Vapor Phase Deposition Using Plasma Spray-PVD™

Plasma spray—physical vapor deposition (PS-PVD) is a low pressure plasma spray technology to deposit coatings out of the vapor phase. PS-PVD is a part of the family of new hybrid processes recently developed by Sulzer Metco AG (Switzerland) on the basis of the well-established low pressure plasma spraying (LPPS) technology. Included in this new process family are plasma spray—chemical vapor deposition (PS-CVD) and plasma spray—thin film (PS-TF) processes. In comparison to conventional vacuum plasma spraying and LPPS, these new processes use a high energy plasma gun operated at a work pressure below 2 mbar. This leads to unconventional plasma jet characteristics which can be used to obtain specific and unique coatings. An important new feature of PS-PVD is the possibility to deposit a coating not only by melting the feed stock material which builds up a layer from liquid splats, but also by vaporizing the injected material. Therefore, the PS-PVD process fills the gap between the conventional PVD technologies and standard thermal spray processes. The possibility to vaporize feedstock material and to produce layers out of the vapor phase results in new and unique coating microstructures. The properties of such coatings are superior to those of thermal spray and EB-PVD coatings. This paper reports on the progress made at Sulzer Metco to develop functional coatings build up from vapor phase of oxide ceramics and metals.     

等离子喷涂-物理气相沉积高温防护涂层研究进展

等离子喷涂-物理气相沉积（PS-PVD）是基于低压等离子喷涂发展起来的一种新型多功能薄膜及涂层制备技术。由于其独特的等离子射流特征,可实现气液固多相涂层沉积,获得非视线沉积。文中首先介绍了国内外PS-PVD技术等离子体数值模拟和在线检测技术的研究现状,其次讨论了PS-PVD羽-柱状结构热障涂层的形成机制及与传统热障涂层在热导率、抗冲蚀等性能方面的差异,阐述了PS-PVD技术制备环境障涂层的研究进展,最后对PS-PVD技术沉积高温防护涂层的优势和存在的问题进行了总结。     

Improved Thermal Cycling Durability of Thermal Barrier Coatings Manufactured by PS-PVD

The plasma spray-physical vapor deposition (PS-PVD) process is a promising method to manufacture thermal barrier coatings (TBCs). It fills the gap between traditional thermal spray processes and electron beam physical vapor deposition (EB-PVD). The durability of PS-PVD manufactured columnar TBCs is strongly influenced by the compatibility of the metallic bondcoat (BC) and the ceramic TBC. Earlier investigations have shown that a smooth BC surface is beneficial for the durability during thermal cycling. Further improvements of the bonding between BC and TBC could be achieved by optimizing the formation of the thermally grown oxide (TGO) layer. In the present study, the parameters of pre-heating and deposition of the first coating layer were investigated in order to adjust the growth of the TGO. Finally, the durability of the PS-PVD coatings was improved while the main advantage of PS-PVD, i.e., much higher deposition rate in comparison to EB-PVD, could be maintained. For such coatings, improved thermal cycling lifetimes more than two times higher than conventionally sprayed TBCs, were measured in burner rigs at ~1250 °C/1050 °C surface/substrate exposure temperatures.     

Design of Experiment Analysis of the Sulzer Metco DJ High Velocity Oxy-Fuel Coating of Hydroxyapatite for Orthopedic Applications

High Velocity Oxy-Fuel (HVOF) has the potential to produce hydroxyapatite (HA; Bio-ceramic) coatings based on its experience with other sprayed ceramic materials. This technique should offer mechanical and biological results comparable to other thermal spraying processes, such as atmospheric plasma thermal spray, currently FDA approved for HA deposition. Deposition of HA via HVOF is a new venture especially using the Sulzer Metco Diamond Jet (DJ) process, and the aim of this article was to establish this technique's potential in providing superior HA coating results compared to the FDA-approved plasma spray technique. In this research, a Design of Experiment (DOE) model was developed to optimize the Sulzer Metco DJ HVOF process for the deposition of HA. In order to select suitable ranges for the production of HA coatings, the parameters were first investigated. Five parameters (factors) were researched over two levels namely: oxygen flow rate, propylene flow rate, air flow rate, spray distance, and powder flow rate. Coating crystallinity and purity were measured at the surface of each sample as the responses to the factors used. The research showed that propylene, air flow rate, spray distance, and powder feed rate had the largest effect on the responses, and the study aimed to find the preferred optimized settings to achieve high crystallinity and purity of percentages of up to 95%. This research found crystallinity and purity values of 93.8 and 99.8%, respectively, for a set of HVOF parameters which showed improvement compared to the crystallinity and purity values of 87.6 and 99.4%, respectively, found using the FDA-approved Sulzer Metco Atmospheric Plasma thermal spray process. Hence, a new technique for HA deposition now exists using the DJ HVOF facility; however, other mechanical and biorelated properties must also be assessed.     

等离子-物理气相沉积（PS-PVD）及其射流非接触检测方法

等离子-物理气相沉积(PS-PVD)是制备高温防护涂层和功能涂层的一种新方法,既可涵盖等离子喷涂和电子束物理气相沉积工艺,还可实现涂层宏观/介观/微观等跨尺度结构的定制化设计与制备,在热障涂层(TBCs)、环境障涂层(EBCs)、环境热障涂层(TEBCs)、透氧薄膜、燃料电池和太阳电池电极薄膜等领域具有广泛应用前景,尤其在航空发动机和燃气轮机防护涂层领域被视为高性能TBCs/EBCs制备技术发展的新方向。比较分析了PS-PVD等离子射流膨胀流动、材料快速加热气化离化和长距离多模式输运沉积的全流程过程,介绍了PS-PVD原理与设备系统,面向等离子射流参数快速无损检测分析的目标,建立了基于光学发射光谱学(OES)的等离子射流和材料特性非接触式检测与诊断装备系统,发展了射流和材料特性参数的定量表征和精确诊断方法。依据电子数密度等检测结果,进一步计算分析等离子温度分布规律。基于射流与材料检测结果,研究了粉末材料在等离子射流中的多相态转变行为,归纳了调控沉积单元多相态转变的工艺控制参数集。这些硬件平台和表征检测方法的建立,为构建PS-PVD理论和研制新型高性能热防护涂层提供了坚实的理论基础和必要的条件支撑。     

低压等离子喷涂技术在功能性涂层的应用进展

与常规等离子喷涂相比,低压等离子喷涂技术在真空或低压下进行等离子喷涂,可制备更低杂质、更高致密度、更高结合强度的涂层。介绍了常规等离子喷涂焰流速度高、工艺稳定性好、沉积效率高、可控性好的特点,详细阐述了低压等离子喷涂技术清洁、高速、长焰流、预热、电清理的工艺优势,说明了低压等离子喷涂技术在热障涂层、抗气蚀涂层、面向等离子体材料等功能性涂层制备上的应用,最后从完善相关理论、与其他技术联用、工艺在线可控、气氛压力更低等方面,以及在航空、航天、电子等领域的运用,对低压等离子喷涂技术的发展进行了展望。     

Columnar-Structured Thermal Barrier Coatings (TBCs) by Thin Film Low-Pressure Plasma Spraying (LPPS-TF)

The very low-pressure plasma Spray (VLPPS) process has been developed with the aim of depositing uniform and thin coatings with coverage of a large area by plasma spraying. At typical pressures of 100-200 Pa, the characteristics of the plasma jet change compared to conventional low-pressure plasma-spraying processes (LPPS) operating at 5-20 kPa. The combination of plasma spraying at low pressures with enhanced electrical input power has led to the development of the LPPS-TF process (TF = thin film). At appropriate parameters, it is possible to evaporate the powder feedstock material providing advanced microstructures of the deposits. This technique offers new possibilities for the manufacturing of thermal barrier coatings (TBCs). Besides the material composition, the microstructure is an important key to reduce thermal conductivity and to increase strain tolerance. In this regard, columnar microstructures deposited from the vapor phase show considerable advantages. Therefore, physical vapor deposition by electron beam evaporation (EB-PVD) is applied to achieve such columnar-structured TBCs. However, the deposition rate is low, and the line-of-sight nature of the process involves specific restrictions. In this article, the deposition of TBCs by the LPPS-TF process is shown. How the evaporation of the feedstock powder could be improved and to what extent the deposition rates could be increased were investigated.     

Microstructural Effects and Properties of Non-line-of-Sight Coating Processing via Plasma Spray-Physical Vapor Deposition

Plasma spray-physical vapor deposition (PS-PVD) is a unique processing method that bridges the gap between conventional thermal spray and vapor phase methods, and enables highly tailorable coatings composed of a variety of materials in thin, dense layers or columnar microstructures with modification of the processing conditions. The strengths of this processing technique are material and microstructural flexibility, deposition speed, and potential for non-line-of-sight (NLOS) capability by vaporization of the feedstock material. The NLOS capability of PS-PVD is investigated here using yttria-stabilized zirconia and gadolinium zirconate, which are materials of interest for turbine engine applications. PS-PVD coatings were applied to static cylindrical substrates approximately 6-19 mm in diameter to study the coating morphology as a function of angle. In addition, coatings were deposited on flat substrates under various impingement configurations. Impingement angle had significant effects on the deposition mode, and microscopy of coatings indicated that there was a shift in the deposition mode at approximately 90° from incidence on the cylindrical samples, which may indicate the onset of more turbulent flow and PVD-like growth. Coatings deposited at non-perpendicular angles exhibited a higher density and nearly a 2× improvement in erosion performance when compared to coatings deposited with the torch normal to the surface.     

Investigations on the Nature of Ceramic Deposits in Plasma Spray–Physical Vapor Deposition

In Plasma Spray–Physical Vapor Deposition (PS-PVD) process, major fractions of the feedstock powder can be evaporated so that coatings are deposited mainly from the vapor phase. In this work, Computational Fluid Dynamics (CFD) results indicate that such evaporation occurs significantly in the plasma torch nozzle and even nucleation and condensation of zirconia is highly possible there. Experimental work has been performed to investigate the nature of the deposits in the PS-PVD process, in particular coatings from condensate vapor and nano-sized clusters produced at two spraying distances of 1000 mm and 400 mm. At long spraying distance, columns in the coatings have pyramidal tops and very sharp faceted microstructures. When the spraying distance is reduced to 400 mm, the tops of columns become relatively flat and a faceted structure is not recognizable. XRD patterns show obvious preferred orientations of (110) and (002) in the coatings sprayed at 400 mm but only limited texture in the coatings sprayed at 1000 mm. Meanwhile, a non-line of sight coating was also investigated, which gives an example for pure vapor deposition. Based on these analyses, a vapor and cluster depositions are suggested to further explain the formation mechanisms of high-quality columnar-structured PS-PVD thermal barrier coatings which have already shown excellent performance in cyclic lifetime test.     

Superior thermal barrier coatings using solution precursor plasma spray

A novel process, solution precursor plasma spray (SPPS), is presented for depositing thermal barrier coatings (TBCs), in which aqueous chemical precursors are injected into a standard direct current plasma spray system. The resulting coatings microstructure has three unique features: (1) ultra fine splats (1 μm), (2) nanometer and micron-sized interconnected porosity, and (3) closely spaced, through-thickness cracks. Coatings over 3 mm thick can be readily deposited using the SPPS process. Coating durability is excellent, with SPPS coatings showing, in furnace cycling tests, 2.5 times the spallation life of air plasma coatings (APS) and 1.5 times the life of electron beam physical vapor deposited (EB-PVD) coatings. The conductivity of SPPS coatings is lower than EB-PVD coatings and higher than the best APS coatings. Manufacturing cost is expected to be similar to APS coatings and much lower than EB-PVD coatings. The SPPS deposition process includes droplet break-up and material arriving at the deposition surface in various physical states ranging from aqueous solution, gel phase, to fully-molten ceramic. The relation between the arrival state of the material and the microstructure is described.     

Thermal Cycling Behavior of Quasi-Columnar YSZ Coatings Deposited by PS-PVD

Columnar-structured thermal barrier coatings, owing to their high strain tolerance, are expected for their potential possibilities to substantially extend turbine lives and improve engine efficiencies. In this paper, plasma spray-physical vapor deposition (PS-PVD) process was used to deposit yttria partially stabilized zirconia (YSZ) coatings with quasi-columnar structures. Thermal cyclic tests on burner rigs and thermal shock tests by heating and water-quenching method were involved to evaluate the thermal cycling and thermal shock behaviors of such kind of structured thermal barrier coatings (TBCs). Evolution of the microstructures, phase composition, residual stresses and failure behaviors of quasi-columnar YSZ coatings before and after the thermal tests was investigated. The quasi-columnar coating obtained had an average life of around 623 cycles when the spallation area reached about 10% of the total coating surface during burner rig tests with the coating surface temperature of ~1250 °C. Failure of the coating is mainly due to the break and pull-out of center columnar segments.     

Low conductivity plasma sprayed thermal barrier coating using hollow psz spheres: Correlation between thermophysical properties and microstructure

Life and thermal properties of plasma sprayed TBCs - widely used in gas turbine engines - are closely related to the microstructure of the ceramic top coating. Especially, the thermal behaviour of this coating is induced by the void shapes and networks which are in turn determined by both the spraying conditions and the feedstock material.A specific hollow yttria partially stabilised zirconia powder was produced in a one-step process by spray drying and an experimental statistical design study was conducted to investigate the influence of spraying variables (primary and secondary gas flow rates, arc current, spraying distance, spraying angle and traverse speed) on structure and properties of resulting plasma sprayed coatings. The coatings were characterized with respect to deposition efficiency, roughness, porosity and thermal conductivity. A reduction of 25% of the thermal conductivity was achieved by improving the spray and powder parameters. A quantitative characterization of the porous structure using image analysis of polished cross-sections was implemented. The parameters that have relevant influence on the coating porous structure were identified, and their relative importance was determined. An attempt was made to identify morphological criteria of the porous network (coarse/fine porosity ratio, cracks total length, cracks orientation) correlating with the thermal conductivity values.     

高速火焰喷涂高质量NiCoCrAlTaReSiY抗氧化涂层

研究了用高速火焰喷涂(HVOF)替代低压等离子喷涂(LPPS)沉积高质量的MCrAlY涂层。试验用粉料为NiCoCrAlTaReSiY,采用以煤油为燃料的K2型HVOF系统沉积涂层,研究喷嘴长度、喷涂工艺参数对粉末沉积工艺过程以及涂层性能的影响;测量涂层的孔隙率及氧含量,观察涂层经真空热处理以及高温空气氧化后的显微结构,测量了Al、O等元素在氧化涂层中的分布。结果表明,所沉积的NiCoCrAlTaReSiY涂层具有优越的抗氧化性。     

热喷涂 Mo 及 Mo 基复合涂层研究进展

热喷涂Mo及Mo基复合涂层因熔点高、硬度高、耐磨损、耐腐蚀及高温性能稳定等诸多特点,而广泛应用于机械零件生产及表面修复。随着以资源有效利用和机械产品再制造为一体的可持续发展战略不断推进,此类涂层将拥有更为广阔的应用前景。首先介绍了国内外在热喷涂Mo及Mo基复合涂层方面的研究发展和应用现状;随后依据热喷涂技术的发展历程,分别总结论述了不同热喷涂技术,即火焰喷涂(普通火焰喷涂、高速火焰喷涂)、等离子喷涂(普通等离子喷涂、超音速等离子喷涂、微束等离子喷涂、低压等离子喷涂)及电热爆炸喷涂中,Mo及Mo基复合涂层的制备工艺、涂层性能特点及存在的问题;接着指出了热喷涂Mo及Mo基复合涂层在新概念武器、航空航天等高科技领域的应用前景。最后,就进一步拓展Mo及Mo基复合涂层在贫油减摩、高温高速耐磨、高温耐腐蚀及氧化等复杂环境下的应用范围,结合热喷涂技术的研究热点及发展方向,指出了未来热喷涂Mo及Mo基复合涂层在材料组分设计和工艺优化研究中应重点关注的方面。     

冷喷涂和低压等离子喷涂Ni-Ti涂层：组织和性能

采用原子比1：1的Ni和Ti为原料,通过冷喷涂(CS)和低压等离子喷涂(LPPS)制备了Ni-Ti复合涂层,研究喷涂工艺对涂层的组织(孔隙率、相组成和显微组织)和性能(硬度、耐磨性和耐蚀性)的影响。结果表明：两种涂层均未发生明显的氧化,但表现出不同的组织结构。高速碰撞后的颗粒发生严重塑性变形使CS涂层具有低的孔隙率,且XRD未检测到其它的相生成;层片状结构的LPPS涂层内部形成了Ni-Ti金属间化合物相,其表现出高的显微硬度和低的磨损率。此外,LPPS涂层高的腐蚀电位和低的腐蚀电流密度,表明其高的耐蚀性。     

Plasma Spray-CVD: A New Thermal Spray Process to Produce Thin Films from Liquid or Gaseous Precursors

New dedicated coating processes which are based on the well-known LPPS™ technology but operating at lower work pressure (100 Pa) are being actively developed. These hybrid technologies contribute to improve the efficiencies in the turbine industry such as aero-engines and land-based gas turbines. They also have a great potential in the domain of new energy concepts in applications like Solid Oxide Fuel Cells, membranes, and photovoltaic with the adoption of new ways of producing coatings by thermal spray. Such processes include Plasma Spray-Thin Film (PS-TF) which gives the possibility to coat thin and dense layers from splats through a classical thermal spray approach but at high velocities (400-800 m/s) and enthalpy (8000-15000 kJ/kg). Plasma Spray-PVD (PS-PVD) which allows producing thick columnar-structured Thermal Barrier Coatings (100-300 μm) from the vapor phase with the employment of the high enthalpy gun and specific powder feedstock material. On the other hand, the Plasma Spray-CVD (PS-CVD) process uses modified conventional thermal spray components operated below 100 Pa which allows producing CVD-like coatings (<1-10 μm) at higher deposition rates using liquid or gaseous precursors as feedstock material. The advantages of such thermal spray-enhanced CVD processes are the high ionization degree and high throughput for the deposition of thin layers. In this article, we present an overview of the possibilities and limitations encountered while producing thin film coatings using liquid and gaseous precursors with this new type of low pressure plasma spray equipment and point out the challenges faced to obtain efficient injection and mixing of the precursors in the plasma jet. In particular, SiO _x thin films from Hexamethyldisiloxane (HMDSO or C₆H₁₈OSi₂) can be deposited on wafers at deposition rates of up to 35 nm/s at an efficiency of about 50%. The process was also used for producing metal oxide coatings (Al₂O₃, ZnO, and SnO₂) by evaporating different metals in combination with an oxygen gas flow. The effect of process parameters on the deposition rate, coating build up, uniformity, and quality of the coatings are discussed. An overview of different potential applications of this new technology will be also presented.     

Development of Low-Oxide MCrAlY Coatings for Gas Turbine Applications

Advanced high-energy plasma systems are being used to achieve the benefits of the high-velocity oxy-fuel (HVOF) system without losing the inherent advantages of plasma for coating of gas turbine parts. MCrAlY coatings play a very important role in the performance and reliability of gas turbine components. One of the important considerations for next generation of gas turbines, which have more demanding conditions and need to withstand ever increasing operating temperatures, is that they should possess very low oxygen content levels in the coating. Low oxygen content coatings are applied by the expensive low-pressure plasma spray (LPPS)/vacuum plasma spray (VPS) technique for critical components in aero- and land-based gas turbines. This work deals with the development of low-cost LPPS equivalent coatings (having low oxygen content) using the high-energy high-velocity plasma spray (HEHVPS) gun and inert gas shroud. A comparison has also been made with CoNiCrAlY coatings by HVOF.     

The effects of heat treatment and gas atmosphere on the thermal conductivity of APS and EB-PVD PYSZ thermal barrier coatings

The effects of heat treatment and gas atmosphere on thermal conductivity of atmospheric plasma sprayed (APS) and electron beam physical vapor deposited (EB-PVD) partially Y₂O₃ stabilized ZrO₂ (PYSZ) thermal barrier coatings (TBCs) were investigated. Two-layer samples that had an EB-PVD coating deposited on bond coated nickel-base superalloy IN625 substrates, free-standing APS and EB-PVD coatings as well as a quasi-free-standing EB-PVD PYSZ coating (coating on semitransparent sapphire) were included in the study. Thermal diffusivity measurements for determining thermal conductivity were made from room temperature up to 1150 °C in vacuum and under argon gas using the laser flash technique. To investigate the effect of heat treatment on thermal conductivity, coatings were annealed at 1100 °C in air. For both the APS and EB-PVD PYSZ coatings the first 100 h heat treatment caused a significant increase in thermal conductivity that can be attributed to microstructural changes caused by sintering processes. Compared to the measurements in vacuum, the thermal conductivity of APS coatings increased by about 10% under argon gas at atmospheric pressure, whereas for the EB-PVD coatings, the influence of gas on thermal conductivity was relatively small. The effect of gas on the thermal conductivity of APS and EB-PVD PYSZ coatings can be attributed to amount, shape, and spatial arrangement of pores in the coating material.     

Effect of Suspension Plasma-Sprayed YSZ Columnar Microstructure and Bond Coat Surface Preparation on Thermal Barrier Coating Properties

Suspension plasma spraying (SPS) is identified as promising for the enhancement of thermal barrier coating (TBC) systems used in gas turbines. Particularly, the emerging columnar microstructure enabled by the SPS process is likely to bring about an interesting TBC lifetime. At the same time, the SPS process opens the way to a decrease in thermal conductivity, one of the main issues for the next generation of gas turbines, compared to the state-of-the-art deposition technique, so-called electron beam physical vapor deposition (EB-PVD). In this paper, yttria-stabilized zirconia (YSZ) coatings presenting columnar structures, performed using both SPS and EB-PVD processes, were studied. Depending on the columnar microstructure readily adaptable in the SPS process, low thermal conductivities can be obtained. At 1100 °C, a decrease from 1.3 W m^?1 K^?1 for EB-PVD YSZ coatings to about 0.7 W m^?1 K^?1 for SPS coatings was shown. The higher content of porosity in the case of SPS coatings increases the thermal resistance through the thickness and decreases thermal conductivity. The lifetime of SPS YSZ coatings was studied by isothermal cyclic tests, showing equivalent or even higher performances compared to EB-PVD ones. Tests were performed using classical bond coats used for EB-PVD TBC coatings. Thermal cyclic fatigue performance of the best SPS coating reached 1000 cycles to failure on AM1 substrates with a β-(Ni,Pt)Al bond coat. Tests were also performed on AM1 substrates with a Pt-diffused γ-Ni/γ′-Ni₃Al bond coat for which more than 2000 cycles to failure were observed for columnar SPS YSZ coatings. The high thermal compliance offered by both the columnar structure and the porosity allowed the reaching of a high lifetime, promising for a TBC application.     

Plasma Spray Physical Vapor Deposition of La1−x Sr x Co y Fe1−y O3−δ Thin-Film Oxygen Transport Membrane on Porous Metallic Supports

Plasma spray physical vapor deposition (PS-PVD) is a very promising route to manufacture ceramic coatings, combining the efficiency of thermal spray processes and characteristic features of thin PVD coatings. Recently, this technique has been investigated to effectively deposit dense thin films of perovskites particularly with the composition of La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) for application in gas separation membranes. Furthermore, asymmetric type of membranes with porous metallic supports has also attracted research attention due to the advantage of good mechanical properties suitable for use at high temperatures and high permeation rates. In this work, both approaches are combined to manufacture oxygen transport membranes made of gastight LSCF thin film by PS-PVD on porous NiCoCrAlY metallic supports. The deposition of homogenous dense thin film is challenged by the tendency of LSCF to decompose during thermal spray processes, irregular surface profile of the porous metallic substrate and crack and pore-formation in typical ceramic thermal spray coatings. Microstructure formation and coating build-up during PS-PVD as well as the annealing behavior at different temperatures of LSCF thin films were investigated. Finally, measurements of leak rates and oxygen permeation rates at elevated temperatures show promising results for the optimized membranes.