掺杂镍对镁合金表面冷喷涂锌基涂层性能的影响

目的研究镍添加对冷喷涂锌基涂层耐蚀性的影响,为镁合金提供有效的防护涂层。方法采用低压冷喷涂技术在镁合金基体表面分别制备锌基和锌/镍基复合涂层,通过微观观察、摩擦磨损实验、电化学极化法和电化学阻抗谱测试及全浸泡腐蚀试验,研究镁合金表面冷喷涂涂层的结构、摩擦磨损行为和耐蚀性。结果镁合金表面冷喷涂锌基涂层后,其硬度和耐磨性得到显著提高,掺镍后的锌/镍基涂层具有更高的硬度和耐磨性。锌基和锌/镍基涂层均能为镁合金提供腐蚀防护,锌/镍基涂层比锌基涂层具有更好的耐蚀性。相对镁合金来说,锌基涂层和锌/镍基涂层的自腐蚀电位分别正移了260 mV和560 mV;长期腐蚀后锌/镍基涂层形成了更致密的腐蚀产物膜,腐蚀电阻显著高于锌基涂层。结论冷喷涂锌基和锌/镍复合涂层均能对镁合金提供防护作用,掺杂镍后的锌/镍基复合涂层具有更高的硬度、耐磨性和耐蚀性。     

镁合金表面冷喷涂层防护研究进展

镁合金作为最轻质的金属结构材料,由于其密度低和比强度高等优良的物理和力学性能,在航空、航天、汽车以及电子等领域引起广泛关注。然而,镁合金化学性质活泼、耐腐蚀和耐磨损性差等缺点严重制约其进一步应用。近些年发展起来的冷喷涂技术,在固态下制备涂层,涂层致密且与基体结合良好,因此可为镁合金表面防护提供一种新的有效方法。主要综述了镁合金表面冷喷涂耐腐蚀涂层(纯铝、铝合金和复合材料涂层)和耐磨损涂层(合金和复合材料涂层),论述了影响冷喷涂层耐腐蚀、耐磨损以及其他力学性能(硬度和涂层/基体结合强度)的主要因素,包括杂质元素含量、合金种类以及复合材料涂层中陶瓷颗粒含量、尺寸和形貌等。对比了几种常用表面处理技术制备的纯铝涂层的耐腐蚀性能,并阐述了冷喷涂技术在镁合金表面防护方面的优势。此外,还分析了热处理对冷喷涂纯铝和复合材料涂层耐蚀性的影响。最后提出了目前冷喷涂技术在镁合金防护方面的局限性以及发展难题,对未来研究趋势进行了展望。     

Erosion-corrosion of thermally sprayed coatings in simulated splash zone

The damage of marine steel structures in the splash zone is very severe. Applying thermally sprayed metal coatings is among the most important protective technologies, but the service life of current coatings is limited. In this paper, arc spray was used to prepare four types of metal coatings, that is, aluminum (Al), zinc bottom coating combined with aluminum topcoat (Zn + Al), aluminum-zinc pseudo alloy (Al/Zn) and aluminum-titanium pseudo alloy (Al/Ti) coatings. These metal coatings were sealed with epoxy priming and aliphatic polyurethane topcoat. Erosion-corrosion experiments were carried out on self-made device by simulating the splash zone working environment of steel structures and protective coatings. The results show that all the sealed coatings could improve the steel resistance to erosion-corrosion, and the aluminum-zinc pseudo alloy is the most excellent coating. In the coating failure process, mechanical erosion rather than corrosion is the key factor causing coating erosion-corrosion in splash zone. Improving the anti-cutting properties could help to prolong the coating life.     

High Pressure Cold Sprayed (HPCS) and Low Pressure Cold Sprayed (LPCS) Coatings Prepared from OFHC Cu Feedstock: Overview from Powder Characteristics to Coating Properties

Cold spraying enables high quality Cu coatings to be deposited for applications where high electrical and/or thermal conductivity is needed. Fully dense Cu coatings can provide an effective corrosion barrier in specific environments. The structure of cold-sprayed Cu coatings is characterized by high deformation which imparts excellent properties. Coating properties depend on powder, the cold spray process and post treatments. First of all, powder characteristics have a strong influence on the formation of pure coatings. Secondly, cold spraying provides dense, adherent, and conductive coatings by using HPCS and LPCS. Furthermore, an addition of Al₂O₃ particles to the Cu powder in LPCS process significantly improves coating properties. Also, heat treatments improve electrical conductivity. This study summarizes optimal characteristics of Cu powder optimized for cold spraying, achieving high coating quality and compares properties of HPCS Cu, LPCS Cu and Cu+Al₂O₃ coatings prepared from the same batch of OFHC Cu powder.     

Ultrafine Particulate Dispersed High-Temperature Coatings by Hybrid Spray Process

Oxide dispersion strengthened alloys (ODS), although not commonly used in coating applications, have long been used for high-temperature structural applications due to their superior creep properties. In this paper, we present the design, synthesis, and characterization of a new class of functionally engineered high-temperature coatings in which ultrafine oxide particulates are dispersed in the matrix alloy to achieve superior creep resistance along with improved high-temperature corrosion and erosion resistance. These coatings were fabricated using a novel technique called “hybrid spray process”. Hybrid spray technique combines arc spray and high-velocity oxy fuel (HVOF) spray processes; the metallic matrix alloys are fused by the wire arcing component of the process, whereas the ultrafine particles are synthesized in-flight by the HVOF component from liquid precursors. These particulate dispersed high-temperature composite coatings were fabricated using liquid precursors for SiO₂, Cr₂O₃, Al₂O₃, and wire feed stock of 55/45 NiCr, in one step. The coatings were then characterized using electron microscopy (SEM/TEM) and thermogravimetric analysis (TGA). High-temperature erosion, oxidation, and corrosion performance of these coatings were also evaluated and compared with 304 stainless steel, arc sprayed NiCr coatings as well as Alloy 625 overlay cladding. The hybrid spray process produced dense coatings with uniform dispersion of the ultrafine oxide particles. Further, these coatings also demonstrated superior corrosion, erosion, and oxidation resistance; SiO₂ particulate dispersion being most effective in terms of high-temperature corrosion resistance.     

Hydroxyapatite-Coated Magnesium-Based Biodegradable Alloy: Cold Spray Deposition and Simulated Body Fluid Studies

A simple modified cold spray process in which the substrate of AZ51 alloys were preheated to 400 °C and sprayed with hydroxyapatite (HAP) using high pressure cold air nozzle spray was designed to get biocompatible coatings of the order of 20-30 μm thickness. The coatings had an average modulus of 9 GPa. The biodegradation behavior of HAP-coated samples was tested by studying with simulated body fluid (SBF). The coating was characterized by FESEM microanalysis. ICPOES analysis was carried out for the SBF solution to know the change in ion concentrations. Control samples showed no aluminum corrosion but heavy Mg corrosion. On the HAP-coated alloy samples, HAP coatings started dissolving after 1 day but showed signs of regeneration after 10 days of holding. All through the testing period while the HAP coating got eroded, the surface of the sample got deposited with different apatite-like compounds and the phase changed with course from DCPD to β-TCP and β-TCMP. The HAP-coated samples clearly improved the biodegradability of Mg alloy, attributed to the dissolution and re-precipitation of apatite showed by the coatings as compared to the control samples.     

Corrosion Properties of Cold-Sprayed Tantalum Coatings

Cold spraying enables the production of pure and dense metallic coatings. Denseness (impermeability) plays an important role in the corrosion resistance of coatings, and good corrosion resistance is based on the formation of a protective oxide layer in case of passivating metals and metal alloys. The aim of this study was to investigate the microstructural details, denseness, and corrosion resistance of two cold-sprayed tantalum coatings with a scanning electron microscope and corrosion tests. Polarization measurements were taken to gain information on the corrosion properties of the coatings in 3.5 wt.% NaCl and 40 wt.% H₂SO₄ solutions at room temperature and temperature of 80 °C. Standard and improved tantalum powders were tested with different spraying conditions. The cold-sprayed tantalum coating prepared from improved tantalum powder with advanced cold spray system showed excellent corrosion resistance: in microstructural analysis, it showed a uniformly dense microstructure, and, in addition, performed well in all corrosion tests.     

Enhancement of the corrosion properties of cold sprayed Ti–6Al–4V coatings on mild steel via silica sealer

The pore formation associated with the cold spray process requires the development of an economical sealer to enhance the corrosion resistance of Ti–6Al–4V coatings on a mild steel substrate. Herein, a sound method is developed to seal pores in the cold sprayed Ti–6Al–4V coatings with silica sealer. Potentiodynamic polarization tests in 3.5 wt% sodium chloride electrolyte were employed to investigate the corrosion resistance of cold sprayed Ti–6Al–4V coatings fabricated at two standoff distances (30 and 70 mm) before and after the sealing process. The polarization resistance of cold sprayed Ti–6Al–4V coatings significantly increased by >80% after the sealing process. The electrochemical responses of cold sprayed Ti–6Al–4V were dependant on sealing the pores with agglomerated silica nanoparticles as observed by scanning electron microscopy and energy-dispersive X-ray analysis. The increase in polarization resistance makes the sealer an effective treatment for cold sprayed Ti–6Al–4V coatings used in marine environments and other engineering applications. This sophisticated sealing process can reduce the deposition cost by reducing the thickness of Ti–6Al–4V coatings and increasing their lifetime on metal components.     

300M钢表面冷喷涂锌镍复合涂层性能研究

目的 研究300M高强钢表面的冷喷涂锌镍复合涂层的涂层性能.方法 采用机械混合的方式将锌粉和镍粉进行混合,利用低温气动喷涂技术在300M高强钢表面制备锌镍复合涂层,采用扫描电子显微镜、能量色散谱和显微硬度测试仪研究涂层的微观组织结构.采用普通中性盐雾加速实验、涂层破损盐雾加速试验及户外暴晒试验,对冷喷涂锌镍涂层的抗腐蚀性能进行综合评价.考核冷喷涂对300M钢基材疲劳性能的影响.结果 根据SEM的表面及截面图片分析,冷啧涂锌镍复合涂层十分致密,且无孔隙及裂纹,涂层的孔隙率平均为0.4％,结合强度40 MPa左右.根据EDS结果分析,锌镍复合涂层中锌的质量分数为85％左右,镍的质量分数为15％左右.锌镍复合涂层的显微硬度为70.8HV0.49.锌镍复合涂层中镍粒子的强化作用,提高了涂层的硬度.冷喷涂锌镍复合涂层具有非常好的抗腐蚀性能,盐雾实验超过770h,即使涂层破损也可以达到600h.户外暴晒实验12个月表面无明显腐蚀,并且冷喷涂对300M钢基材的疲劳性能没有影响.结论 冷喷涂锌镍复合涂层作为抗腐蚀涂层,可以对300M高强钢提供保护.     

Corrosion inhibitors in conversion coatings. IV

This review covers main approaches to development of inhibited conversion formulations for chemical oxidation of aluminum alloys. A mechanism explaining the formation of conversion coatings on aluminum alloys from chromate conversion baths is proposed; the protective properties of the resulting coatings are characterized. It is demonstrated that various modified methods for the preparation of chromate conversion coatings on aluminum enhance their protective properties, however, without solving ecological problems. Among alternative corrosion inhibitors used in chemical oxidation of aluminum alloys, molybdate-containing formulations are worth noting and have been much investigated. The most promising approach is to develop corrosion inhibitors for use during both the formation of a conversion coating and its subsequent filling with compounds chemisorbable at the modified oxide. Original Russian Text ? S.V. Oleinik, Yu.I. Kuznetsov, 2007, published in Zashchita Metallov, 2007, Vol. 43, No. 4, pp. 421–428.     

Effects of Arc Spray Process Parameters on Corrosion Resistance of Ti Coatings

In order to improve the corrosion resistance of carbon steel structures in marine environment, Ti wires were sprayed to a steel substrate using arc spray technique, and orthogonal experimental design was used to investigate the effects of the fluctuation in the main parameters of spray process on the microstructure and the corrosion resistance of sprayed coatings. The results show that the corrosion resistance of sprayed coatings is very sensitive to spray process parameters, corrosion current density can decrease from 997.7 to 5.08 μA cm⁻² by optimizing process parameters. The coatings are composed of TiN and Ti₂O, and the corrosion resistance of coatings can be improved with the decrease in the contents of oxides. The spray distance should be exactly monitored and controlled in arc spray process because of its great effects on the quality of sprayed coatings.     

Effect of Ceramic Particle Velocity on Cold Spray Deposition of Metal-Ceramic Coatings

In this paper, metal-ceramic coatings are cold sprayed taking into account the spray parameters of both metal and ceramic particles. The effect of the ceramic particle velocity on the process of metal-ceramic coating formation and the coating properties is analyzed. Copper and aluminum powders are used as metal components. Two fractions of aluminum oxide and silicon carbide are sprayed in the tests. The ceramic particle velocity is varied by the particle injection into different zones of the gas flow: the subsonic and supersonic parts of the nozzle and the free jet after the nozzle exit. The experiments demonstrated the importance of the ceramic particle velocity for the stability of the process: Ceramic particles accelerated to a high enough velocity penetrate into the coating, while low-velocity ceramic particles rebound from its surface.     

电弧喷涂Zn-Al伪合金涂层耐腐蚀性能研究进展

通过在钢基体表面制备涂层可以很好地延长钢铁材料的服役时间,减少因腐蚀造成的重大事故和人员伤亡。相较于传统的纯Zn涂层、纯Al涂层以及Zn-Al合金涂层,Zn-Al伪合金涂层能够为基体材料提供长久有效的腐蚀防护,在钢铁材料的腐蚀防护中具有巨大的应用潜力。简述了Zn-Al伪合金涂层电弧喷涂制备工艺的特点;介绍了Zn、Al、Zn-Al合金及Zn-Al伪合金涂层在模拟海洋环境下的腐蚀防护原理;在此基础上从组分、喷涂工艺参数(喷涂距离、喷涂电流和喷涂电压)、元素掺杂(Mg、Si及Re)及后处理工艺(封孔、激光重熔)等角度,论述了其对Zn-Al伪合金涂层耐蚀性的影响;讨论了Zn-Al伪合金涂层防腐体系在桥梁、海洋钢结构件、地下运输管道中的应用现状;最后总结了目前研究工作中存在的挑战,提出了电弧喷涂Zn-Al伪合金涂层尚需深入研究的重点问题,为提高钢铁材料使用寿命提供了参考。     

Investigations on the Behavior of HVOF and Cold Sprayed Ni-20Cr Coating on T22 Boiler Steel in Actual Boiler Environment

High temperature corrosion accompanied by erosion is a severe problem, which may result in premature failure of the boiler tubes. One countermeasure to overcome this problem is the use of thermal spray protective coatings. In the current investigation high velocity oxy-fuel (HVOF) and cold spray processes have been used to deposit commercial Ni-20Cr powder on T22 boiler steel. To evaluate the performance of the coatings in actual conditions the bare as well as the coated steels were subjected to cyclic exposures, in the superheater zone of a coal fired boiler for 15 cycles. The weight change and thickness loss data were used to establish kinetics of the erosion-corrosion. X-ray diffraction, surface and cross-sectional field emission scanning electron microscope/energy dispersive spectroscopy (FE-SEM/EDS) and x-ray mapping techniques were used to analyse the as-sprayed and corroded specimens. The HVOF sprayed coating performed better than its cold sprayed counterpart in actual boiler environment.     

Corrosion behaviour of Mg–Al alloys with Al–11Si thermal spray coatings

The corrosion resistance of AZ31, AZ80 and AZ91D Mg–Al alloys with Al–11Si thermal spray coatings was evaluated by electrochemical and gravimetric measurements in 3.5 wt% NaCl solution. The changes in the morphology and corrosion behaviour of the Al–11Si coatings induced by a cold‐pressing post‐treatment under 32 MPa were also examined. The as‐sprayed Al–11Si coatings revealed high degree of porosity and poor corrosion protection, which resulted in galvanic acceleration of the corrosion of the magnesium substrates. The application of a cold‐pressing post‐treatment produced more compact Al–11Si coatings with better bonding at the substrate/coating interface and slightly higher corrosion resistance. However, interconnected pores remained in the cold‐pressed coatings due to the low plasticity of the Al–11Si powder and galvanic corrosion of the substrate was observed after immersion in 3.5 wt% NaCl for 10 days.     

铁质文物腐蚀防护技术研究进展

中国是有着五千年灿烂文化的文明古国和文化遗产大国。文物保护是中华儿女传承古老文明的历史责任。铁质文物在中国拥有漫长的历史，但由于铁作为金属的活泼性较强，易腐蚀，现存的铁质文物面临保存现状差且防护难度大的严峻挑战，因此如何对铁质文物进行系统性防护成为研究工作的重点。鉴于目前铁质文物腐蚀防护技术受到国内学者和文物界越来越多的关注，基于大量的文献调研和长期对国内外腐蚀防护技术研究动态的跟踪，对铁质文物腐蚀防护技术的研究进展进行了总结。首先，结合铁质文物具体保护实例简介了铁质文物的腐蚀机理。其次，讨论了铁质文物传统的腐蚀防护技术，主要包括除锈技术、脱盐技术、缓蚀技术和封护技术。除锈技术主要分为物理除锈技术和化学除锈技术，对比了两者的技术优势和劣势，重点阐述了激光清洗的作用机理以及除锈效果;脱盐技术的方法众多，主要通过实例介绍了索氏提取法和碱性溶液浸泡法的脱盐机理;缓蚀技术的核心为缓蚀剂，阐述了多种缓蚀剂对不同铁质文物的缓蚀效果;封护技术主要介绍了微晶石蜡、丙烯酸树脂和氟碳涂料3种材料在铁质文物上的应用。随着材料科学的发展，在铁质文物表面制备防护性涂层可实现对基体的有效保护，但由于金属涂层制备技术多以激光束、等离子束、电子束等高能量密度束为热源，导致涂层制备过程热输入过大，对铁质文物基体的损伤较大。根据铁质文物的防护性要求——“不改变文物原状”与“最小干预”原则，介绍了一种基于低温环境下将微米级金属粉末或复合粉末加速至超音速状态并沉积于基体材料表面形成涂层的新型表面防护技术——冷喷涂技术，重点介绍了几种不同金属基材料在铁碳合金表面形成涂层的实际性能，主要表现为显微组织均匀致密，且与基体之间形成了较好的界面结合，有望应用于铁质文物的修复与防护领域。最后，指出了铁质文物腐蚀防护研究进展尚存的关键问题，并对铁质文物腐蚀防护技术的发展前景进行了展望，为文物保护工作者的研究实践提供新思路。     

WC-Co/Al Multilayer Coatings by Warm Spray Deposition

WC-Co/aluminum multilayer coatings have been developed by using warm spray deposition to improve fracture toughness and damage tolerance of conventional WC-Co coatings and to investigate the effects of ductile layer addition on their fracture properties. Prior to depositing the multilayer coatings, the mechanical properties of three metal coatings of aluminum, copper, and titanium, which were deposited by warm spraying, were evaluated. The aluminum coating showed excellent ductility among them and was selected for use as ductile layers for the multilayer coatings. The fracture behavior of WC-Co/Al coatings was examined by the four-point bending test. The multilayer coatings did not break in a brittle manner after reaching maximum load, but exhibited a plateau as a result of the ductility of the aluminum layers. The fracture behavior was compared with the finite element analysis results, and they showed good agreement in a general trend. It has been concluded that ductile metal reinforcements, by advanced thermal spray techniques such as warm spray deposition, are very effective to enhance the toughness and damage tolerance of sprayed cermet coatings.     

Production of Annealed Cold-Sprayed 316L Stainless Steel Coatings for Biomedical Applications and Their in-vitro Corrosion Response

316L powders were successfully deposited onto Al5052 aluminium substrates by cold spray method. Annealing was treated on the coated samples at 250–1000°C temperatures under Ar atmosphere. The in vitro performances of the coatings have been compared with using electrochemical corrosion test technique in the simulated body fluid (SBF) at body temperature (37°C). A scanning electron microscope (SEM-EDS) and X-ray diffraction (XRD) have been used for microstructural characterization and phases identifications of the coatings, respectively. The results were shown that there are high adhesions at particle and substrate interfaces and between the particles deposited as well. Also, the increasing annealing temperature increases corrosion resistance of the cold sprayed 316L stainless steel coatings. The corrosion susceptibility of the coating annealed at 1000°C was similar that of standard 316L stainless steel implant material in Ringer’s solution. The microstructural observations revealed that corrosion starts between the inter-splat powders and continues throughout the surface not in-depth.     

冷喷涂金属基复合涂层及材料研究进展

冷喷涂是近年来一种发展十分迅速的材料固态沉积技术,其具有喷涂温度低和颗粒沉积速度高的特点,在金属基复合涂层及材料制备方面展现出了良好的应用前景。 在大量文献整理和分析的基础上,对冷喷涂金属基复合涂层及材料的最新研究进展进行了系统的介绍。 首先归纳了机械混合法、球磨法、包覆法以及造粒法等复合粉末的制备方法及其优缺点,为复合粉末的制备和选择提供了参考;其次,分类介绍了采用冷喷涂制备的铝基、镍基、铜基、钴基以及其他金属基复合涂层及材料;再次,分析了退火、激光、搅拌摩擦焊和热机械等后续处理方法对冷喷涂金属基复合涂层及材料组织结构和性能的影响,并介绍了不同后续处理方法的优缺点;最后,总结了冷喷涂金属基复合涂层及材料的潜在应用领域和存在问题。     

A comparative study of high velocity oxygen fuel,vacuum plasma spray,and axial plasma spray for the deposition of CoNiCrAlY bond coat alloy

In the aerospace field as well as in the stationary gas turbine field, thermally sprayed coatings are used to improve the surface properties of nickel-super-alloys materials. Coatings are commonly used as bond coat and antioxidation materials (mainly MCrAlY alloys) and as thermal barrier coatings (mainly yttria partially stabilized zirconia). The purpose of the current study was to assess the properties of thermally sprayed bond coat CoNiCrAlY alloys comparing the performance of three different techniques: vacuum plasma spray (VPS), high velocity oxygen fuel (HVOF), and axial plasma spray (AxPS). The quality of the deposited films has been assessed and compared from the point of view of microstructural (porosity, oxide concentration, unmelted particles presence) and mechanical (hardness) characteristics. The surface composition and morphology of the coatings were also determined. Specific efficiency tests were performed for the three examined technologies. The highest quality coatings are obtained by VPS, but also high velocity oxygen fuel and AxPS sprayed films have interesting properties, which can make their use interesting for some applications.