Numerical Simulation of Droplet Breakup and Collision in the Solution Precursor Plasma Spraying

Finely structured ceramic coatings can be obtained by solution precursor plasma spraying. The final structure of the coating highly depends on the droplet size and velocity distribution at the injection, the evolution of the spray in the jet, and droplet breakup and collision within the spray. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. O’Rourke’s droplet collision model is used to take into account the influence of droplet collision. The influence of droplet breakup is also considered by implementing TAB droplet breakup models into the plasma jet model. The effects of droplet collisions and breakup on the droplet size, velocity, and temperature distribution of the solution spray are investigated. The results indicate that droplet breakup and collision play an important role in determining the final particle size and velocity distributions on the substrate. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Liquid Precursor Plasma Spraying: Modeling the Interactions Between the Transient Plasma Jet and the Droplets

Plasma spraying using liquid feedstock makes it possible to produce thin coatings (<100 μm) with more refined microstructures than in conventional plasma spraying. However, the low density of the feedstock droplets makes them very sensitive to the instantaneous characteristics of the fluctuating plasma jet at the location where they are injected. In this study, the interactions between the fluctuating plasma jet and droplets are explored by using numerical simulations. The computations are based on a three-dimensional and time-dependent model of the plasma jet that couples the dynamic behaviour of the arc inside the torch and the plasma jet issuing from the plasma torch. The turbulence that develops in the jet flow issuing in air is modeled by a large Eddy simulation model that computes the largest structures of the flow which carry most of the energy and momentum. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

前驱体溶液等离子喷涂参数对涂层形貌的影响及沉积行为机理研究

目的对不同喷涂工艺参数下涂层的相结构、显微形貌进行研究,确定优化的喷涂工艺参数,讨论分析涂层的沉积行为机理。方法采用前驱体溶液等离子喷涂(SPPS)的方法制备纳米Yb_2O_3稳定的ZrO_2(YbSZ)涂层。在传统等离子喷涂的基础上,增加液料雾化装置,雾化喷嘴将溶液雾化后直接注入到等离子弧中,通过控制喷涂距离及喷涂功率,研究了涂层相结构、结晶度、晶粒尺寸以及显微形貌的变化趋势,并且结合显微形貌讨论了沉积机理。结果涂层呈现团聚大颗粒、纳米级粒子、大小均匀的孔隙三种显微形貌,大颗粒之间呈堆积形态。当喷涂功率为30 kW时,涂层呈现m-ZrO_2,平均晶粒尺寸达669 nm。随着喷涂距离、喷涂功率的增加,样品中检测到单一的t-ZrO_2相,而且纳米尺寸颗粒的数量大大增加,孔径变小。随着喷涂距离由60 mm增加到100 mm,平均晶粒尺寸先由429 nm减小到177 nm,随后又增加到319 nm。结论喷涂参数影响晶粒的结晶度、晶粒尺寸以及涂层的显微形貌,低功率下得到的涂层存在糊状未结晶组织。增大喷涂功率,可以有效增大结晶度和晶粒尺寸;随着喷涂距离的增大,晶粒尺寸先减小后增大。雾化液滴在等离子火焰中一般要经历浓缩、饱和、固化、析晶形核长大、粒子重熔扁平化的历程,喷涂功率越高,经历温区越高,液滴演变就越充分,通过优化工艺参数可以得到不同结构性能的功能涂层。     

溶液前驱体等离子喷涂热障涂层的高温稳定性

以锆盐和钇盐水溶液为原料,采用溶液前驱体等离子喷涂(SPPS)技术制备了氧化钇部分稳定氧化锆(7YSZ)热障涂层,利用X射线衍射仪(XRD)、拉曼光谱(Raman)和扫描电镜(SEM)研究了SPPS涂层在1 200~1 400℃下的相结构和微观结构稳定性。结果表明:沉积态SPPS涂层为亚稳四方相(t′),在1 200℃和1 300℃时未发生亚稳四方相(t′)向单斜相(m)的转变,在1 400℃热处理100h后出现了少量单斜相。在1 200~1 400℃下,SPPS涂层发生了不同程度的烧结现象;随热处理温度升高,SPPS涂层晶粒长大速率增加,在1 200、1 300和1 400℃热处理100h后,最大晶粒尺寸分别约为350、700和1 100nm。同时,在1 400℃下热处理100h后,涂层中仍然存在大量1μm的微孔,表明其具有较好的微孔保持能力。     

Thermal Barrier Coatings Made by the Solution Precursor Plasma Spray Process

The solution precursor plasma spray (SPPS) process is a relatively new and flexible thermal spray process that can produce a wide variety of novel materials, including some with superior properties. The SPPS process involves injecting atomized droplets of a precursor solution into the plasma. The properties of resultant deposits depend on the time-temperature history of the droplets in the plasma, ranging from ultra-fine splats to unmelted crystalline particles to unpyrolized particles. By controlling the volume fraction of these three different constituents, a variety of coatings can be produced, all with a nanograin size. In this article, we will be reviewing research related to thermal barrier coatings, emphasizing the processing conditions necessary to obtain a range of microstructures and associated properties. The SPPS process produces a unique strain-tolerant, low-thermal conductivity microstructure consisting of (i) three-dimensional micrometer and nanometer pores, (ii) through-coating thickness (vertical) cracks, (iii) ultra-fine splats, and (iv) inter-pass boundaries. Both thin (0.12 mm) and thick (4 mm) coatings have been fabricated. The volume fraction of porosity can be varied from 10% to 40% while retaining the characteristic microstructure of vertical cracks and ultra-fine splats. The mechanism of vertical crack formation will be described.     

Microstructure and Electrochemical Behavior of La0.8Sr0.2MnO3 Deposited by Solution Precursor Plasma Spraying

采用液料等离子喷涂方法(SPPS)制备固体氧化物燃料电池多孔La0.8Sr0.2MnO3(LSM)阴极。用SEM观察LSM的微结构,用XRD研究其相结构。考察了喷涂距离和热处理温度对LSM微结构的影响规律。结果表明,SPPSLSM在1050℃热处理2h后形成连续的具有微纳介孔结构的涂层,且LSM具有单一的钙钛矿结构。利用电化学交流阻抗谱方法研究了LSM极化行为。微结构对极化性能有显著影响,1000℃时,LSM在喷涂距离为60mm时具有最佳的电化学性能,阴极极化电阻约为0.3Ω·cm2。通过工艺的控制,SPPS可以实现SOFC阴极相和微结构的优化。     

Clogging and Lump Formation During Atmospheric Plasma Spraying with Powder Injection Downstream the Plasma Gun

This study aimed to numerically and experimentally investigate lump formation during atmospheric plasma spraying with powder injection downstream the plasma gun exit. A first set of investigations was focused on the location and orientation of the powder port injector. It turned out impossible to keep the coating quality while avoiding lumps by simply moving the powder injector. A new geometry of the powder port ring holder was designed and optimized to prevent nozzle clogging, and lump formation using a gas screen. This solution was successfully tested for applications with Ni-5wt.%Al and ZrO₂-7wt.%Y₂O₃ powders used in production. The possible secondary effect of plasma jet shrouding by the gas screen, and its consequence on powder particles prior to impact was also studied.     

Deformation of Alumina Droplets on Micro-Patterned Substrates Under Plasma Spraying Conditions

The deformation of plasma-sprayed alumina droplets of 35-55 μm diameter d with an impact velocity of around 90 m/s has been investigated over various micro-patterned substrates with an arithmetic mean roughness of 0.5 μm. On a line-and-space pattern, droplets exhibited elliptical splats extending in the direction perpendicular to the line, when the normalized pattern spacing λ (= x/d) was 0.1-0.3, where x is the pattern spacing. The fingering of the splats was also caused by a concave pattern as well as by a convex pattern and the number of fingers significantly increased at λ = 0.2. In addition, holes suggesting air entrapment were observed off center in the bottom side of each splat by approximately 1.5 times the radius of the droplets, regardless of the pattern. These results suggest the importance of the surface design of substrate on the micrometer scale in plasma spraying.     

Si掺杂对溶液等离子喷涂TiO2涂层结构及光催化性能的影响

目的采用溶液前驱体等离子喷涂制备TiO_2以及Si掺杂TiO_2涂层,并分别研究H2流量和Si掺杂对TiO_2涂层光催化性能的影响。方法通过X射线衍射、扫描电子显微镜、拉曼光谱和傅里叶变换近红外光谱表征样品的晶相、表面形貌以及化学结构,然后以甲基橙为目标物,借此模拟有机污染物,利用光化学反应仪测试TiO_2以及Si掺杂TiO_2涂层的光催化性能。结果适量Si掺杂可以细化晶粒,提升TiO_2涂层中锐钛相含量(从7.4%提高到49%),同时形成Ti—O—Si键,Si掺TiO_2涂层甲基橙的降解率达到95%左右,高于纯TiO_2涂层80%的降解率。随着H2流量增加,TiO_2涂层中的晶粒明显粗化,主要以金红石相的形式存在,H2流量为8 L/min的TiO_2涂层甲基橙降解率达到82%,要远高于H2流量为4、10 L/min的52%和33%。结论 Si掺杂TiO_2涂层比纯TiO_2涂层的光催化性能更优,当H2流量为8 L/min时,光催化性能最好。     

等离子喷涂过程基体温度场分布的数值模拟

等离子喷涂的热源温度高,涂层成形区域温度梯度大、热量累积快,涂层中常存在较大的残余应力。研究通过数值模拟并辅以必要的试验测试研究了等离子喷涂过程基体表面热量累积行为：建立了二维静态喷枪加热模型,研究了在不同喷涂距离时基体表面温度场分布规律;建立了移动热源加热模型,研究了在不同喷枪移动速度和扫描遍数时基体热量累积规律。结果表明：在静态喷枪加热作用下,基体温度场呈中间高两端低的对称分布状态;随着喷涂距离减小,基体表面最高温度与平均温度显著升高,温度梯度变化明显,高温区域半径显著增大。在动态喷枪加热过程中,基体左右边界热量累积现象明显,且喷枪移动速度越快,基体表面热量累积越少,温度分布梯度越小;随着喷枪扫描遍数的增加,基体中心区域温度呈波浪式上升,温度增长幅度逐渐变小。     

Fluid Mechanics and Heat Transfer of Liquid Precursor Droplets Injected into High-Temperature Plasmas

Thermo-physical processes in liquid ceramic precursor droplets in plasma were modeled. Models include aerodynamic droplet break-up, droplet transport, as well as heat and mass transfer within individual droplets. Droplet size, solute concentration, and plasma temperature effects are studied. Results are discussed with the perspective of selecting processing conditions and injection parameters to obtain certain types of coating microstructures. Small droplets (<5 microns) are found to undergo volumetric precipitation and coating deposition with small unpyrolized material. Droplets can be made to undergo shear break-up by reducing surface tension and small droplets promote volumetric precipitation. Small particles reach substrate as molten splats resulting in denser coatings. Model predicts that larger droplets (>5 microns) tend to surface precipitate-forming shells with liquid core. They may be subjected to internal pressurization leading to shattering of shells and secondary atomization of liquid within. They arrive at the substrate as broken shells and unpyrolized material.     

Modeling of Precipitate Formation in Solution Precursor Droplets in a Microwave Plasma

A comprehensive computational model based on finite difference method was developed to study the heat and mass transport within solution precursor droplets injected into a laminar microwave air plasma flow field. Plasma flow field was simulated as hot gas flowing in a quartz tube generated by volumetric heat addition in the microwave coupling region. The resulting air plasma had a maximum temperature of 6000 K. Droplets containing zirconium acetate precursor of different diameters and solute concentrations were injected into the axisymmetric laminar plasma flow along the centerline of the plasma. Variation of transport properties of the plasma surrounding spherical droplets and absorption of microwave radiation within these droplets were considered in the model. Model predictions suggest that solution droplets are not affected by the microwave radiation in the presence of high convective heat flux from microwave plasma. Smaller droplets and high solute concentrations result in formation of thicker precipitate shells around them based on the homogeneous precipitation hypothesis. Mass transport is found to be slower than heat transfer in the droplets. Microwave plasma allowing the possibility of injecting droplets axially into the high temperature plasma environment present the opportunity to produce more consistent precipitate states as compared to DC arc plasmas into which droplets are typically injected transversely in thermal spray applications.     

Parameters Controlling Liquid Plasma Spraying: Solutions, Sols, or Suspensions

This article presents what is our present knowledge in plasma spraying of suspension, sol, and solution in order to achieve finely or nano-structured coatings. First, it describes the different plasma torches used, the way liquid jet is injected, and the different measurements techniques. Then, drops or jet fragmentation is discussed with especially the influence of arc root fluctuations for direct current plasma jets. The heat treatment of drops and droplets is described successively for suspensions, sols, and solutions both in direct current or radio-frequency plasmas, with a special emphasize on the heat treatment, during spraying, of beads and passes deposited. The resulting coating morphologies are commented and finally examples of applications presented: Solid Oxide Fuel Cells, Thermal Barrier coatings, photocatalytic titania, hydroxyapatite, WC-Co, complex oxides or metastable phases, and functional materials coatings.     

Liquid Precursor Plasma Spraying of Functional Materials: A Case Study for Yttrium Aluminum Garnet (YAG)

RF precursor plasma spray synthesis (RFPPS) is an innovative and rapid technique to deposit functional oxide coatings by starting from liquid inorganic precursors and directly producing ceramic coatings. RFPPS offers excellent opportunities in exploring the nonequilibrium phase evolution during plasma spraying of molecularly mixed precursors to form multicomponent oxides. A detailed discussion of progress, critical issues and consideration in precursor development, RF plasma spraying, coating development, and phase evolution of yttrium aluminum garnet (YAG) is presented as a case study. Appropriate selection of precursors and proper tuning of spray parameters resulted in amorphous or crystalline coatings in the as-sprayed condition. YAG phase selection has also been investigated using a discrete, low-density combinatorial synthesis approach.     

Solution Precursor Plasma Spray of Nickel-Yittia Stabilized Zirconia Anodes for Solid Oxide Fuel Cell Application

In conventional plasma spray of SOFC components, the large NiO and YSZ particles used, about 50-150 microns for high porosity coating, reduce the density of three-phase sites for electrode reaction. In this article, the SPPS process was used to synthesize and deposit Ni-YSZ anodes. The results show that several process parameters have significant effects on the microstructure and phase composition of the deposited material. The deposits were composed of tower-like, irregularly shaped agglomerates and smooth surface deposits. The sizes of the agglomerates increase with the decrease of the plasma-torch power and most are not completely molten during the impact. After heat treatment to reduce the NiO present in the as deposited coatings, the coatings were found to contain spherical YSZ particles about 0.5 μm in diameter distributed in a continuous Ni matrix, which is verified by both SEM observation and electrical resistance measurement. The coatings have 30-50% porosity. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

超音速等离子喷涂NiCr-Cr3C2工艺的参数优化

采用四因素三水平正交试验,通过在线监测喷涂粒子的温度和速度,对电流、电压、喷涂距离和主气流量四个超音速等离子喷涂的主要参数进行优化设计.结果表明:四个因素对喷涂粒子温度的影响均较大,电压和主气流量对喷涂粒子速度的影响较大;优化的工艺参数为电压150 V、电流400A、喷涂距离85 cm、氩气流量4.2m3/h,采用该优...     

喷枪扫描速度对等离子喷涂Mo/8YSZ梯度 热障涂层温度场的影响规律研究

目的 突破新型动力热障涂层高温环境易剥落的技术瓶颈,揭示等离子喷涂过程中,喷枪扫描速度对梯度热障涂层温度分布的影响规律。方法 利用ANSYS有限元仿真模拟软件,建立了等离子喷涂Mo/8YSZ梯度热障涂层温度场的仿真模型,模型中考虑了材料热物性参数随温度的变化情况及材料的相变潜热。 结果 当喷枪扫描速度由550 mm/s增加至1000 mm/s时,喷枪与基体或已沉积涂层间交互作用的时间缩短,在喷涂构件自身热传导及喷涂构件与外界环境对流换热等综合因素作用下,致使喷涂作业结束时,喷涂构件的最高温度由475 ℃降低至371 ℃,涂层厚度方向的最大温度梯度由2.15×107 ℃/m降低至2.05×107 ℃/m。由于喷涂构件的温度、温度梯度及等离子射流热源用于粉末粒子直接温升的比例均与材料的热物性参数密切相关,致使在喷涂作业结束时,喷涂构件各部分最高温度及涂层厚度方向的最大温度梯度均呈现陶瓷层最高、过渡层次之、粘结层最低的分布规律。由于等离子喷涂过程中,先沉积的涂层对后沉积的涂层存在一个预热作用,故伴随着涂层厚度的增加,喷涂构件的最高温度增加。结论 在等离子喷涂过程中,通过增大喷枪扫描速度,可在牺牲涂层最高温度的条件下,降低喷涂构件的最大温度梯度。热障涂层采用梯度结构,可实现涂层厚度方向材料热物性参数的连续梯度变化,进而实现对喷涂构件空间温度分布的有效调控。     

Suspension Plasma Spraying of YPSZ Coatings: Suspension Atomization and Injection

Among processes evaluated to produce some parts of or the whole solid-oxide fuel cell, Suspension Plasma Spraying (SPS) is of prime interest. Aqueous suspensions of yttria partially stabilized zirconia atomized into a spray by an internal-mixing co-axial twin-fluid atomizer were injected into a DC plasma jet. The dispersion and stability of the suspensions were enhanced by adjusting the amount of dispersant (ammonium salt of polyacrylic acid, PAA). A polyvinyl alcohol (PVA) was further added to the suspension to tailor its viscosity. The PVA also improved the dispersion and stability of the suspensions. The atomization of optimized formulations is described implementing Weber and Ohnesorge dimensionless numbers as well as gas-to-liquid mass ratio (ALR) value. Drop size distributions changed from monomodal distributions at low We to multimodal distributions when We number increases. The viscosity of the suspensions has a clear influence on the drop size distribution and suspension spray pattern. The secondary fragmentation of the drops due to the plasma jet was evidenced and the final size of the sheared drops was shown to depend on the characteristics of the suspension. Rather dense zirconia coatings have been prepared, which is a promising way to produce electrolyte.     

Numerical Simulation of Temperature Field in Nanostructured Al2O3-13TiO2 Feedstock in Supersonic Plasma Spraying

Velocity and temperature of nanostructured Al2O3-13TiO2 feedstocks in supersonic plasma spraying was detected applying CCD thermal spray monitor.Based on the detect results,temperature field in the feedstock in spraying process was analyzed via finite element method.Result shows that the highest velocity of the flying particles exceed to 800m/s.With the increase of spraying distance,velocity decline parabolic.Surface temperature of the feedstock increase firstly and then decrease and the highest temperature exceed to 2600℃.Internal temperature of the feedstock is higher than the melting point when the distance reaches to 80mm.As the spraying distance increase,temperature gradient in the particle decreased gradually.     

Development of Expert Controller for Plasma Spraying Process

SOME PLASMA SPRAYING EQUIPMENTS ofnewly-developed have been added system monitorfunction and system self-diagnosis,alarming andamendment are realized,and the coating qualitycontrol can be achieved by setting up information baseof control parameters.But investigation of plasmaspraying technology is mainly concentrated onspraying process and coating properties in our country['2].In this paper,plasma spraying parameters andcoating properties and relationship between them areanalyzed by …