等离子喷涂过程中粒子的氧化及其对涂层性能的影响

利用粒子收集装置和附加氩气保护罩,研究了铁粒子和NiCoCrAlY粒子在等离子喷涂过程中的氧化行为及其对涂层性能的影响.结果表明,粒子在飞行过程中存在对流氧化和扩散氧化两种氧化机制,粒子的氧化方式取决于离开喷嘴的距离;离开喷嘴距离越长,粒子氧化越严重;采用附加氩气保护罩能明显减少喷涂过程中外界空气对粒子的氧化,降低涂层孔隙率,提高NiCoCrAlY涂层的抗高温氧化性能.

Abstract：

The oxidation mechanisms of iron particles and NiCoCrAlY particles during plasma spraying process and its effect on the sprayed coatings were investigated by the in-flight particles collection setup and the gas shrouding. The results show that there are two oxidation mechanisms during in-flight oxidation: one is the diffusion oxidation; the other is the convective oxidation, which are decided by the distance from the spraying particles to the nozzle. The oxidation content increases with the increasing of the standoff distance. The shrouded gas can decrease the oxidation content of inflight particles and increase the oxidation resistance of NiCoCrAIY coatings.     

CoCrNiAlY涂层制备工艺对组织形态及高温氧化行为的影响

为了研究CoCrNiAlY涂层微观组织结构对高温氧化行为和剥落行为的影响规律,采用激光熔覆技术和等离子喷涂工艺在718高温合金表面制备CoCrNiAlY涂层,观察其微观组织形态。利用XRD和SEM对1150 ℃高温氧化试验样品进行氧化层物相分析和形貌观察。结果表明,激光熔覆制备的CoCrNiAlY涂层中形成了胞状亚结构的等轴晶凝固组织,相对于等离子喷涂制备的CoCrNiAlY涂层结构更致密,具有更优异的抗高温氧化性能。在高温氧化过程中,等离子喷涂CoCrNiAlY涂层生成了以Cr₂O₃结构为主的复合氧化膜。激光熔覆CoCrNiAlY涂层生成Al₂O₃结构的单一氧化膜,而且熔覆层中原位形成的Y₂O₃钉扎作用能有效提高氧化膜的抗剥落性。文中系统分析讨论了两种不同工艺制备的组织形态对高温氧化膜形成机制的影响,激光熔覆涂层在高温下主要是以界面扩散方式形成致密的Al₂O₃膜,等离子喷涂涂层在高温下以界面反应的方式快速形成Cr₂O₃复合氧化膜。     

喷涂工艺对MoSi2-Al2O3涂层组织与性能的影响

目的在不锈钢表面制备一种可服役于高温富氧环境中的抗高温氧化防护涂层。方法采用MoSi_2-Al_2O_3团聚烧结粉末为喷涂原料,分别利用等离子喷涂和火焰喷涂两种工艺在310S不锈钢表面制备MoSi_2-Al_2O_3抗高温氧化涂层。采用SEM、EDS、XRD和粗糙度测量仪分析涂层的组织结构,使用拉伸法检测涂层的结合强度,采用高温氧化实验表征涂层的抗高温氧化性能。结果等离子喷涂涂层中的粉末熔化程度较火焰喷涂涂层更高,涂层呈现致密的堆叠结构且Si、O元素分布更为均匀。等离子喷涂涂层的结合强度为24.25 MPa,较火焰喷涂涂层提高了约68%。经1200℃高温氧化试验后,火焰喷涂涂层出现粉化,氧化剧烈并发生剥落,而等离子喷涂涂层未出现粉化现象,涂层结构完好。在高温氧化过程中,由于等离子喷涂涂层组织致密,可有效避免涂层粉化,均匀分布的Si元素在涂层氧化过程中更易产生SiO_2并对涂层裂纹进行有效填补,阻碍了氧原子向涂层内部扩散,因此涂层抗高温氧化性优异。结论采用等离子喷涂技术能够在310S不锈钢表面制备出组织结构、结合强度及高温性能更好的MoSi_2-Al_2O_3涂层。     

附加屏蔽气体的大气等离子喷涂对热障涂层性能影响

对比研究了附加屏蔽气体的大气等离子喷涂和普通大气等离子喷涂对热障涂层组织结构和性能的影响．结果表明,附加屏蔽气体的大气等离子喷涂粘结层表面未熔或半熔粒子较少,涂层中氧化物夹杂和孔隙率降低,热障涂层在1080℃下具有更好的抗氧化性能．附加屏蔽气体的大气等离子喷涂的热障涂层具有更好的抗氧化性能的原因,在于外加保护气氛减轻了...     

NiCoCrAlY粘结层喷涂工艺对8YSZ热障涂层抗氧化性能的影响

目的 提高热障涂层粘结层的抗高温氧化性能。方法 分别采用爆炸喷涂和等离子喷涂工艺制备了不同结构的NiCoCrAlY粘结层,之后通过等离子喷涂制备8YSZ陶瓷层,分析了两种粘结层结构的热障涂层的抗高温氧化性能。利用XRD、SEM和EDS对涂层物相、微观结构和成分进行分析,并对其与基体结合状态、抗高温氧化性能进行研究。结果 爆炸喷涂粘结层内部组织致密,缺陷较少,与基体结合处孔隙少;而等离子喷涂粘结层内部的层状特征明显,孔隙较多,表面粗糙度较低。爆炸喷涂粘结层氧化5 h后,表面生成了一层富Al2O3的致密氧化物膜;而等离子喷涂粘结层表面形成了富NiO、CoO、Cr2O3和Ni(Cr,Al)2O4的氧化物层,并出现了许多微裂纹和片层状氧化物。爆炸喷涂制备的热障涂层试样在前5 h氧化增重速率高于等离子喷涂试样,随后变平缓,而等离子喷涂试样氧化速率依然较高。爆炸喷涂热障涂层的热生长氧化物层（Thermally grown oxide, TGO）经50 h氧化后,仍呈连续状,厚度均匀,粘结层内氧化物缺陷较少。结论 爆炸喷涂粘结层组织均匀、致密,喷涂时涂层的氧化以及热处理的内氧化较少,使得足够的Al较快速地在粘结层表面形成致密的氧化铝,表面一定厚度的氧化铝层抑制了氧和其他金属原子的相向扩散反应,提高了涂层的抗高温氧化性能。     

高能高速等离子喷涂MCrAlY涂层的抗高温氧化性能

为提高Ni3Al基高温合金IC6的抗高温氧化性能,采用高能高速等离子喷涂设备在其表面制备了MCrAlY涂层,测试了1 000℃高温条件下经300h氧化后涂层的抗氧化性能。结果表明:300h试验后,涂层的单位面积氧化增重为5.584g/m2,氧化速率为0.019g/m2·h,达到了完全抗氧化级。分析认为:高能高速等离子喷涂工艺制备的MCrAlY涂层与基体结合紧密,孔隙、裂纹及氧化物夹杂含量少,有效的阻隔了氧气的扩散通道,使得氧化物的生长缓慢。同时在高温氧化过程中,涂层表面生成了大量的Al2O3膜,阻碍了金属原子与氧原子的扩散,降低了涂层的氧化速率。另外涂层中含有的Y及Y2O3增加了氧化膜的粘附性,对氧元素的扩散具有抑制作用。     

TiAl合金表面抗高温氧化涂层研究

研究了TiAl合金表面双层辉光离子渗Cr层、等离子喷涂以及激光重熔MCrAlY涂层在850℃的循环氧化行为.用扫描电镜(SEM)、能谱仪(EDS),辉光放电光谱分析仪(GDS)和X射线衍射仪(XRD)分析了涂层氧化前后的表面形貌、微观组织和相组成.结果表明,渗Cr层组织均匀、致密,且与TiAl合金基体为梯度冶金结合;经过激光重熔处理后,等离子喷涂MCrAlY层的片层状组织得以消失,致密性提高;几种涂层均不同程度地提高了TiAl合金的抗高温氧化性能,其中渗Cr层在氧化初期表现出较好的抗氧化性能,但在长期循环氧化过程中存在局部氧化层剥落现象,等离子喷涂MCrAlY层能显著提高TiAl合金的抗高温氧化性能,经过激光重熔后可进一步提高其抗高温氧化性能.     

粉末中C抑制FeAl熔滴氧化机制及其对等离子喷涂层组织与性能的影响*

大气等离子喷涂（APS）金属时,熔滴不可避免地发生氧化是难以获得粒子间结合充分的致密涂层的主要原因。以FeAl金属间化合物为例,提出一种在粉末中添加亚微米金刚石颗粒引入碳源,以期利用碳在高温下优先氧化的特性抑制等离子喷涂飞行粒子中Fe、Al元素的氧化,获得无氧化物的高温熔滴从而制备低氧含量（质量分数）、粒子间充分结合的FeAl金属间化合物涂层的新方法。采用APS制备Fe Al涂层,研究金刚石的添加对涂层氧含量、碳含量、涂层内粒子间结合质量与硬度的影响规律,探讨FeAl熔滴飞行中的氧化行为。采用商用热喷涂粒子诊断系统测量APS喷涂中的粒子温度,通过SEM与XRD表征了涂层的组织结构,并表征涂层的结合强度与硬度。结果表明,在等离子射流的加热和Fe、Al元素放热反应的联合作用下,飞行中FeAl熔滴的表面温度可达2 000℃以上,满足C原位脱氧的热力学条件。与不含碳的传统Fe Al涂层中的氧含量随喷涂距离的增加而显著增加的规律完全不同,用Fe/Al/2.5C粉末喷涂时涂层中的氧含量随距离的增加而减小,表明飞行中熔滴的氧化得到抑制,实现了C原位脱氧抑制金属元素氧化的自清洁氧化物的效应。FeAl/...     

MCrAlYs高温封严涂层制备工艺的优化及其性能

采用真空等离子喷涂与大气等离子喷涂的复合方法在K77基体材料表面制备出具有三层结构的MCrAlYs高温封严涂层,分别测量了涂层的金相组织、结合强度、表面洛氏硬度(HR15Y)以及抗粒子冲刷能力等性能.研究结果表明:喷涂功率是影响高温封严涂层性能的关键因素,喷涂功率高,粒子熔化好、涂层结合好、抗粒子冲刷性能相对较高;但是喷涂功率过高,涂层表面洛氏硬度相对较高,使用过程中,涂层易对转子叶片造成磨损伤害.因此选择合适的喷涂功率以在涂层结合效果与表面硬度之间建立一个平衡是高温封严涂层应用的关键.研究发现:在试验范围内,31 kW为最合适的喷涂功率.     

Cr3C2-NiCr涂层的高温抗氧化和热耐腐蚀性

采用大气等离子喷涂技术制备Cr3C2-NiCr复合涂层,并对制备的Cr3C2-NiCr涂层试样进行800 ℃×100 h氧化和熔盐（Na2SO4+25 wt%NaCl）热腐蚀试验。利用X射线衍射仪（XRD）和带能谱的扫描电镜(SEM/EDX)分析氧化、腐蚀涂层表面和截面的成分及结构变化,探讨其高温氧化、腐蚀机理。结果表明：等离子喷涂Cr3C2-NiCr涂层具有层状组织结构,喷涂过程中无明显相分解或氧化。高温氧化后的Cr3C2-NiCr涂层表面及层片界面形成了连续、致密的Cr2O3保护膜,涂层表现出优异的抗高温氧化性能。在热腐蚀过程中,腐蚀盐破坏了涂层表面及层片界面形成的氧化膜,腐蚀性元素沿着涂层中的孔洞及层片界面扩散到涂层内部,涂层发生“活化氧化”,耐腐蚀性较差。     

Oxidation control in atmospheric plasma spraying coating

Thermal spray coatings are formed by successive impingements and interbonding materials among the splats, solidified individual molten particles. Depending on the processing conditions employed during the spray process, deposits are produced with an assortment of microstructures and properties. This study highlights how the coating oxidation differences are influenced by the mechanisms involved during the spray process. The commercial steel powder referenced Amdry XPT 512 is chosen for a systematic study of comparison across different spraying techniques. Steel particles were sprayed with a F4 plasma torch and with a shrouded plasma spray process used in order to protect particles against atmospheric oxidation. The plasma jet was successively shielding by an inert gas shroud and by an oxidizing gas shroud. In-flight oxidation and post impact oxidation present in coatings are discussed in detail and the effects of these mechanisms on coating properties are addressed. The comparison was made on in-flight particle characteristics and on coating properties in terms of oxide content and porosity level. Using shrouded gas, in-flight characteristics are quite similarly independent of the nature of the shrouded gas. This way, the comparison of oxide contents present in the coatings corresponds to in-flight oxidation and is completely dependent on the nature of the shrouded gas. Comparing these results to those obtained by APS, a decrease in both velocity and temperature of in-flight particles was observed leading also to a significant decrease in oxide contents and to a slight increase in porosity level compared to coatings sprayed with air shrouding.     

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。     

Spraying of Metallic Powders by Hybrid Gas/Water Torch and the Effects of Inert Gas Shrouding

A hybrid DC arc plasma torch, combining water and gas stabilization, offers a high flexibility in plasma characteristics. These can be controlled in a wide range by the torch operational parameters, such as arc current and secondary gas flow rate. In this study, their influence on plasma spraying of tungsten and copper was investigated. To suppress the in-flight oxidation of the metals, inert gas shrouding was applied. In-flight particle diagnostics and analysis of free-flight particles and coatings was performed for spraying experiments in the open atmosphere and with argon shrouding. Both in-flight particle behavior and coating properties were found to be sensitive to the torch parameters. The application of shrouding was found to affect particle in-flight parameters, reduce the oxide content in the coatings and generally improve their properties, such as thermal conductivity. However, a different degree of these effects was observed for copper and tungsten.     

The Influence of Spray Parameters on the Characteristics of Hydroxyapatite In-Flight Particles,Splats and Coatings by Micro-plasma Spraying

Hydroxyapatite (HA) is one of the most important bioceramic materials used in medical implants. The structure of HA coatings is closely related to their manufacturing process. In the present study, HA coatings were deposited on Ti-6Al-4V substrate by micro-plasma spraying. Results show that three distinct HA coatings could be obtained by changing the spraying power from 0.5 to 1.0 kW and spraying stand-off distance from 60 to 110 mm: (1) high crystallinity (93.3%) coatings with porous structure, (2) high crystallinity coatings (86%) with columnar structure, (3) higher amorphous calcium phosphate (ACP, 50%) coatings with dense structure. The in-flight particles melting state and splat topography was analyzed to better understand the formation mechanism of three distinct HA coatings. Results show that HA coatings sprayed at low spraying power and short stand-off distance exhibit high crystallinity and porosity is attributed to the presence of partially melted particles. High crystallinity HA coatings with (002) crystallographic texture could be deposited due to the complete melting of the in-flight particles and low cooling rate of the disk shape splats under higher spraying power and shorter SOD. However, splashed shape splats with relative high cooling can be provided by increasing SOD, which leads to the formation of ACP.     

Plasma Spraying of Copper by Hybrid Water-Gas DC Arc Plasma Torch

Water-stabilized DC arc plasma torches offer a good alternative to common plasma sources used for plasma spraying applications. Unique properties of the generated plasma are determined by a specific plasma torch construction. This article is focused on a study of the plasma spraying process performed by a hybrid torch WSP500^®-H, which combines two principles of arc stabilization—water vortex and gas flow. Spraying tests with copper powder have been carried out in a wide range of plasma torch parameters. First, analyses of particle in-flight behavior for various spraying conditions were done. After, particles were collected in liquid nitrogen, which enabled analyses of the particle in-flight oxidation. A series of spraying tests were carried out and coatings were analyzed for their microstructure, porosity, oxide content, mechanical, and thermal properties.     

喷嘴形状对Al2O3-3TiO2粒子扁平化及其涂层性能的影响*

采用SprayWatch在线监测系统测量了F6大气等离子喷枪在不同喷嘴条件下产生的等离子射流中Al2O3-3TiO2粒子的温度和速度。利用201不锈钢和Q235钢作为基体,分别用来收集粒子和制备涂层。分析了不同喷嘴对飞行粒子温度和速度的影响,并通过扫描电镜(SEM)对扁平粒子的铺展程度和涂层显微组织进行了分析,并对比了涂层的结合强度、显微硬度和磨损失重量的差异。结果表明:在相同的测量位置,圆柱形喷嘴喷出粒子的速度比Laval喷嘴条件下的高出一倍,但是温度比Laval喷嘴条件下略低。圆柱形喷嘴获得的扁平粒子比Laval喷嘴获得的扁平粒子铺展程度要大;圆柱形喷嘴获得的涂层的孔隙率及磨损失重量比Laval喷嘴制备的小,其涂层的结合强度、显微硬度均高于Laval喷嘴制备的涂层。     

Analysis and optimization of the HVOF process by combined experimental and numerical approaches

Thermal spraying with the HVOF technology is a well known approach to dense metallic, ceramic and cermets coatings with good mechanical properties. Any attempt for improving HVOF coating properties requires a fundamental understanding of the mechanisms that occur during HVOF spraying. Thermal spray processes are not only optimized by empirical testing and by correlation analysis between process parameters and coating properties but also with numerical approaches. Recent attempts to understand the momentum and heat transfer mechanisms between flame and particles, and thus improve the control of the thermokinetic deposition process by analysis of fundamental thermophysical and fluid mechanical processes, have led to computational modeling of the spraying process and verification of simulation results by in-flight particle analysis.This paper focuses on modeling (tracking) of the particle properties during HVOF spraying using alumina powder. The particle properties are sensitive to a large number of process parameters (e.g., gas temperature, gas expansion velocity, pressure, spraying distance, spray powder particle diameter, nozzle geometry, etc.). Variation of the operating parameters of the HVOF process (gas flow rates, stoichiometric oxy/fuel ratio, nozzle design, etc.) is performed during modeling and simulation. The SprayWatch® system for particle in-flight measurement is used for verification of the numerical analysis result.     

The Role of Spraying Parameters and Inert Gas Shrouding in Hybrid Water-Argon Plasma Spraying of Tungsten and Copper for Nuclear Fusion Applications

Tungsten-based coatings have potential application in the plasma-facing components in future nuclear fusion reactors. By the combination of refractory tungsten with highly thermal conducting copper, or steel as a construction material, functionally graded coatings can be easily obtained by plasma spraying, and may result in the development of a material with favorable properties. During plasma spraying of these materials in the open atmosphere, oxidation is an important issue, which could have adverse effects on their properties. Among the means to control it is the application of inert gas shrouding, which forms the subject of this study and represents a lower-cost alternative to vacuum or low-pressure plasma spraying, potentially applicable also for spraying of large surfaces or spacious components. It is a continuation of recent studies focused on the effects of various parameters of the hybrid water-argon torch on the in-flight behavior of copper and tungsten powders and the resultant coatings. In the current study, argon shrouding with various configurations of the shroud was applied. The effects of torch parameters, such as power and argon flow rate, and powder morphology were also investigated. Their influence on the particle in-flight behavior as well as the structure, composition and properties of the coatings were quantified. With the help of auxiliary calculations, the mass changes of the powder particles, associated with oxidation and evaporation, were assessed.