _p that are high enough for partial melting of small (∼10 μm) zirconia particles, T _p=(1.10−0.95)T _m. Further analysis shows that for larger particles (38 μm), adherent coatings are produced when the particle temperature, T _p=0.59−0.60 T _m, suggesting that sintering may have a role in zirconia particle deposition during HVOF spray. These results suggest two different bonding mechanisms for powders having a broad particle size distribution.     

Spheroidization of Nd-Fe-B Powders by RF Induction Plasma Processing

以不规则形的钕铁硼粉为原料,使用射频等离子体球化处理工艺,制备球形钕铁硼粉.研究了原料的加料速率和粉末粒度对粉末球化率的影响.通过扫描电子显微镜观察对比了等离子球化处理前后粉末及截面形貌,采用X射线衍射方法测试分析了球化过程中氧化物的生成.检测了球化前后粉末的松装密度及其粒度分布.结果表明:不规则形状的钕铁硼粉经等离子球化处理后其球化率可达到100％,松装密度由2.778 g/cm3提高到3.785 g/cm3,粉末流动性由43.3 s/50 g提高到27.5 s/50 g.该粉末适用于凝胶注膜成型及注射成型.     

Next Generation Thermal Barrier Coatings for the Gas Turbine Industry

The aim of this study is to develop the next generation of production ready air plasma sprayed thermal barrier coating with a low conductivity and long lifetime. A number of coating architectures were produced using commercially available plasma spray guns. Modifications were made to powder chemistry, including high purity powders, dysprosia stabilized zirconia powders, and powders containing porosity formers. Agglomerated & sintered and homogenized oven spheroidized powder morphologies were used to attain beneficial microstructures. Dual layer coatings were produced using the two powders. Laser flash technique was used to evaluate the thermal conductivity of the coating systems from room temperature to 1200 °C. Tests were performed on as-sprayed samples and samples were heat treated for 100 h at 1150 °C. Thermal conductivity results were correlated to the coating microstructure using image analysis of porosity and cracks. The results show the influence of beneficial porosity on reducing the thermal conductivity of the produced coatings.     

Effect of the suspension composition on the microstructural properties of high velocity suspension flame sprayed (HVSFS) Al2O3 coatings

Seven different Al₂O₃-based suspensions were prepared by dispersing two nano-sized Al₂O₃ powders (having analogous size distribution and chemical composition but different surface chemistry), one micron-sized powder and their mixtures in a water + isopropanol solution. High velocity suspension flame sprayed (HVSFS) coatings were deposited using these suspensions as feedstock and adopting two different sets of spray parameters.The characteristics of the suspension, particularly its agglomeration behaviour, have a significant influence on the coating deposition mechanism and, hence, on its properties (microstructure, hardness, elastic modulus). Dense and very smooth (Ra ~ 1.3 μm) coatings, consisting of well-flattened lamellae having a homogeneous size distribution, are obtained when micron-sized (~ 1-2 μm) powders with low tendency to agglomeration are employed. Spray parameters favouring the break-up of the few agglomerates present in the suspension enhance the deposition efficiency (up to > 50%), as no particle or agglomerate larger than ~ 2.5 μm can be fully melted. Nano-sized powders, by contrast, generally form stronger agglomerates, which cannot be significantly disrupted by adjusting the spray parameters. If the chosen nanopowder forms small agglomerates (up to a few microns), the deposition efficiency is satisfactory and the coating porosity is limited, although the lamellae generally have a wider size distribution, so that roughness is somewhat higher. If the nanopowder forms large agglomerates (on account of its surface chemistry), poor deposition efficiencies and porous layers are obtained.Although suspensions containing the pure micron-sized powder produce the densest coatings, the highest deposition efficiency (~ 70%) is obtained by suitable mixtures of micron- and nano-sized powders, on account of synergistic effects.     

Microstructure and composition analysis in plasma sprayed coatings of Al2O3/ZrSiO4 mixtures

Plasma spraying of Al₂O₃/ZrSiO₄ was performed using spray dried and plasma spheroidised powder feedstock. The mixtures were sprayed using different spray stand-off distances and plasma power levels. X-Ray diffraction (XRD) was used to characterise the phase composition and scanning electron microscopy (SEM) examined the morphology of the sprayed surface and polished cross-sections. The results showed that the plasma spray process parameters played an important role in the final outcome of microstructures of the coatings. The coatings produced with spheroidised powders displayed a much denser structure than those produced with the spray-dried powders. The phase composition analysis showed the presence of amorphous phases in addition to crystalline alumina, zircon and tetragonal (t) zirconia (ZrO₂). Transmission electron microscopy (TEM) showed that amorphous phases and t-ZrO₂ crystals with particle size 100–200 nm could coexist within a single splat due to the relatively low local cooling rate.     

Antibacterial Property of Cold-Sprayed HA-Ag/PEEK Coating

The antibacterial behavior of HA-Ag (silver-doped hydroxyapatite) nanopowder and their composite coatings were investigated against Escherichia coli (DH5α). HA-Ag nanopowder and PEEK (poly-ether-ether-ketone)-based HA-Ag composite powders were synthesized using in-house powder processing techniques. Bacteria culture assay of HA-Ag nanopowder and their composite powders displayed excellent bacteriostatic activity against E. coli. The antibacterial activity increased with increasing concentration of HA-Ag nanoparticle in these composite powders. These nanocomposite powders were subsequently used as feedstock to generate antibacterial coatings via cold spray technology. The ratios of HA-Ag to PEEK in their composite powders were 80:20, 60:40, 40:60, and 20:80 (wt.%). Microstructural characterization and phase analysis of feedstock powders and as-deposited coatings were carried out using FESEM/EDX and XRD. Antibacterial nanocomposite HA-Ag/PEEK coatings were successfully deposited using cold spraying parameters of 11-12 bars at preheated air temperature between 150 and 160 °C. These as-sprayed coatings of HA-Ag/PEEK composite powders comprising varying HA-Ag and PEEK ratios retained their inherent antibacterial property as verified from bacterial assay. The results indicated that the antibacterial activity increased with increasing HA-Ag nanopowder concentration in the composite powder feedstock and cold-sprayed coating.     

The thermal spray processing of HA powders and coatings

In recent years, coated implants have been actively researched and put to use in many biomedical engineering applications. The coating used on the implants is hydroxyapatite (HA), a calcium-phosphate compound with attractive bioactive and biocompatible properties that can enhance the fixation process of biomedical implants. Thermal spraying provides a potent means for depositing the HA coatings on implants. Among the populat thermal-spray techniques are combustion-flame spray, plasma spray, and high-velocity oxy-fuel spray. This article investigates the versatility of thermal-spray techniques to perform spheroidization of HA powders, the preparation of HA-based biocomposite powders and coatings, and the deposition of HA coatings.     

Optimizing the vacuum plasma spray deposition of metal,ceramic, and cermet coatings using designed experiments

The vacuum plasma spray (VPS) deposition of metal, ceramic, and cermet coatings has been investigated using designed statistical experiments. Processing conditions that were considered likely to have a significant influence on the melting characteristics of the precursor powders and hence deposition efficiency were incorporated into full and fractional factorial experimental designs. The processing of an alumina powder was very sensitive to variations in the deposition conditions, particularly the injection velocity of the powder into the plasma flame, the plasma gas composition, and the power supplied to the gun. Using a combination of full and fractional factorial experimental designs, it was possible to rapidly identify the important spraying variables and adjust these to produce a deposition efficiency approaching 80%. The deposition of a nickel-base alloy metal powder was less sensitive to processing conditions. Generally, however, a high degree of particle melting was achieved for a wide range of spray conditions. Preliminary experiments performed using a tungsten carbide/cobalt cermet powder indicated that spray efficiency was not sensitive to deposition conditions. However, microstructural analysis revealed considerable variations in the degree of tungsten carbide dissolution. The structure and properties of the optimized coatings produced in the factorial experiments are also discussed.     

Hydroxyapatite coatings for biomedical applications deposited by different thermal spray techniques

Thermally sprayed hydroxyapatite (HAp) coatings are widely used for various biomedical applications due to the fact that HAp is a bioactive, osteoconductive material capable of forming a direct and firm biological fixation with surrounding bone tissue.Bioceramic coatings based on nanoscale HAp suspension and microscale HAp powder were thermally sprayed on Ti plates by high-velocity suspension flame spraying (HVSFS) technique and atmospheric plasma spraying (APS) as well as high velocity oxy fuel spraying (HVOF) technique. HVSFS is a novel thermal spray process developed at IMTCCC, for direct processing of submicron and nano-sized particles dispersed in a liquid feedstock.The deposited coatings were mechanically characterized including surface roughness, micro hardness and coating porosity. The bond strength of the layer composites were analyzed by the pull-off method and compared for the different spray techniques. Phase content and crystallinity of the coatings were evaluated using X-ray diffraction (XRD). The coating composite specimen and initial feedstock were further analysed by scanning electron microscope (SEM) and rheology analysis.     

真空感应熔炼气雾化法制备高强度PH13-8Mo钢粉末的特性表征

采用真空感应熔炼气雾化(VIGA)法制备出球形高强度PH13-8Mo钢粉末,通过不同目数的筛网对粉末进行筛分,得到120~212μm,53~120μm,15~53μm和<15μm不同粒度区间的高强度PH13-8Mo钢粉末。利用氧氮分析仪、扫描电镜(SEM)、激光粒度分布仪和智能粉体特性测试仪等分析手段研究了不同粒径区间的PH13-8Mo钢粉末的氧含量、表面形貌、表面及内部微观组织、流动性和松装密度。结果表明:随着粉末粒度区间减小,PH13-8Mo钢粉末的比表面积从0.017 m^2/g显著增大到0.243 m^2/g,粉末中的O含量从0.017%增大到0.033%;当PH13-8Mo钢粉末粒径的范围为15~53μm区间时,粉末中的O含量相对较低,冷却速率较大,卫星球颗粒少,表面和内部组织主要由胞状晶和微晶组成,且该粒度范围的PH13-8Mo钢粉末的松装密度和流动性指数高。