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.     

New results in High Velocity Suspension Flame Spraying (HVSFS)

High Velocity Suspension Flame Spraying (HVSFS) is a new approach for spraying micron, submicron and nanoparticles with hypersonic speed by feeding a suspension directly into the combustion chamber of a HVOF torch. The aim in mind is to achieve dense coatings with an improved microstructure — probably reaching the nanoscale, from which superior physical properties are expected. Compared to the alternative approach, i.e.. using agglomerated (nano- and micron-sized) powders, direct spraying of suspensions shows much higher flexibility in combining and processing different materials and is far less expensive. Several suspensions consisting of an organic solvent and a solid phase consisting of a micron or a nanopowder have been prepared and HVSFS sprayed. Suspensions containing oxide nanopowders of titanium oxide (n-TiO₂), chromium (III) oxide (n-Cr₂O₃), yttrium stabilized zirconia (n-YSZ) and a n-hydroxyapatite (n-HAP). Furthermore two suspensions containing glass powders (grain size 2-3 μμm after milling) were also sprayed: a Zr-Al-Si containing glass (FOA) and a phosphor containing bioglass (AW). HVSFS coatings were characterized regarding their phase composition and microstructure. Mechanical and tribological properties are compared with standard coatings produced by APS and HVOF.     

Comparison Between High-Velocity Suspension Flame Spraying and Suspension Plasma Spraying of Alumina

Two different spray processes??suspension plasma spraying (SPS) and high-velocity suspension flame spraying (HVSFS)??are under focus in the field of suspension spraying. Both techniques are suitable for manufacturing finely structured coatings. The differences in the particle velocity and temperature of these two processes cause varying coating characteristics. The high particle velocity of the HVSFS process leads to more dense coatings with low porosity values. Coatings with a higher and also homogeneous porosity, which can be generated by SPS, have also high potential, for example, for thermal barrier coatings. In this study, both the processes??SPS and HVSFS??were compared using alumina as feedstock material mixed with different solvents. Besides the characterization of the microstructure and phase composition of the applied coatings, the focus of this study was the investigation of the melting behavior of the particles in-flight and of single splat characteristics.     

Introduction to High-Velocity Suspension Flame Spraying (HVSFS)

High-velocity suspension flame spraying (HVSFS) has been developed to thermally spray suspensions containing micron, submicron, and nanoparticles with hypersonic speed. For this purpose, the suspension is introduced directly into the combustion chamber of a modified HVOF torch. The aim in mind is to achieve dense coatings with a refined microstructure. Especially from nanostructured coatings superior physical properties are expected for many potential applications. Direct spraying of suspensions offers flexibility in combining and processing different materials. It is a cost-saving process and allows the allocation of entirely new application fields. The paper gives an overview of the HVSFS spray method and will present some actual results that have been achieved by spraying the nanooxide ceramic materials Al₂O₃, TiO₂, 3YSZ, and Cr₂O₃.     

WC-based cermet coatings produced by cold gas dynamic and pulsed gas dynamic spraying processes

Due to their mechanical properties, WC-based cermet coatings are extensively used in wear-resistant applications. These coatings are usually produced using thermal spray processes. However, due to the nature and the environment of these spraying processes, the feedstock powder structure and properties suffer from decomposition, which subsequently degrade the performance of the coatings produced. The cold gas dynamic spraying process appears to be a promising alternative technique to preserve the properties of the feedstock powder during the coating preparation. Although the latter technique can minimize or eliminate the degradation of the sprayed material, the deposition of cermet using this technique is a difficult task. In this study, two types of cermet powders, the nanocrystalline (WC-15Co) and the conventional (WC-10Co4Cr) powders were deposited using the cold gas dynamic spraying and the pulsed gas dynamic spraying processes. The feedstock powders and coatings microstructures were investigated by OM, SEM and XRD, as well as their hardness. The results revealed the possibility of depositing cermet coatings onto aluminum substrates using both processes without any degradation of the carbide phase of the feedstock powder. The cold gas dynamic spraying process experienced difficulty in depositing and building up dense coatings without major defects. The pulsed gas dynamic process produced thick cermet (conventional and nanocrystalline) coatings with low porosity as long as the feedstock powder was preheated above 573 K.     

Microstructure and properties of flame sprayed tungsten carbide coatings

This article reports on feasibility experiments carried out with oxy-acetylene spray system with various oxygen to fuel ratios using two different tungsten carbide powders and powder feeding methods, to evaluate the newly developed fused WC, synthesised by transferred arc thermal plasma method. Transferred arc thermal plasma method is more economical and less energy intensive than the conventional arc method and results in a fused carbide powder with higher hardness. The microstructure and phase composition of powders and coatings were analysed by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Carbon content of the powders and coatings were determined to study the decarburisation of the material during spraying process. Coatings were also characterised by their hardness and abrasive wear. The effects of metallurgical transformation and phase content are related to wear performance. The results demonstrate that the powders exhibit various degree of phase transformation during the spray process depending on the type of powder, powder feeding and spray parameters. The carbon loss during the spray process in excess of 45% resulted in reduced hardness and wear resistance of the coatings. Coatings with high amount of WC and W₂C along with FeW₃C showed higher wear resistance. Thus, coatings of high wear resistance can be produced using fused tungsten carbide powder with WC and W₂C phases, which can be economically synthesised by thermal plasma transferred arc method.     

感应等离子体球化热喷涂粉体材料研究进展

介绍了传统非等离子体法制备球形粉体方法--雾化法和喷雾造粒法,分析了其在热喷涂球形粉体制备过程中存在的优势和局限性。综述了等离子球化技术在热喷涂粉体材料领域中的应用现状,并深入讨论了感应等离子体球化过程中不同的工艺条件对粉体球化率和形貌的影响:原料粉体状态决定了球化后粉体的平均粒径,降低粉体原始粒径可以提高熔融程度,粒径分布较窄的原始粉体有利于得到高球形度粉体;适当增大输入功率和工作气体流量,可降低细小颗粒的粘附现象;工作气体的种类会影响等离子焰炬的热焓值;送粉速率需要结合粉体性质择优选取。这些关键影响因素对热喷涂粉体性能的调控机制,以及深入认识等离子体作用条件下的热喷涂粉体球化机理,提供了有力的理论支撑。总结和展望了感应等离子球化技术在热喷涂陶瓷粉体材料制备中存在的问题和发展方向,感应等离子体球化技术作为制备高纯度、无污染热喷涂球形粉体材料的一种新技术,具有广阔的应用前景。     

Microstructure and properties of thermally sprayed silicon nitride-based coatings

The preparation of thermally sprayed, dense, Si₃N₄-based coatings can be accomplished using composite spray powders with Si₃N₄ embedded in a complex oxide binder matrix. Powders with excellent processability were developed and produced by agglomeration (spray drying) and sintering. Optimization of the heat transfer into the powder particles was found to be the most decisive factor necessary for the production of dense and well-adhering coatings. In the present work, different thermal spray processes such as detonation gun spraying (DGS), atmospheric plasma spraying (APS) with axial powder injection, and high-velocity oxyfuel spraying (HVOF) were used. The coatings were characterized using optical and scanning electron microscopy (SEM), x-ray diffraction (XRD), and microhardness testing. The wear resistance was tested using a rubber wheel abrasion wear test (ASTM G65). In addition, thermoshock and corrosion resistances were determined. The microstructure and the performance of the best coatings were found to be sufficient, suggesting the technical applicability of this new type of coating.     

Microstructural and Tribological Investigation of High-Velocity Suspension Flame Sprayed (HVSFS) Al2O3 Coatings

Al₂O₃ coatings were manufactured by the high-velocity suspension flame spraying (HVSFS) technique using a nanopowder suspension. Their structural and microstructural characteristics, micromechanical behavior, and tribological properties were studied and compared to conventional atmospheric plasma sprayed and high-velocity oxygen-fuel-sprayed Al₂O₃ coatings manufactured using commercially available feedstock. The HVSFS process enables near full melting of the nanopowder particles, resulting in very small and well flattened lamellae (thickness range 100 nm to 1 μm), almost free of transverse microcracking, with very few unmelted inclusions. Thus, porosity is much lower and pores are smaller than in conventional coatings. Moreover, few interlamellar or intralamellar cracks exist, resulting in reduced pore interconnectivity (evaluated by electrochemical impedance spectroscopy). Such strong interlamellar cohesion favors much better dry sliding wear resistance at room temperature and at 400 °C.     

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.     

镍铝材料状态对火焰喷涂层组织结构和性能的影响

针对煤矿机械液压支柱热喷涂修复中涂层结合强度低的实际,研究了在27SiMn钢基体上火焰喷涂新研制的镍铝合金丝制备镍铝涂层,并与火焰喷涂镍包铝粉末、镍铝复合丝制备的镍铝涂层在组织结构、表面形貌、结合强度等方面进行了比较分析.结果表明,镍铝合金丝制备的涂层与基体之间主要为冶金结合,结合强度比镍包铝粉末涂层提高46.8％,比镍铝复合丝涂层提高8％,涂层组织结构致密,气孔率低、质杂少.     

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.     

Erosion-corrosion properties of different WC-Co-Cr coatings deposited by the HVOF process—influence of metallic matrix composition and spray powder size distribution

WC-Co-Cr coatings were sprayed by the High Velocity Oxygen Fuel (HVOF) process and characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD) and erosion corrosion tests. Powders with different relative amounts of Co and Cr in the matrix and different powder grain size distributions were examined. At constant spray conditions the powders gave coatings of different quality as regards erosion-corrosion performance. At low erosive conditions the erosion-corrosion resistance increased when increasing Cr-content from 5 to 8.5 wt.%. However, when the erosivity was increased by increasing test velocity, an increase of Cr content from 5 to 8.5 wt.% showed no improvement in coating quality. Powder grain size distribution was found to be an important parameter, strongly affecting the coating quality. Powders with narrow grain size distributions gave coatings of higher quality than powders with wider grain size distributions. A reduction of the heat input during spraying reduced the degree of WC decomposition and improved the coating properties when the spray powder contained a large fraction of small grains.     

Numerical Investigation of High Velocity Suspension Flame Spraying

High-velocity suspension flame spraying (HVSFS) has recently developed as a possible alternative to conventional HVOF-spraying employing liquid suspensions instead of dry powder feedstock enables the use of nanoparticles. From the fluid dynamics point of view, the HVSFS system is complex and involves three-phase (gas, liquid and solid particles) turbulent flow, heat transfer, evaporation of the suspension solvent, chemical reactions of main fuel (propane) and suspension solvent (ethanol) and supersonic/subsonic flow transitions. Computational fluid dynamic techniques were carried out to solve the mass, momentum, and energy conservation equations. The realizable k-?? turbulence model was used to account for the effect of turbulence. The HVSFS process involves two combustion reactions. A primary combustion process is the premixed oxygen-propane reaction and secondary process is the non-premixed oxygen-gaseous ethanol reaction. For each reaction, one step global reaction, which takes dissociations and intermediate reactions into account, was derived from the equilibrium chemistry code developed by Gordon and McBride and eddy dissipation model was used to calculate the rate of reactions based on the transport equations for all species (10 species) mass fractions. Droplets were tracked in the continuum in a Lagrangian approach. In this paper, flow field inside and outside the gun simulated to provide clear and complete insight about the HVSFS processes. Moreover, the effect of some operative parameters (oxy-fuel flow rate, ethanol flow rate, droplets injection velocity and droplets size) on the gas flow field along the centerline and droplets evaporation behavior was discussed.     

球磨工艺参数对A12O3弥散强化NiCr合金粉及其

采用不同的球磨工艺制备了A12O3弥散强化NiCr合金粉末，粉末经雾化造粒后，进行微束等离子喷涂（MPS）试验。采用XRD、SEM等方法研究了弥散强化粉末及其喷涂层的微观组织结构及硬度。结果表明：采用较长的球磨时间以及相对高的A12O3含量可以得到组织结构均匀，硬质相弥散分布的球磨粉末，MPS喷涂后涂层结构均匀，显微硬度为原NiCr粉末涂层的3倍左右。     

Finely grained nanometric and submicrometric coatings by thermal spraying: A review

Technology, microstructure and properties of nanostructured coatings obtained using different feedstock including: (i) powders composed of agglomerated nanocrystals; (ii) solutions; and (iii) suspensions are discussed. The methods of nanostructured coarse powders manufacturing are reviewed together with the problems related to formulation of solutions and suspensions. A particular attention is paid to the key problem at liquid feedstock spraying, namely to their delivery and injection into jets or flames. The physical and chemical phenomena occurring at flight of injected liquid droplet of solution and suspension are shown and related to the formation of coatings and their microstructure. Some microstructural, chemical, mechanical and electrical properties of coatings are collected and related to the operational processing parameters by regression equations derived from the design of spray experiments. Finally, the possible applications of nanostructured coatings are briefly discussed.     

TiB2-SiC粉末喷雾造粒及其等离子喷涂沉积机理研究

利用喷雾干燥对TiB_2-SiC复合粉末进行造粒,研究了浆料固含量、粘结剂含量及SiC含量对喷雾干燥粉体颗粒形貌等的影响。采用大气等离子喷涂技术,以抛光的石墨为基体,在不同预热温度和不同喷距下对TiB_2-SiC粉末进行粒子收集,研究不同工艺参数对TiB_2-SiC粒子铺展形貌的影响,并制备了TiB_2-SiC涂层。结果表明:当浆料固含量为50%,粘结剂含量为5%,SiC含量为10%时,喷雾造粒获得球形度高、流动性好的TiB_2-SiC粉末;随着基体预热温度的升高,喷距的增大,扁平粒子的溅射逐渐减弱,形成规则的圆盘状粒子;在等离子焰流作用下,TiB_2-SiC粒子熔化加速并与基体发生碰撞,熔融粒子扁平化,急速冷却凝固,不断堆叠、搭接为宏观涂层。     

Numerical approach and optimization of the combustion and gas dynamics in High Velocity Suspension Flame Spraying (HVSFS)

The interest in submicron and nano-structured layers applied by thermal spray technologies on different surfaces has been significantly increased during the last decade. Conventional HVOF spraying processes are not suitable to achieve submicron and nano-particles. Therefore, High Velocity Suspension Flame Spraying (HVSFS) has been developed for the processing of nano-structured spray material to achieve dense surface layers in supersonic mode with a refined micro- or nano-structure, from which superior mechanical and physical properties are expected.However, the chemical and thermodynamic phenomena occurring in the HVSFS reacting flow field are a challenging, multidisciplinary issue. This study is intended to analyze and understand the HVSFS combustion and flow dynamic system on the basis of a CFD model and numerical calculation. The final aim is an optimization of the process parameters by variations during simulation experiments.