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.     

Production and characterization of HA and SiHA coatings

Plasma sprayed hydroxyapatite (HA) coatings on metallic prostheses have been used clinically in dentistry and orthopedics since the mid 1980s. The coating properties are dependent on the spraying parameters. Since silicon-substituted hydroxyapatite (SiHA) has been shown to offer improved bioactivity over phase pure HA, SiHA coatings have the potential for enhanced performance in clinical application. In this study, phase pure HA and 0.8 wt% SiHA powders were synthesized with similar particle size distribution and morphology. The powders were plasma sprayed onto Ti–6Al–4V substrates at 37 kW and 40 kW plasma gun input power respectively. Four kinds of samples were prepared, HAC 37, HAC 40, SiHAC 37 and SiHAC 40. Materials characterization showed that the coatings were of relatively high phase purity. In vitro cell culture demonstrated that human osteoblast cells grew well on all samples, with the highest cell growth observed on SiHA coatings produced under the lower plasma gun input power.     

Improvement in mechanical properties of plasma sprayed hydroxyapatite coatings by Al2O3 reinforcement

Thermal sprayed hydroxyapatite coatings suffer from poor mechanical properties like tensile strength, wear resistance, hardness, toughness and fatigue. The mechanical properties of hydroxyapatite coatings can be enhanced via incorporation of secondary bioinert reinforcement material. In this study an attempt has been made to improve the mechanical properties of plasma sprayed hydroxyapatite by reinforcing it with 10, 20 and 30% Al₂O₃. The plasma sprayed coatings have been characterized using FE-SEM/EDAX, XRD, AFM and FTIR spectroscopy. Corrosion studies have been done in simulated body fluid and abrasive wear studies have been performed on flat specimens on a disk wear tester. Microhardness, tensile strength and wear resistance are found to be increased with increasing Al₂O₃ content. All types of coatings show superior resistance against corrosion in simulated body fluid.     

Plasma spraying of biologically derived hydroxyapatite on implantable materials

Plasma spraying of hydroxyapatite (HA) coatings on human implants is considered to provide a promising means of enhancing their biocompatibility and improving tissue growth. This paper briefly describes a method of extracting HA powder from a biological source, namely human teeth. The physical and chemical characteristics of the derived powder are studied and the suitability of this powder for plasma spraying applications is ascertained. The deposited coatings are found to retain the chemistry characteristic of the apatite. Typical results of metallographic and scanning electron microscopy (SEM) studies and hardness measurements on the sprayed HA coatings are presented.     

Ti-6Al-4V合金基体等离子喷涂生物活性羟基磷灰涂层的研究进展

系统阐述了在钛合金(Ti-6Al-4V)表面等离子喷涂羟基磷灰石(HA)涂层的研究进展.描述了等离子喷涂制备HA涂层的工艺过程、微观形貌和化学组成.综述几种综合性能较高的复合型涂层:HA/BG(生物活性玻璃)复合涂层,HA/ZrO2复合增强型涂层,HA/Ti涂层,HA/Ti-6Al-4V梯度涂层;并对HA涂层发展趋势进行了展望.     

In vivo biological responses of plasma sprayed hydroxyapatite coatings with an electric polarized treatment in alkaline solution

The plasma sprayed hydroxyapatite coatings were post-treated by an electric polarized treatment in alkaline solution (PAS). The compositions, stabilities, surface charges, bone-like apatite formation abilities of the PAS coatings were investigated. The bioactivity of the PAS coatings was characterized in vivo. The results showed that the stabilities of the PAS coatings were improved because of the increased crystallinity and the decreased impurity phase. The bone-like apatite formation abilities were also improved after the PAS treatment because of the negative charges formed on the coating surfaces. Animal experiments showed that the PAS coatings could accelerate the initial fixation of the implant. The results indicated that the PAS is a promising post-treatment method to improve the biological properties of the plasma sprayed hydroxyapatite coatings.     

MANUFACTURE AND PROPERTIES OF PLASMA SPRAYED Cr2O3

Low porosity (some %) chromia coatings have been plasma sprayed onto several substrates by atmospherical and vacuum plasma spraying. Different phases appear in the sprayed product; metallic Cr and the metastable tetragonal Cr₃O₄ phase have been identified. A post annealing treatment completely removes these phases. This behaviour can be correlated with differences between the coefficients of thermal expansion comparing the as-sprayed with the annealed material. Hot Isostatic Pressing improves the interface bonding between coating and substrate and reduces porosity as can be seen from the results of metallographical investigations. If aluminium is present in the substrate alloy, chemical interactions have been observed. First results from measurements of residual stresses in coatings show the influence of coefficients of expansion and substrate temperature during spraying. Gastightness of the sprayed chromia could not yet be established.     

Microstructural characterization of hydroxyapatite coating on titanium

The microstructure of hydroxyapatite plasma sprayed onto titanium alloy has been studied by using transmission electron microscopy. It has been shown that while substantial portions of the coating are crystalline hydroxyapatite, regions of amorphous calcium phosphate with Ca/P ratios of 0.6–1.0 are also present, both in the coatings and at the metal-ceramic interface. The microstructures observed have also been found to be consistent with devitrification of the amorphous calcium phosphates producing regions of very fine grained hydroxyapatite. A calcium titanate phase has also been detected at the metal-ceramic interface produced by the chemical reaction of hydroxyapatite to titanium.     

Surface Modification of Biomaterials in Hard Tissue Applications

Surface modification technologies are quite common in the biomedical field to improve the mechanical,chemical, physical and biological properties of implants such as artificial joint and cardiovascular devices. In this paper, recent progress in the investigation of the bioactivity and biocompatibility enhancement of implants using plasma spraying and plasmabased ion implantation (PIII) is described. Plasma sprayed hydroxyapatite (HA) coatings are commonly used as bioactive coatings but the relatively poor adhesion between the coatings and titanium is one of main disadvantages which have limited their biomedical applications. In our recent studies, novel bioactive coatings, such as wollastonite and dicalcium silicate, were deposited onto titanium to enhance the surfaces bioactivity and biocompatibility. Our results indicate that plasma sprayed wollastonite and dicalcium silicate coatings possess excellent bioactivity as well as relatively high bonding strength. Plasma immersion ion implantation was also employed to improve the anti-corrosion and biological properties of implants.     

喷涂工艺对Fe-Ni-B喷涂涂层组织性能的影响

采用高速火焰喷涂技术以及等离子喷涂技术制备了Fe-Ni-B涂层.利用扫描电子显微镜(SEM)、X射线荧光光谱仪(EDX)分析了粉末以及涂层的微观结构、涂层到基体的成分分布.利用X射线衍射(XRD)分析了喷涂态的涂层物相.并对涂层的结合强度及抗热震性能进行了试验研究.研究结果认为:等离子喷涂层组织更为致密,但其热喷涂涂层存在的层状结构也更加明显.熔融液滴在涂层表面的平铺效果都比较好.Fe、Ni元素的分布从涂层到基体基本成均匀分布,避免了局部元素偏析所造成的应力集中.热震后,等离子喷涂涂层中的裂纹分布细小且无规律.高速火焰喷涂涂层裂纹主要集中在涂层与基体结合部位.根据材料抗热震性能的能量理论和弹性理论,等离子喷涂涂层的抗热震能力更强.并且涂层的断裂失效主要产生在结合部位.     

Plasma spraying of zirconia-reinforced hydroxyapatite composite coatings on titanium: Part II Dissolution behaviour in simulated body fluid and bonding degradation

The change of phase, morphology and bond strength of plasma sprayed hydroxyapatite (HA) coating and ZrO2/HA composite coatings immersed in simulated body fluid (SBF) for various periods of time was studied. X-ray diffractometry (XRD) and scanning electron microscopy (SEM) were used to identify the phase and observe the morphology of the coating surface before and after immersion. In addition, inductively coupled plasma emission spectroscopy (ICP) was used to measure the ion release rate of coatings in SBF for various periods of time. Observation of the morphology by SEM shows that the composite coating with the addition of ZrO2 in HA significantly reduced the dissolution rate of impurity phases in simulated body fluid. The argument was supported by measurement of Ca2+ ion concentration in SBF. During plasma spraying, less OH- ions were lost in a ZrO2-containing composite coating. This factor, together with the reduced effective surface of the ZrO2-containing HA coating, were attributed to the reduced dissolution rate of the composite coatings. All the plasma sprayed coatings degraded after immersion in SBF owing to dissolution of constituents in the coating, however, the addition of ZrO2 in HA improved the bonding strength of HA coating after immersion in SBF.     

BSAS喷涂粉体制备工艺及其对涂层性能的影响

采用不同工艺制备BSAS(BaO-SrO-Al_2O_3-SiO_2)喷涂粉体。研究喷涂粉体特性及其对等离子喷涂工艺制备的环境障涂层结构和性能的影响。结果表明:粉体造粒工艺制备的BSAS喷涂粉体颗粒不均匀,流动性差。制备的涂层粗糙,孔隙率高,结合强度为24.1MPa;造粒烧结工艺制备的BSAS喷涂粉体表面圆滑,流动性好,沉积效率高。制备的涂层结构均匀,少孔隙,无裂纹,结合强度达到29.8MPa,涂层中BSAS相保留率最高,达到53.2%;熔融破碎工艺制备的BSAS粉体呈致密不规则块状,虽然流动性好沉积效率高,制备的涂层光滑且孔隙极少,但微裂纹较多,结合强度仅为14.2MPa,粉体经喷涂后发生相结构重组,BSAS相保留率为20.5%,对涂层的高温性能不利。分析认为,造粒烧结工艺制备BSAS粉体具有工艺过程简化、粉体质量好、相稳定性高等优点,更适合于等离子喷涂的要求。     

羟基磷灰石生物涂层的复合制备与生物相容性

采用等离子喷涂CaHPO4和水热处理复合制备羟基磷灰石生物涂层,研究了羟基磷灰石涂层的结合强度和溶解性,用成骨细胞考察了生物相容性,结果表明,喷涂涂层由C aHPO4,β－Ca2P2O7和α-C3(PO4)2组成,其相比例,结晶性和形貌取决于喷涂电流和喷涂距离;喷涂涂导经过水热处理可转化为针状结晶的缺钙羟基磷灰石,这种羟基磷灰石涂层具有高的结合强度和稳定性,与成骨细胞的生物相容性良好。     

PLASMA SPRAYED ZrO2 THICK THERMAL BARRIER COATINGS

ZrO₂ thermal barrier coatings have been plasma sprayed onto steel substrates with a FeCrAlY bond layer. During spraying the conditions have been varied by cooling the back side of the substrate in ice-water or heating it on a hot plate, and simultaneously cooling the sprayed surface with air at various pressures. The residual strain distributions have been measured in the as-sprayed couples using the incremental blind-hole method. The measurements show that residual strains can be controlled through temperature manipulation, and the method can be used to determine the optimum spraying conditions. The microstructure has been observed in a transmission electron microscope, and the effect of microstructural features on the microstrains are briefly discussed.     

Surface Refinement of Metal Foams

Aluminium foams produced via the PM‐process are characterized by a moderate specific strength, a high surface roughness, and a poor wear behavior; to increase their mechanical properties and to improve the surface finish, wear and corrosion resistance; thermally sprayed coatings can be applied. The quality of the coating depends on the coating material, the chosen process, the preparation of the surface and spraying parameters. Aluminium alloys and iron based alloys for abrasive applications were deposited via electric arc spraying, ceramic coatings against wear were deposited by means of plasma spraying. Hard metallic coatings for severe abrasive applications were applied by high‐velocity‐oxyfuel spraying (HVOF). The results proved the suitability of this technique to significantly enhance the mechanical properties and the surface finish of metal foams. The specific strength and stiffness of the new composite materials outperform pure metal foams. The corrosion behavior was tested performing a salt spray test.     

Formation of high heat resistant coatings by using gas tunnel type plasma spraying

Zirconia sprayed coatings are widely used as thermal barrier coatings (TBC) for high temperature protection of metallic structures. However, their use in diesel engine combustion chamber components has the long run durability problems, such as the spallation at the interface between the coating and substrate due to the interface oxidation. Although zirconia coatings have been used in many applications, the interface spallation problem is still waiting to be solved under the critical conditions such as high temperature and high corrosion environment. The gas tunnel type plasma spraying developed by the author can make high quality ceramic coatings such as Al2O3 and ZrO2 coating compared to other plasma spraying method. A high hardness ceramic coating such as Al2O3 coating by the gas tunnel type plasma spraying, were investigated in the previous study. The Vickers hardness of the zirconia (ZrO2) coating increased with decreasing spraying distance, and a higher Vickers hardness of about Hv = 1200 could be obtained at a shorter spraying distance of L = 30 mm. ZrO2 coating formed has a high hardness layer at the surface side, which shows the graded functionality of hardness. In this study, ZrO2 composite coatings (TBCs) with Al2O3 were deposited on SS304 substrates by gas tunnel type plasma spraying. The performance such as the mechanical properties, thermal behavior and high temperature oxidation resistance of the functionally graded TBCs was investigated and discussed. The resultant coating samples with different spraying powders and thickness are compared in their corrosion resistance with coating thickness as variables. Corrosion potential was measured and analyzed corresponding to the microstructure of the coatings. Keywords: High Heat Resistant Coatings, Gas Tunnel Type Plasma Spraying, Hardness,     

Prozeßidentifikation beim Plasmaspritzen temperatursensitiver Werkstoffe mit Hilfe einer Infrarot-Hochtemperatur-Thermokamera

Process-Identification at Plasma Spraying Thermally Sensitive Materials Using an Infra-red Thermal Imaging System Nowadays so called thermally sensitive materials are deposited by thermal spray techniques. Due to the high temperature process an undesired alteration (evaporation, chemical decomposition) of the material could occur. Therefore, optimisation of the deposition based only on empirical methods may be deremental with respect to the coating properties. This study shows the potential of an IR thermal imaging technique as a process control for evaluation and optimisation of the deposition through better understanding of the thermal spray process. The spray trials presented are based on preliminary examinations carried out with diagnostic tools. Therefore it was possible to achieve defined air plasma sprayed coatings of hydroxyapatite with different coating and component properties. This is particularly of interest, since there exists only a standard for hydroxyapatite as starting material but not for plasma sprayed coatings. Hence the coatings had either high or low contents of undesired phases, different degrees of cristallinity and bond strengths-varying from 5 to 42 MPa. Besides the power levels and the way to obtain the power the carrier gas flow significantly influences the properties of the coatings.     

Plasma Spraying of Al2O3 and ZrSiO4 to Form ZrO2- Mullite Composites

Zirconia is effective in improving fracture toughness of a number of ceramics when introduced as a reinforcement either in the form of participates, dispersed phase or whiskers because of its unique tetragonal-monoclinic (t → m) transformation. In this paper, the authors attempt to prepare ZrO₂, reinforced mullite by plasma spraying mixtures of zircon and alumina. Pre-mixed powders of zircon and alumina are injected onto a D.C. plasma jet. The plasma sprayed particles are collected in distilled water and analyzed. The results indicate that the plasma sprayed powders consist of zirconia, zircon, and alumina. It was found that fine grained, even amorphous and chemically homogeneous composite powders could be obtained by ball milling and plasma spraying. Recrystallization of amorphous phases and formation of mullite occurred at about 1OOO^°C in plasma sprayed powders. This value is more than 500^°C lower than the formation of mullite in asmilled powders. Uniform coatings with good structural integrity were obtained by plasma spraying. The relative quantity of mullite in coatings after heat treatment is about 4 times as much as that obtained in the spheroidized powders. Preheat treatment of the spheroidized powder promoted dissociation of zircon. Zirconia remained as tetragonal under 1000^°C in the sprayed coatings.     

Thermisch gespritzte titankarbidverstärkte Eisenbasisschichten als Alternative zu konventionellen karbidischen Werkstoffen

Thermal sprayed titanium carbide strengthened iron coatings as alternative for conventional carbide materials High velocity oxygen fuel (HVOF) sprayed carbide based materials are industrially well established as wear and corrosion protection coatings. Because of the high carbide content of typically 75 weight percent and more they are providing a very high hardness and excellent wear resistance. However, at the same time this characteristic is resulting in major difficulties during post‐processing steps. Cost‐effective machining processes such as turning and milling are usually not applicable and any sprayed oversize has to be reduced by grinding. To overcome these drawbacks a novel carbide‐based material concept, which is already in use for sintering processes, is offering promising properties. Titanium carbides at a reduced content of 33 weight percent embedded in a ferrous matrix can provide distinctly improved characteristics for optimal machinability. Depending on the carbon content the iron‐base material can additionally offer a temperable matrix for enhanced wear behaviour. Within this study spray trials have been carried out to investigate the sprayability of titanium carbide strengthened iron powders with a gaseous and a liquid fuel driven high velocity oxygen fuel spraying system. Optimised parameters were developed by implementing the statistical method of design of experiment (DoE). The resulting coatings were analysed with respect to microstructure, hardness and phase composition and compared to sintered reference materials. Furthermore thermally sprayed iron‐based coatings strengthened with titanium carbides were heat treated to proof the retained temperability of the iron matrix after thermal spray processing.     

Plasma sprayed hydroxy apatite coatings

This paper describes the method of producing plasma sprayed coatings of hydroxy apatite (HA) on metallic substrates of Ti-6Al-4V. Hydroxy apatite is a material which has similar composition to that of the mineral phase of the human bone. Poor mechanical properties however inhibits its use in the load bearing applications. The powders prepared in our laboratory are sprayed using a plasma spray torch operating in ambient. The deposited coatings are charaterized by X-ray diffraction and found to retain HA in the coatings as per requirements. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995.