3D Modeling of Transport Phenomena and the Injection of the Solution Droplets in the Solution Precursor Plasma Spraying

Solution precursor plasma spraying has been used to produce finely structured ceramic coatings with nano- and sub-micrometric features. This process involves the injection of a solution spray of ceramic salts into a DC plasma jet under atmospheric condition. During the process, the solvent vaporizes as the droplet travel downstream. Solid particles are finally formed due to the precipitation of the solute, and the particle are heated up and accelerated to the substrate to generate the coating. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. The jet-spray two-way interactions are considered. A simplified model is employed to simulate the evolution process and the formation of the solid particle from the solution droplet in the plasma jet. The temperature and velocity fields of the jet are obtained and validated. The particle size, velocity, temperature, and position distribution on the substrate are predicted. 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.     

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.     

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。     

高速电弧喷涂熔滴速度的数值模拟及试验

熔滴速度是电弧喷涂涂层性能的主要影响因素之一。本基于空气动力学和二相流流体力学理论建立了高速电弧喷涂雾化气流化和熔滴速度的数学模型，并进行了数值模拟；同时用试验方法测试了气流速度及Al,3Cr13熵滴在不同喷涂距离处的平均速度；数值计算结果与试验数据基本吻合。结果表明，雾化气流的速度和距喷嘴一定距离内将保持初始速度（约650m/s)，然后随喷涂距离的增大而衰减，这与超音速气流通过Laval喷管后所产生的膨胀波和压缩波相互作用有关；熔滴在雾化飞行过程中经历了先加速后减速的过程，小熔滴能在较短的距离内被加速到最大速度；达到最大速度之后，小熔滴由于惯性力较小而迅速减速，而大熔滴则因较大的惯性力而减速不明显；熔滴速度的变化是由熔滴的Reynolds数决定的。Al和3Cr13熵滴的最大速度在0．3m喷涂距离之内均超过音速。     

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。     

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.     

晶须强化等离子喷涂涂层中的熔滴扁平化及晶须偏转行为的模拟

目的了解等离子喷涂涂层过程中的晶须偏转行为,为提高涂层的抗冲蚀性能提供新思路。方法分别采用计算流体动力学软件FLUENT和有限元分析软件ANSYS,模拟研究等离子喷涂熔滴碰撞基体后的扁平过程,以及熔滴扁平期间晶须在力矩作用下的偏转行为。结果熔滴碰撞基体后,可以观察到熔滴的扁平化过程大约持续1.5μs。在力矩从1×10-18N·m变化到3×10-18N·m时,最大偏转角度从23°增长到70°。结论通过研究熔滴形状和最大扁平速度随时间的变化,得到了扁平化完成时间。熔滴沿基体表面的最大铺展速度与碰撞速度有关。当力矩在一定范围内改变时,晶须发生偏转。     

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。     

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.     

Numerical Simulation of Droplet Impact on Patterned Surfaces

This work presents numerical simulation results for molten nickel and zirconia (YZS) droplets impacting on different microscale-patterned surfaces of silicon. The numerical simulation clearly showed the effect of surface roughness and solidification on the shape of the final splat, as well as the pore creation beneath the sprayed material. Simulations were performed using computational fluid dynamic software, SimDrop. The code uses a three-dimensional finite-difference algorithm solving the full Navier-Stokes equation, including heat transfer and phase change. A volume of fluid (VOF) tracking algorithm is used to track the droplet-free surface. Thermal contact resistance at the droplet-substrate interface is also included in the model. Specific attention is paid to the simulation of droplet impact under plasma spraying conditions. Droplet sizes ranged from 15 to 60 microns with initial velocities of 70-250 m/s. Substrate surfaces were patterned with regular arrays of cubes 1-3 μm high, spaced either 1 μm or 5 μm from each other. Different splat morphologies produced by simulations are compared with those obtained from the experiment conducted under the same impact and surface conditions. 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 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.     

SHS反应火焰喷涂粒子与基体的碰撞及其数值模拟

以Ti-B4C-C为反应喷涂体系，通过碰撞实验和ANSYS有限元分析方法，研究了反应火焰喷涂TiC-TiB2复相涂层时，喷涂粒子与基体碰撞形成摊片的温度变化情况及其对涂层与基体结合的影响。研究表明，完成自蔓延反应、处于熔融状态的喷涂粒子与基体碰撞形成的摊片各部分温差较大，温度较低，不易使基体表面熔化，难以与基体形成良好结合；自蔓延反应进行中的喷涂粒子与基体碰撞形成的摊片各部分温差较小，温度较高，能较好地实现与基体的结合。模拟结果与实验结果基本吻合。     

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 …     

自反应火焰喷涂过程中碰撞沉积物的形成及分析

以Ti-B4C-C为反应喷涂体系,基于SHS反应火焰喷涂制备TiC-TiB2复相陶瓷涂层技术,进行粒子与基体碰撞试验,获得了自蔓延反应火焰喷涂粒子与基体碰撞变形后的各种形貌图,通过对飞行粒子结构与粒子变形特点的研究得出:飞行粒子的形态与结构决定了粒子的变形特点,五种形态的碰撞沉积物来自各自对应的飞行粒子;基体预热温度、喷涂距离和喷涂团聚粉粒制备质量对碰撞沉积物的沉积率及扁平化有重要影响;不同变形粒子间的相互作用对涂层组织与性能会造成不同的影响,扁平粒子的薄膜飞溅主要由陶瓷熔滴内的气泡引起。     

自反应火焰喷涂过程中碰撞沉积物的形成及分析

以Ti-B4C-C为反应喷涂体系，基于SHS反应火焰喷涂制备TiC-TiB2复相陶瓷涂层技术，进行粒子与基体碰撞试验，获得了自蔓延反应火焰喷涂粒子与基体碰撞变形后的各种形貌图，通过对飞行粒子结构与粒子变形特点的研究得出：飞行粒子的形态与结构决定了粒子的变形特点，五种形态的碰撞沉积物来自各自对应的飞行粒子；基体预热温度、喷涂距离和喷涂团聚粉粒制备质量对碰撞沉积物的沉积率及扁平化有重要影响：不同变形粒子问的相互作用对涂层组织与性能会造成不同的影响，扁平粒子的薄膜飞溅主要由陶瓷熔滴内的气泡引起。     

正弦织构化表面等离子喷涂熔滴铺展成形分析

目的 分析等离子喷涂熔滴在表面织构内的铺展、凝固规律,为了解表面织构化对等离子喷涂涂层结合机制的影响以提升涂层的结合强度提供理论辅助.方法 基于Flow 3D建立熔滴填充微织构的数值模型,研究等离子喷涂熔滴填充正弦形织构的温度场及铺展成形规律,并对比分析织构边缘凸起及织构形状的影响.同时,基于激光织构化表面等离子喷涂试验,分析不同织构对涂层形貌的影响.结果 无边缘凸起织构的散热速度比有边缘凸起织构的快约0.7μs,凹坑织构的散热速度最慢,计算结束时,其最高温依然高于熔滴液相线(1728.4 K)约44.7 K.基体最高温度约1680.5 K,其主要分布于织构边缘凸起顶端、基体平面与织构内壁的拐点以及织构内壁上的凸点位置.有边缘凸起正弦织构的凝固熔滴由中间向两侧逐渐变薄,熔滴在无边缘凸起织构外部呈规则的圆盘状,凹坑织构底部存在"空腔"特征.涂层截面形貌分析发现,有边缘凸起的织构表面的涂层形貌较优,凹坑织构涂层含有较多缺陷,形貌最差.结论 镍基涂层与织构化表面为机械结合.相比凹坑织构,正弦和直线织构更有利于提高涂层的质量.织构边缘凸起的存在对提高喷涂质量也是有利的.