Effects of Feedstock and Laser Post-spray Treatment on Plasma Sprayed Bioceramic Coatings*

Hydroxyapatite (HA) is a bioactive material with Ca to P ratio similar to that of natural bone. This can encourage early bonding between bony tissues and the implant surface. Plasma spraying is efficient in coating HA onto biomedical implants. However, the biocompatibility of hydroxyapatite (HA) changes after plasma spraying. This paper reports the preparation and characterization of HA coatings using different feedstocks; calcined HA (CHA) that has angular geometry, and spray dried HA (SDHA) that is predominantly spherical in shape. The results indicates that the state of the starting powder adversely influences the coating characteristics. Both types of HA, calcined and crushed HA powders and spray dried HA powders, are plasma sprayed on steel substrates to produce HA coatings. The results indicate that particle cohesion, size range and thermal treatment during thermal spray processing alter the phase and structure of the as-sprayed coatings. Post-spray treatment by pulsed lasers is performed on the coatings to modify the surface characteristics and phase composition of the surface layer. This, in addition, may be necessary to produce a dense and well-bonded coating having the desired biocompatible properties. Laser treatments show overall melting of the HAcoating to yield a smooth surface. However, the presence of crack networks is undesirable.     

The Effect of flux types on the formation of green light emitting phosphor particles with spherical shape and filled morphology

(CeTb)MgAl₁₁O₁₉ (CTMA) phosphor particles were prepared by high-temperature spray pyrolysis from spray solutions with various types of flux materials. The particles prepared from spray solutions with ammonium dihydrogen phosphate and lithium carbonate fluxes had spherical shape and filled morphology at temperatures of 900^∘C and 1650^∘C. On the other hand, the particles prepared from spray solutions without flux material had hollow and fractured morphology at temperatures of 900^∘C and 1650^∘C. The melting of flux material formed the spherical intermediate particles with filled morphology. These spherical intermediate particles were formed from spray solutions with flux material that transformed into spherical CTMA phosphor particles with filled morphology at a high-preparation temperature. The phosphor particles prepared by spray pyrolysis from the spray solution with appropriate flux materials at 1650^∘C had high photoluminescence intensities, spherical shape, and filled morphology.     

Role of powder treatment and carbon nanotube dispersion in the fracture toughening of plasma-sprayed aluminum oxide-carbon nanotube nanocomposite

Al2O3 ceramic reinforced with 4-wt% multiwalled carbon nanotube (CNT) is plasma sprayed for improving the fracture toughness of the nanocomposite coating. Two different methodologies of CNT addition have been adopted in the powder feedstock to assist CNT dispersion in the nano-Al2O3 matrix. First, spray-dried nano-Al2O3 agglomerates are blended with 4 wt% CNT as powder-feedstock, which is subsequently plasma sprayed resulting in the fracture toughness improvement of 19.9%. Secondly, spray dried composite nano-Al2O3 and 4 wt% CNT powder was used as feedstock for attaining improved dispersion of CNTs. Plasma sprayed coating of composite spray dried powder resulted in increase of 42.9% in the fracture toughness. Coating synthesized from the blended powder displayed impact alignment of CNTs along splat interface, and CNTs chain loop structure anchoring the fused Al2O3 melt whereas coating synthesized from composite spray dried powder evinced anchoring of CNTs in the solid state sintered region and CNT mesh formation. Enhanced fracture toughness is attributed to significance of CNT dispersion.     

Characteristics of spray flames and the effect of group combustion on the morphology of flame-made nanoparticles

Characteristics of burning and non-burning sprays generated by a coaxial air-assist nozzle, previously used for the synthesis of ceramic nanoparticles by flame spray pyrolysis (FSP), are studied using phase Doppler anemometry. Also, the effect of droplet interaction on the overall combustion behavior of the spray (group combustion) and, consequently, on the characteristics of flame-made ceramic particles is investigated. A physical model is proposed which correlates the formation of inhomogeneous mixtures of micron-sized hollow particles and solid nanoparticles to the combustion mode: the precursor droplets which entirely evaporate in the hot flame are responsible for the formation of nanoparticles. The vapor species react, forming intermediate and product molecules and clusters that quickly grow to nanosized ceramic particles. On the other hand, under certain conditions, a small number of the droplets, particularly with large initial sizes, escape from the spray boundaries and become extinguished, producing large hollow ceramic particles. It is also possible that some of the large droplets, which lie within the spray core, do not entirely evaporate. These surviving droplets then form large particles which are usually hollow but can collapse to solid particles at sufficiently high temperatures. Also, a criterion for the formation of homogeneous ceramic nanoparticles is presented.     

Plasma spraying of an indigenous yttria stabilized zirconia powder prepared by the sol-gel technique

An indigenous sol-gel derived yttria-partially stabilized zirconia (Y-PSZ) powder has been characterized and its suitability for plasma spraying applications evaluated. The powder, determined to have about 5·1% yttria content, predominantly consisted of spherical particles with an average equivalent particle diameter close to 25μm. Furthermore, it was found that the powder did not contain any particles >50μm, which is considered the ideal upper size limit for spray-grade ceramic powders in order to ensure complete melting during spraying. The sol-gel produced powder exhibited good flow characteristics and the plasma sprayed coatings developed using this powder were also found to have excellent thermal shock resistance. The corresponding results obtained using an imported Y-PSZ powder are also presented for the purpose of comparison.     

O/W/O多重乳液法制备毫米级氧化铝空心球

采用O/W/O多重乳液法, 以液体石蜡为内核, 氧化铝溶胶为外壳层组成的复合液滴作为前驱体, 制备毫米级氧化铝空心球, 研究了装置几何结构对前驱体的形成和固化过程对空心球结构的影响。结果表明, 内部油相通过直流通道直接注射到水相液滴内部时, 形成的复合液滴具有均一核壳结构, 壁厚和直径在30~80 μm和800~2200 μm可控。液滴置于水平方向旋转固化, 保持转速在20~60 r/min, 所得凝胶球可以保持完整的球形度和核壳结构。1200℃高温煅烧制备出的氧化铝空心微球维持高的球形度和空心结构, 表面粗糙度大约22 nm, 壁厚达到几十微米, 直径达到毫米级, 主要晶型为稳定的α-Al₂O₃。     

Plasma spheroidization of nickel powders in a plasma reactor

Thermal spray coatings of surfaces with metal, alloy and ceramic materials for protection against corrosion, erosion and wear is an intense field of research. The technique involves injection of the powder into a plasma flame, melting, acceleration of the powder particles, impact and bonding with the substrate. Feedstock powders of metals, alloys and ceramics for thermal spray applications have to meet several requirements. Particle shape, size and its distribution, powder flow characteristics and density are the important factors to be considered in order to ensure high spray efficiency and better coating properties. For smooth and uniform feeding of powders into plasma jet, the powder particles have to be spherical in shape. High temperatures and steep temperatures present in thermal plasma is exploited to spheroidize particles in the present investigation. Nickel powder particles in the size range from 40–100 μm were spheroidized using plasma processing. SEM and optical micrographs showed spherical shape of processed particles.     

SIMULATION OF SPRAY PYROLYSIS FOR CERAMIC POWDER PREPARATION

A mathematical model was developed for spray pyrolysis to produce hollow spherical ceramic particles. The mechanism was established based on the previous experimental results. The transfer of mass, momentum, and heat inside and around the aerosol droplets was considered simultaneously. Simulation was carried out to study the effects of operating parameters on the quality of derived particles. The simulated and experimental results were in agreement and showed that: (a) raising the pyrolysis temperature increased the size and size distribution of resultant particles, and decreased the specific surface area and the bulk density; (b) lowering the concentration of starting solution decreased the size and size distribution of resultant particles, and increased the specific surface area and bulk density.     

Revealing the formation mechanism of granules by drying simulation of slurry droplet

The formation mechanism of granules in spray drying process was investigated by DEM-CIP method simulation coupled with a new binder segregation model. To confirm the validity of proposed binder segregation model, experiment on drying of aqueous slurry containing fine particles and binder was performed. The experimental concentration distribution of binder in a dried powder bed agreed well with the simulated one and this result shows that the proposed segregation model is valid to represent segregation phenomenon in the dried granule. Spherical hollow granules were formed with increasing of binder concentration, and the granules were depressed in higher concentration of binder. When the binder concentration in the surface region of a slurry droplet increased during drying, a crust of granule was formed because particle migration was hindered by high fluid viscosity. For the rigid crust layer, granules were hollow. When the crust layer was formed early in drying and its thickness was thin, granule surface partially collapsed inward, whereas the granule resulted in depression granules.     

Rapid hard tooling by plasma spraying for injection molding and sheet metal forming

Amidst the harsh competition over the development of new products around the world, rapid prototyping, especially rapid tooling methods have received widespread attention. Amongst the rapid hard tooling methods, thermal spraying can manufacture metal molds without limitation of pattern size. However, it has the disadvantage that only soft metals with low melting points such as zinc alloy can be sprayed to original mold, such as a rapid prototyping model or a natural material pattern, due to their lack of heat resistance and shrinkage of spray metals. So the wear resistance of spray tool is poor, it can be used only for trial or small-lot production. In this study, attempts were made to improve the heat resistance by using composite materials made of ceramic and metal powders as the sprayed original mold materials, and using stainless steel, tungsten carbide alloy, iron–nickel–chromium alloy with excellent wear resistance as spraying materials, respectively. The results show that injection molding spray mold and sheet metal forming spray die can be made by transferring from natural patterns and rapid prototyping models. As the durability and dimensional accuracy of the sprayed tools has sharply improved, the tools can be used for mass production.     

Mechanical and microstructural behavior of nanocomposites produced via cold spray

Cold spraying is an innovative coating technology mainly based on the high speed impact of metals and ceramic particles on different substrates. Through the employment of low temperature gases (Air, He, N₂) spray particles (usually 1–50 μm in diameter) are accelerated to a high velocity (typically 300–1200 m/s) that is generated through a convergent–divergent de Laval type nozzle. Severe plastic deformation of particles impacting on the substrate occurs at temperature well below the melting point leading to the unique mechanical properties experienced by such kinds of coatings. In the present paper the main processing parameters affecting the microstructural and mechanical behavior of metal–metal cold spray deposits are described. The effect of processing parameters on grain refinement and mechanical properties were analyzed for different particles (Ti–TiAl₃, Al–Al₂O₃, Ni–Cr₃C₂, Ni–BN, Cu–Al₂O₃, Co–SiC). The results belonging to the properties of the formed nanocomposites were compared with those of the pure parent materials sprayed in the same conditions. Many experimental conditions have been analyzed in terms of particle dimensions and composition, substrate temperature and composition, gas temperature and pressure, nozzle properties. In particular, those conditions leading to a strong grain refinement with an acceptable level of the mechanical deposit properties such as porosity, adhesion strength and hardness were underlined.     

Spray forming of high density sheets

Porosity is one of the most important quality criteria of spray‐formed materials in the as‐sprayed condition. Typically, spray‐formed sheets have a porous rim close to the substrate and depending on the spray conditions cold or hot porosity may also be present in the core of the deposit. This porosity has to be removed or minimized to make further processing steps such as rolling, forging or extrusion possible. In this paper, the influence of both substrate temperature and deposit surface temperature on porosity in spray‐formed sheets is studied. For this purpose spray forming experiments (sheet size 1000 mm × 250 mm) were carried out using three different materials: aluminium‐bronze, tin‐bronze and a nitriding steel. For the copper‐base alloys preheated steel‐substrates with different temperatures were moved through a scanning spray cone. In the case of steel a ceramic substrate at room temperature was used. In addition to the variation of the substrate temperature, the gas to metal mass flow ratio (GMR) was varied to achieve different deposit surface temperatures. During the run the surface temperature in the deposition zone was measured using a scanning, multi‐wavelength pyrometer. Samples of the deposits were polished and rasterized by light microscopy. The local porosity was characterized by digital image analysis. The influence of the substrate temperature and the GMR on the porosity in the vicinity of the substrate is evaluated and discussed in detail. The impact of the deposit surface temperature on the porosity was analyzed and is discussed as well. It was found that the deposit surface temperature has a strong impact on porosity for spray‐formed sheets. Finally, experimental results were used to develop a new approach to predict the porosity in spray‐formed sheets. The results clearly show the dependence on material properties. This approach can be used to identify process parameters to generate high density sheets in the future.     

The effects of substrate materials and powder type on the properties of plasma sprayed ferrite

The effect of the method of powder production and substrate materials on the physical and magnetic properties of plasma sprayed nickel ferrite films is discussed, including the production of films by spraying an oxalate powder and a solution of nitrates in methanol. Films deposited onto substrates having a larger thermal expansion coefficient than ferrite were found to exhibit better magnetic properties, including squarer hysteresis loops. An optimum choice is proposed for good surface finish, porosity and magnetic properties, consisting of spraying fully fired ferrite powder, of particle size 10 to 30 Μm, onto fosterite substrates. The magnetic properties were then comparable with bulk nickel ferrite. If surface finish is not a prime consideration satisfactory results could be obtained from the oxalate powder and the method could be used to produce non-stochiometric ferrites, possibly with improved properties. Films sprayed with the nitrate solution exhibited very favourable grain structures after annealing and it is probable that the method could be useful once problems associated with atomizing the liquid are overcome. Attempts to spray mixed oxides led to films with extreme roughness, due, in part, to a tendency of the powder to agglomerate. The films, as sprayed, were strongly magnetic demonstrating that solid state reaction had occurred, probably on the surface of the hot substrate.     

Effect of substrate surface conditions and impact velocity of sprayed particles on coatings produced by plasma spraying

In high temperature plasma spraying, surface conditions of the substrate and the impact velocity of sprayed particles are particularly important in the consideration of factors influencing the resultant coatings. In this study an induction plasma torch was used to spray aluminum, tungsten and nickel particles onto flat (111) single-crystal silicon substrates with different surface preparations. In addition to experiments with silicon substrates with clean surfaces and substrates with previously evaporated aluminum over oxide coatings, oxide films and water vapor, hydraulic oil and grease contaminant films were used to investigate the influence of these surface conditions on adhesion formation. The impact velocity of the sprayed particles was controlled by controlling the speed of a centrifugal disc on which the substrate was installed to traverse the plasma effluent.Scanning electron microscopy was used extensively to characterize features of the particle-substrate interaction and to compare the individual behaviors of the metal particles used. Microcavitations and dislocations resulting from the plastic deformation of the substrate were revealed by the successive use of a metal and a special dislocation etchant.     

A novel approach to the synthesis of hollow silica nanoparticles

Hollow silica nanoparticles were synthesized with incorporation of silanol groups (SiOH) onto polymer particles in dispersion polymerization and the polycondensation reaction of tetraethyl orthosilicate (TEOS) exclusively took place at the particles surface in the presence of ammonia following the so-called Stöber process and the silica-coated polymer powers were calcined at 800 °C. The diameters of hollow silica spheres are found to be very close to the original diameter and the average pore diameter is less than 100 nm. Moreover, the hollow silica nanoparticles have uniform aperture, do not agglomerate and collapse.     

Self-organization of colloidal particles during drying of a droplet: Modeling and experimental study

Formation of structurized micro/nanoparticle aggregates in spray drying process is analyzed theoretically and experimentally. Colloids of mono- and bimodal particle size distribution are used as the precursors to demonstrate different patterns of particle self-organization inside the drying droplet. In case of monodisperse primary particles their self-organization in the final aggregate results in either a hollow or a full (packed) spherical structure. For primary particles with bimodal size distribution, either the layered structure of aggregates is formed (with smaller particles forming outer layer and the bigger particles captured inside) or the ordering of bigger particles on the aggregate surface is observed, depending on process parameters. Numerical investigations allow to predict and explain the conditions at which self-assembling of particles within powder aggregates takes place.     

Plasma spraying of zirconia-titania-silica bio-ceramic composite coating for implant application

Zirconia-titania-silica (ZTS) bio-ceramic composite coating was deposited on titanium surface via plasma spray process. The original feedstock was prepared by mixing equal amounts (wt.%) of each powder in ceramic pot followed by stirring with ceramic ball. The resulting composite powder was sprayed at two different stand-off distances (SOD: 45 and 50 mm). Silica particles are distributed uniformly in the coating matrix. Amorphous silica was detected by energy-dispersive X-ray spectroscopy (EDXS) and FT-IR analysis which showed the spectra of Si-O and Ti-O stretching bonds. Anatase phase, the main phase of titania in feedstock, was transformed into rutile phase in the coating structure. The spraying efficiency was increased as the stand-off distance decreased. High intensity of tetrahedral zirconia phase was detected in the composite coating sprayed at 50 mm SOD.     

正十八烷相变纳胶囊/多壁碳纳米管流体的制备及性能表征

采用原位聚合法合成了一种以正十八烷为芯材,密胺树脂为壁材的相变纳米级胶囊;通过超声搅拌将相变纳胶囊和功能化的多壁碳纳米管复合,得到一种稳定的复合相变流体,并通过红外光谱(FT-IR)、扫描电镜(SEM)、Zeta电位和差示量热(DSC)等手段对其进行表征。结果表明:Fenton试剂处理过的多壁碳纳米管表面带有大量的—OH和—COOH等亲水性基团;合成的正十八烷相变纳胶囊为直径200~400nm的表面光滑的圆球形;Zeta电位测试结果显示,当表面活性剂曲拉通X-100和十六烷基三甲基溴化铵(CTAB)的用量都为3.3%时,复合相变流体的分散稳定性最好;DSC结果显示,复合相变流体使用前、后烘干物的熔融焓和结晶焓都在110J/g左右。     

Numerical simulation of coating growth and pore formation in rapid plasma spray tooling

Rapid plasma spray tooling (RPST) is a process that can quickly make molds from rapid prototyping or nature patterns without limitation of pattern's size or material. In this paper, the process of coating growth and pore formation in RPST has been analyzed by numerical simulation. The objective of this work was to determine the porosity in plasma sprayed coatings and verify the developed computer model, which might serve for future thermal residual stress studies of plasma sprayed coatings. The analysis was divided into two steps: particle flattening and coating growth. In the analysis, a ballistic model was used for modeling the in-flight powder particles. The method allows for the calculation of off-normal spray angle, which is common in plasma spraying of engineering components. Also, a set of rules for coating growth as well as pore formation in the coating has been proposed. Based on these works, a computer program was developed to calculate the effects of process parameters, such as gun scanning velocity, spray angle, etc., on the porosity of the coating. Finally, an experiment was carried out to verify the effects of spray parameters on the porosity. The results agree with the prediction of the model.     

Effects of spray parameters on the microstructure and property of Al2O3 coatings sprayed by a low power plasma torch with a novel hollow cathode

Al₂O₃ coating is deposited using a low power plasma torch with a novel hollow cathode through axial powder injection under a plasma power up to several kilowatts. The effects of the main processing parameters including plasma arc power, operating gas flow and spray distance on particle velocity during spraying, and the microstructure and property of the coating are investigated. The microstructure of the Al₂O₃ coating is examined using optical microscopy and X-ray diffraction analysis. The property of the coating is characterized by dry rubber wheel abrasive wear test. The velocity of in-flight particle is measured using a velocity/temperature measurement system for spray particle based on thermal radiation from the particle. The dependency of the microstructure and property of the coating on spray particle conditions are examined by comparing the particle velocity, and microstructure and abrasive wear weight loss of subsequent coating deposited by low power plasma spray with those of the coating by conventional plasma spray at a power one order higher. X-ray diffraction analysis of the coating revealed that Al₂O₃ particles during low power plasma spraying reach to sufficiently melting state prior to impact on the substrate with a velocity comparable to that in conventional plasma spraying. The experiment results have shown that processing parameters have significant influence on the particle conditions and performance of deposited Al₂O₃ coating. The coating of comparable microstructure and properties to that deposited by conventional plasma spray can be produced under a power one order lower. From the present study, it can be suggested that a comparable coating can be produced despite plasma power level if the comparable particle velocity and molten state are achieved.