等离子喷涂氧化铝基复合涂层研究进展

随着等离子喷涂技术的发展,等离子喷涂氧化铝基复合涂层在防腐蚀、耐磨损和航天航空等领域得到了广泛应用。首先简要介绍了新型等离子喷涂技术(激光等离子喷涂、悬浮液等离子喷涂和超音速等离子等)和主要喷涂工艺参数(喷涂功率、送粉方式和喷涂距离等),然后从改善涂层耐腐蚀性能的角度出发,阐述了第二相、喷涂工艺参数和后处理工艺对涂层气孔率的影响及与涂层耐腐蚀性能的关系。重点分析了硬度、喂料特征和激光熔覆技术对氧化铝基复合涂层耐磨损性能的影响,详述了影响硬度的因素,以及喷涂粉末特征和激光熔覆处理对复合涂层微观结构的影响。在电磁波吸收性能研究方面,论述了吸收剂含量、涂层厚度和多种电磁波吸收剂匹配以及喷涂参数的调整对等离子喷涂氧化铝基复合涂层吸波性能的影响。最后对以等离子喷涂技术制备性能更加优异的氧化铝基复合涂层提出了展望。     

Cold spray deposition of a WC-25Co cermet onto Al7075-T6 and carbon steel substrates

This work focussed on the deposition of wear-resistant and corrosion-resistant WC-25Co cermet powders on carbon steel and aluminium (Al7075-T6) substrates by cold gas spraying (CGS). The unique combination of mechanical, physical and chemical properties of WC-Co cermets has led to their widespread use for the manufacture of wear-resistant parts. X-ray diffraction tests were run on the powder and coatings to determine possible phase changes during the spraying process. The bonding strength of the coatings was measured by adhesion tests (ASTM C633-08). The sliding (ASTM G99-04) and abrasive (ASTM G65-00) wear resistance of the coatings were also studied. Corrosion resistance was determined by electrochemical measurements and salt fog spray tests (ASTM B117-03). CGS achieved thick, dense and hard WC-25Co coatings on both aluminium alloy Al7075-T6 and carbon steel substrates, with excellent tribological and electrochemical properties. We thus conclude that this method is very competitive compared with conventional thermal spraying techniques, giving thick, dense and hard coatings on both aluminium alloy Al7075-T6 and carbon steel substrates, with excellent tribological and electrochemical properties.     

The use of Al-Al2O3 cold spray coatings to improve the surface properties of magnesium alloys

Pure Al and 6061 aluminium alloy based Al₂O₃ particle-reinforced composite coatings were produced on AZ91E substrates using cold spray. The strength of the coating/substrate interface in tension was found to be stronger than the coating itself. The coatings have corrosion resistance similar to that of bulk pure aluminium in both salt spray and electrochemical tests. The wear resistance of the coatings is significantly better than that of the AZ91 Mg substrate, but the significant result is that the wear rate of the coatings is several decades lower than that of various bulk Al alloys tested for comparison. The effect of post-spray heat treatment, the volume fraction of Al₂O₃ within the coating and of the type of Al powder used in the coatings on the corrosion and wear resistance was also discussed.     

Al2O3/YSZ Composite Coatings Prepared by a Novel Sol–Gel Process and Their High-Temperature Oxidation Resistance

In this study, a novel sol–gel process has been utilized to fabricate Al₂O₃/YSZ (6 wt% yttria partially stabilized zirconia) composite coatings on Ni-based superalloy. The green coatings were obtained by electrophoretic deposition (EPD) in a suspension containing aluminium oxide sol, nano-Al₂O₃ and micro-YSZ particles, and then treated by so-called pressure filtration microwave sintering (PFMS) process. The as-sintered composite coatings were dense, uniform and crack-free and the phases mainly present α-Al₂O₃, m-ZrO₂ and t-ZrO₂ as aluminium oxide sol content decreasing. The cyclic oxidation tests at 1000 °C for 200 h demonstrate that both of high-temperature oxidation and spallation resistance for the coated samples were remarkably improved. These beneficial effects could be attributed to the special microstructure that micro-YSZ particles embedded in nano/submicron Al₂O₃ matrix. Meanwhile, the mechanisms of the inhibition of the oxygen diffusion and thermal match are further discussed.     

非晶态Ni-P合金与纳米Al2O3微粒复合镀层的制备

利用化学镀技术,制备了非晶态Ni-P合金基纳米Al2O3复合镀层,研究了纳米Al2O3微粒的加入量、加入方式以及搅拌方式等对复合镀层组织和形貌的影响.结果表明,纳米Al2O3在加入到镀液中以前,应先选用适当的表面活性剂和分散介质制成单分散添加液,然后再加到镀槽中才可保证纳米粒子在镀层中的均匀弥散分布,在超声振动搅拌方式下,镀液中只需加入1g/L纳米Al2O3,即可得到颗粒细小、分散均匀的非晶态Ni-P合金基纳米Al2O3的复合镀层.     

Abrasive wear characteristics and mechanisms of Al2O3／PA1010 composite coatings

The abrasive wear characteristics of Al2O3/PA1010 composite coatings on the surface of quenched and low-temperature temper steel 45 were tested on the tumplate abrasive wear testing machine and the same uncoated steel 45 was used as a reference material. Experimental results showed that the abrasive wear resistance of Al2O3/PA 1010 composite coatings has a good linear relationship with the volume fraction of Al2O3 particles in Al2O3/PA1010 composite coatings, and the linear correlative coefficient is 0.979. Under the experimental conditions, the size of Al2O3 particles (40.5-161.0μm) has little influence on the abrasive wear resistance of Al2O3/PA1010 composite coatings. By treating the surface of Al2O3 parti-cles with a suitable bonding agent, the distribution of Al2O3 particles in matrix PA1010 is more homogeneous and the bonding state between Al2O3 particles and matrix PA1010 is better. Therefore, the Al2O3 particles in Al2O3/PA1010 compos-ite coatings make the Al2O3/PA1010 composite coatings have better abrasive wear resistance than PA1010 coatings. The wear resistance of Al2O3/PA1010 composite coatings is about 45% compared with that of steel 45.     

稀土掺杂Gd2 O3对YSZ/（Ni，Al）热障涂层组织与性能的影响

目的提高YSZ/(Ni,Al)复合涂层与基体的结合强度和抗高温氧化性。方法采用电泳沉积的方法,在Inconel 600高温合金表面上沉积YSZ/(Ni,Al)复合涂层和掺杂稀土Gd2O3-YSZ/(Ni,Al)(简称G-YSZ/(Al,Ni))复合涂层,后进行真空烧结,然后对制备好的热障复合涂层进行划痕实验和等温循环氧化实验。通过对样品进行等温循环氧化实验,获取不同氧化时间段的复合涂层样品,并采用SEM和XRD对复合涂层组织和形貌进行分析。结果在1100℃等温氧化过程中,未掺杂稀土元素的氧化增重速率为0.0057 mg/mm2,而掺杂钆元素的氧化速率为0.0049 mg/mm2,氧化增重速率比未掺杂稀土YSZ/(Ni,Al)复合涂层的低。G-YSZ/(Ni,Al)热障复合涂层在等温氧化过程中颗粒长大较小、裂纹少、表面更加致密。真空烧结后的YSZ/(Al,Ni)复合涂层和G-YSZ/(Al,Ni)复合涂层与基体的结合强度约为4.0 N,氧化100 h后,掺杂稀土的G-YSZ/(Al,Ni)复合涂层结合强度为3.5 N,未掺杂稀土的YSZ/(Al,Ni)复合涂层与基体的结合强度为2.6 N。G-YSZ/(Ni,Al)热障复合涂层中存在Gd2Zr2O7相和稳定的Ni Al2O4相,Gd2Zr2O7相具有良好的稳定性以及耐高温氧化。结论掺杂稀土氧化钆的G-YSZ/(Al,Ni)涂层的抗高温氧化性能显著提高。在等温氧化过程中,掺杂稀土元素的G-YSZ/(Al,Ni)复合涂层,其颗粒趋向于均匀化,裂纹明显变少,使得涂层更加致密,表面更加平整。等温氧化100 h后,掺杂了稀土氧化钆的G-YSZ/(Al,Ni)复合涂层基体之间具有更好的结合力,抗剥落性和服役寿命较好。     

Electrochemical corrosion behaviour of Mg–Al alloys with thermal spray Al/SiCp composite coatings

The corrosion protection of Mg–Al alloys by flame thermal spraying of Al/SiC particles (SiCp) composite coatings was evaluated by electrochemical impedance spectroscopy in 3.5 wt.% NaCl solution. The volume fraction of SiCp varied between 5 and 30%. The as-sprayed Al/SiCp composite coatings revealed a high number of microchannels, largely in the vicinity of the SiCp, that facilitated the penetration of the electrolyte and the subsequent galvanic corrosion of the magnesium substrates. The application of a cold-pressing post-treatment reduced the degree of porosity of the coatings and improved the bonding at the coating/substrate and Al/SiC interfaces. This resulted in improved corrosion resistance of the coated specimens. The effectiveness of the coatings slightly decreased with the addition of 5–30 vol.% SiCp compared with the unreinforced thermal spray aluminium coatings.     

表面活性剂对镍-磷-纳米氧化铝复合镀的影响

研究了阴离子型表面活性剂(十二烷基苯磺酸钠、十二烷基硫酸钠)和阳离子型表面活性剂(三乙醇胺)对镍-磷-纳米氧化铝复合镀性能的影响.讨论了表面活性剂的种类、加入量对沉积速度、镀层的硬度和耐磨性能的影响.通过扫描电镜(SEM)观察各种复合镀层形貌,利用能谱仪(EDS)测量镀层中纳米A l2O3粒子的复合量.结果表明:纳米复合化学镀液中两种阴离子型表面活性剂的较佳加入量均为50 mg/L,阳离子型表面活性剂较佳加入量为100mg/L;采用阳离子表面活性剂时所得镀层的纳米粒子复合量较大,镀速快,耐磨性能好且纳米氧化铝分散较均匀;相比化学镀N i-P和微米A l2O3复合化学镀N i-P工艺所得镀层,纳米复合镀层具有较高的硬度和较好的耐磨性.     

摩擦喷射纳米Al2O3/Ni复合镀层的组织形貌及其性能研究

采用摩擦喷射电沉积工艺制备了纳米Al2O3／Ni复合镀层，考察了该镀层的表面和断面形貌，并对镀层性能进行了测试分析。研究表明，摩擦喷射纳米Al2O3／Ni复合镀层表面较为平整，镀层与基体结合紧密。一次性镀覆厚度达到1．40mm，远高于电刷镀纳米Al2O3／Ni复合镀层（0．35mm），镀层硬度达到650HV。在试验条件下，该镀层的耐磨性是摩擦喷射Ni镀层的1．44倍，是纳米Al2O3／Ni刷镀层的1．15倍，摩擦因数也低于摩擦喷射Ni镀层和电刷镀纳米Al2O3／Ni复合镀层。     

Al2O3对等离子喷涂Cr2O3/TiO2/Al2O3/SiO2复合陶瓷涂层性能影响研究

目的研究Al_2O_3添加量对Cr_2O_3/TiO_2/Al_2O_3/SiO_2四元复合陶瓷涂层性能的影响。方法采用等离子喷涂技术在油气管道X80管线钢基体表面制备出具有不同Al_2O_3含量的四元复合陶瓷涂层。另外,为探究基体温度对涂层性能的影响,所有涂层均在等离子喷枪预热及室温的两种基体上制备。所制涂层的气孔率、硬度、结合力及电化学腐蚀性能分别采用煮沸称重法、维氏硬度计、划痕仪、电化学工作站进行检测,并用X射线衍射仪(XRD)、扫描电镜(SEM)分析不同Al_2O_3含量涂层的物相组成和形貌特征,研究Al_2O_3含量对涂层各性能的影响。结果随着Al_2O_3含量的增加,Cr_2O_3/TiO_2/Al_2O_3/SiO_2四元复合陶瓷涂层的气孔率呈现先降低后增加的趋势,相对应的四元复合陶瓷涂层的结合力、维氏硬度则先增加后降低。当Al_2O_3质量分数为60%时,四元复合陶瓷涂层的性能最优,气孔率为3.6%,硬度为824.6HV,结合力为53.8N。电化学腐蚀测试表明,Al_2O_3能增强涂层的耐腐蚀性能,Al_2O_3质量分数为60%时,涂层自腐蚀电位最高,为-0.28 V。另外,在基体预热和不预热条件下,所制涂层性能随Al_2O_3含量的变化一致,但是基体预热比不预热更有利于涂层性能的提高。结论 Al_2O_3的添加不仅能够有效降低涂层Cr含量,还能显著提升四元复合陶瓷涂层的各项性能,特别是耐腐蚀性。此外,等离子喷涂前对基体进行预热,有利于涂层性能提高。     

Nano‐enamel: a new way to produce glass‐like protective coatings for metals

Nanoparticles and nanostructured films have gained an increasing interest for industrial application in the last years. Based on chemical nanotechnology glass‐like protective coatings thermally processed at comparatively lower temperatures around 500°C were developed for metal substrates by two different ways. Starting from polymeric sols (suspension consisting of branched macromolecules) containing multicomponent oxide of the SiO₂‐B₂O₃‐P₂O₅‐Na₂O system produced by hydrolysis and polycondensation of an alkoxide mixture under acidic condition, thin, hard, transparent, crack‐free and corrosion resistant coatings could be applied to aluminium and steel. Coatings from particulate sols (suspension consisting of solid particles) containing multicomponent oxide synthesized under basic condition by electrophoretic deposition (EPD) proved to be a promising method when very thick coatings are required. Both routes offer the potential of a new type of purely inorganic coatings for corrosion and abrasion protection.     

Corrosion behaviour of Mg/Al alloys with composite coatings

The corrosion behaviour of aluminium/silicon carbide (Al/SiC) composite coatings deposited by thermal spray on AZ31, AZ80 and AZ91D magnesium-aluminium alloys was investigated by electrochemical and gravimetric measurements in 3.5 wt.% NaCl solution at 22 °C. Corrosion products were examined by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis and low-angle X-ray diffraction (XRD). Al/SiC composite coatings in the as-sprayed state revealed high level of porosity with poor bonding at the Al/SiC and coating/substrate interfaces, which facilitated degradation of the magnesium substrates by a mechanism of galvanic corrosion. Cold-pressing post-treatment produced more compact coatings with improved corrosion performance in 3.5 wt.% NaCl compared with as-sprayed coatings.     

熔盐电解共渗铝硅及渗层的抗高温腐蚀性能

在渗铝涂层中加入少量硅可进一步提高涂层的抗高温氧化和热腐蚀性能。本文作者采用一种新的方法—高温熔盐电解法,在熔融氯化物盐浴中进行电解共渗铝硅,在铁和铁—铬合金上获得了渗铝硅涂层。 用氯化物作为电解质主要优点是无毒和价廉。高温熔盐电解渗铝硅可获得表面光洁、厚度均匀、与基体结合良好的致密渗层。通过控制电解温度、时间和电流密度可容易地控制渗层厚度,所得到的渗层不需随后热处理。 1000℃氧化试验和900℃热腐蚀(盐膜法)结果表明渗铝硅涂层比单纯渗铝涂层具有更好的保护性能。     

多种氧化物原位反应制备的Al2O3/Al复合材料

提出了多种氧化物与Al原位反应制备陶瓷颗粒增强铝基复合材料的新方法，并通过3种反应体系CuO／Al，(CuO SiO2)／Al，(CuO SiO2 TiO2)／Al制备了3种铝基复合材料。对原位反应过程进行了热力学分析。对复合材料的显微组织、硬度和力学性能进行了分析和研究。结果表明，多种氧化物与Al的原位反应能发生并自动进行下去，其反应状况良好。(CuO SiO2)／Al，(CuO SiO2 TiO2)／Al原位反应所获得的增强相颗粒分别是Al2O3和Al2O3 Al3Ti，增强相颗粒在复合材料中均匀分布，并且其所制得的复合材料的硬度与力学性能明显好于单一氧化物CuO所制得的复合材料。     

Ni-P/Al2O3化学复合镀工艺研究

采用正交设计法对Ni-P/Al2O3化学复合镀工艺进行了优化。研究了镀液成分，工艺参数对复合镀层厚度，显微硬度，耐蚀性，耐磨性的影响，结果表明，Ni-P/Al2O3化学复合镀层的显微硬度，耐磨性优于Ni-P化学镀层的，弥散分布的Al2O3颗粒能显著减缓复合镀层在较高温度下的软化趋势。     

Effect of Phase Transformation Mechanism on the Microstructure of Cold-sprayed Ni/Al-Al2O3 Composite Coatings during Post-spray Annealing Treatment

NiAl-Al₂O₃ intermetallic-based composite coatings were prepared by cold spraying of Ni/Al-Al₂O₃ composite powders followed by post-spray annealing treatment. The phase transformation mechanism from Ni/Al mechanical alloy to intermetallic compounds and its influence on the microstructure were examined to aim at controlling the coating microstructure. Results show that with the porous Ni/Al and Ni/Al-Al₂O₃ green compacts, a self-propagating high-temperature synthesis (SHS) reaction is ignited at a temperature of 500-600 °C. However, a SHS reaction could not be ignited for the cold-sprayed dense Ni/Al and Ni/Al-Al₂O₃ alloy coatings with or without a substrate. The phase transformation from Ni/Al mechanical alloy to NiAl intermetallic compound during post-spray annealing evidently can be attributed to a diffusion mechanism. Compared to the quite porous structure of the composites resulting from SHS, the composite coatings via diffusion phase transformation during post-spray annealing treatment present a relatively dense microstructure with neither large pores nor micro-sized cracks.     

溶胶-凝胶制备的Al_2O_3-SiO_2复合陶瓷涂层抗原子氧侵蚀性能研究

采用溶胶-凝胶法,以异丙醇铝、正硅酸乙酯为原料制得了稳定、均一的溶胶,浸涂在聚酰亚胺表面干燥后获得了致密透明的涂层.采用空间综合环境地面模拟设备对试样进行了原子氧(Atomic Oxygen, AO)暴露实验.测试表明,溶胶-凝胶制备的Al_2O_3-SiO_2涂层抗原子氧侵蚀性能优异,抗原子氧侵蚀性能比聚酰亚胺基体提高了2个数量级以上.经原子氧暴露后的复合陶瓷涂层质量几乎没有发生变化.经FTIR和XPS分析表明,在原子氧暴露后涂层表面产生的是Al_2O_3-SiO_2复合物.SEM分析表明,无涂层的聚酰亚胺原子氧暴露后表面非常粗糙且表面呈现地毯状形貌,而涂覆涂层的试样暴露前后表面形貌没有发生变化.采用紫外-可见光-近红外分光光度计对涂覆溶胶-凝胶复合陶瓷涂层后的试样分析表明原子氧暴露前后试样表面的光学性能也未发生变化.     

INVESTIGATION ON MICROSTRUCTURE AND TRIBOLOGICAL PROPERITIES OF CORED WIRE ARC SPRAYED Al/Al 2 O 3 COATINGS

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Parameter optimization for plasma-sprayed Al_2O_(3P)/Al composite coatings on AZ31 magnesium alloy

Al_2O_(3P)/Al composite coatings were prepared on the surface of AZ31 magnesium alloy by plasma spraying technology with mixed powders of Al and Al_2O_3. An orthogonal test containing six factors and five levels was carried out to acquire the optimum technical parameters. Microstructures and properties of the composite coatings were studied. The results show that the coatings consist of Al_2O_3 particulates distributed uniformly and Al matrix, and the interface between the particulate and matrix is continuous, compact and clean. With increasing the mass fraction of Al_2O_3 in the mixed powders, the volume fraction of Al_2O_3 in the coatings increases. The Al_2O_(3P)/Al composite coating with 14% Al_2O_3 volume fraction has more compact microstructure and more satisfactory properties.