热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气环境中的腐蚀行为研究

目的 为详细研究热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气下的腐蚀行为及作用机理,同时为热浸镀Zn-Al-Mg镀层在湿热海洋大气环境中服役提供数据参考。方法 采用腐蚀失重、XRD、SEM、电化学等测试方法对热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气环境下的腐蚀行为进行研究。结果 腐蚀产物主要由Zn₅(OH)₈Cl₂·H₂O组成,腐蚀一段时间后,发现少量ZnO、Zn₅(OH)₆CO₃,腐蚀产物具有与锌腐蚀类似的层状结构,1 848 h呈“三明治”型,相比于上下两层暗色物质,中层亮色腐蚀产物富集更多的Cl元素。热浸镀Zn-Al-Mg镀层腐蚀速率大体随时间延长呈上升趋势,只在672～840 h腐蚀速率下降,对比镀锌在模拟环境和锌在湿热大气环境中的腐蚀,热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气中表现出较好的耐蚀性。结论热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气下腐蚀产物演变与腐蚀过程中Mg的参与有关。腐蚀672～840h阶段腐蚀速率...     

The thermal spray processing of HA powders and coatings

In recent years, coated implants have been actively researched and put to use in many biomedical engineering applications. The coating used on the implants is hydroxyapatite (HA), a calcium-phosphate compound with attractive bioactive and biocompatible properties that can enhance the fixation process of biomedical implants. Thermal spraying provides a potent means for depositing the HA coatings on implants. Among the populat thermal-spray techniques are combustion-flame spray, plasma spray, and high-velocity oxy-fuel spray. This article investigates the versatility of thermal-spray techniques to perform spheroidization of HA powders, the preparation of HA-based biocomposite powders and coatings, and the deposition of HA coatings.     

Phosphoric acid anodization of Ti-6Al-4V - Structural and corrosion aspects

Electrodeposited anodic oxide coatings were produced on Ti-6Al-4V from phosphoric acid electrolyte. Different coatings were produced by varying the time periods. Structure of the coatings was analysed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The coatings were exposed to simulated body fluid for a period of 1 month and the weight loss is used to calculate the corrosion rate. Electrochemical polarization and ac impedance studies were performed on the coatings in simulated body fluid and it was found that coatings produced from shorter times showed very good resistance to the attack by this medium.     

Development of carbon nanotubes reinforced hydroxyapatite composite coatings on titanium by electrodeposition method

Carbon nanotubes (CNTs) are outstanding reinforcement material for imparting strength and toughness to brittle hydroxyapatite (HAP). This work reports the electrodeposition of CNTs reinforced HAP on titanium substrate at −1.4 V vs. SCE during 30 min with the functionalised CNTs concentration ranging from 0 to 2 wt.%. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysis (EDX), high resolution transmission electron microscopy (HRTEM), mechanical and biological studies were used to characterise the coatings. Also, the corrosion resistance of the coatings was evaluated by electrochemical techniques in simulated body fluid (SBF) solution.     

Investigation and Comparison of In-Flight Particle Velocity During the Plasma-Spray Process as Measured by Laser Doppler Anemometry and DPV-2000

Plasma spraying has become one of the most important thermal-spray technologies due to low operating costs, high deposition rates, and a high efficiency. It is especially suitable for producing coatings used to improve thermal, corrosion, and wear protection. The quality of coatings produced by thermal-spray processes are determined by particle characteristics, such as in-flight velocity, which can be investigated using various diagnostic systems. Velocity is a particularly relevant parameter for small particles, but it is difficult to measure. Hence, different velocity diagnostics must be validated for small injected particles. We compared the laser Doppler anemometry (LDA) system with the DPV-2000 system and measured the particle velocities of a F4 plasma torch. The results agreed well when the limited detectability of small particles by LDA was taken into account.     

The structure and properties of chromium nitride coatings deposited using dc, pulsed dc and modulated pulse power magnetron sputtering

The time averaged ion energy distributions and ion fluxes of continuous dc magnetron sputtering (dcMS), middle frequency pulsed dc magnetron sputtering (PMS), and modulated pulse power (MPP) magnetron sputtering plasmas were compared during sputtering of a Cr target in an Ar/N₂ atmosphere in a closed field unbalanced magnetron sputtering system. The results showed that the dcMS plasma exhibited a low ion energy and ion flux; the PMS plasma generated a moderate ion flux of multiple high ion energy regions; while the MPP plasma exhibited a significantly increased number of target Cr⁺ and gas ions with a low ion energy as compared to the dcMS and PMS plasmas. Cubic CrN coatings were deposited using these three techniques with a floating substrate bias. The structure and properties of the coatings were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nanoindentation, microscratch and ball-on-disk wear tests. It was found that the deposition rate of the MPP CrN depositions was slightly lower than those of the dcMS depositions, but higher than in the PMS depositions at similar average target powers. The coatings deposited in the dcMS and PMS conditions without the aid of the substrate bias exhibited large columnar grains with clear grain boundaries. On the other hand, the interruption of the large columnar grain growth accompanied with the renucleation and growth of the grains was revealed in the MPP CrN coatings. The MPP CrN coatings exhibited a dense microstructure, fine grain size and smooth surface with high hardness (24.5 and 26 GPa), improved wear resistance (COF = 0.33 and 0.36) and adhesion, which are the results of the low ion energy and high ion flux bombardment from the MPP plasma.     

Synthesis and evaluation of corrosion resistance of molybdate-based conversion coatings on electroplated zinc

Three molybdate-based conversion coatings on electroplated zinc have been prepared and the composition, morphology, and structure of these coatings are measured by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and X-ray diffraction (XRD), respectively. It was found that these coatings with ‘meshwork’ surface were complex coatings composed of multiple compounds. Molybdenum species were present in the conversion coating as Mo (VI) and Mo (IV) compounds. The results of neutral salt spray test showed that molybdate-based conversion coatings with the addition of H₃PO₄, SiO₂ and TiOSO₄ in the passivation baths possess higher corrosion resistance compared with chromate conversion coatings, which was due to the compactness and anti-corrosion essence of the conversion coating.     

Mechanical properties and scratch test resistance of nickel-boron coated aluminium alloy after heat treatments

Electroless nickel-boron deposits were synthesized on aluminium alloys and submitted to heat treatments under neutral (95% Ar + 5% H₂) atmosphere. Two set of treatment conditions were used: 1 h at 400 °C and 4 h at 180 °C. Micro- and nanohardness measurements were carried out on the free surface of the sample and on polished cross-sections. A comparative hardness study was conducted to assess the influence of load, indent position (free surface or cross section), and heat treatment on the results of the indentation tests. Scratch tests were made on selected coatings to assess their adhesive properties and scratch resistance. Roughness measurements were carried out on the coatings before and after heat treatments. The samples were also investigated by XRD (X-ray Diffraction), SEM (Scanning electron microscopy) and optical microscopy to link their mechanical properties to their composition, structure and morphology.     

Preparation of calcium phosphate coatings on Mg-1.0Ca alloy

The calcium phosphate coatings were prepared by virtue of electrochemical deposition in order to improve the corrosion resistance of Mg-1.0Ca alloys in simulated body fluids.The chemical compositions,structures and morphologies of the coatings were investigated by energy dispersive spectroscopy(EDS),X-ray diffractometry(XRD)and scanning electron microscopy(SEM), respectively.The potentiodynamic electrochemical technique was employed to investigate the bio-degradation behavior of Mg-1.0Ca alloys with Ca-P coatings in Hank's solutions.The experimental results show that the deposited coatings predominately consist of flake-shape brushite(DCPD,CaHPO4·2H2O)crystallites.The corrosion resistance of the substrates with coatings is improved in Hank's solutions significantly.     

The atmospheric corrosion resistance of electrodeposited tin-cadmium and tin-zinc coatings on steel

Abstract

A study has been made of the corrosion-resisting properties of tin-cadmium and tin-zinc coatings on steel in which both laminar and alloy coatings have been tested using atmospheric exposure and accelerated tests. It is concluded that electrodeposited coatings of zinc on a tin substrate or zinc alone possess a greater resistance to atmospheric corrosion in an industrial atmosphere than equivalent coatings of cadmium on tin or tin on cadmium, or tin-zinc alloy coatings. The corrosion resistance of tin-zinc laminar coatings depends primarily on the amount of zinc present. Alloy coatings of tin-zinc and tin-cadmium generally possess similar corrosion resistance to those of the tin and cadmium laminar coatings. Under simulated marine conditions (A.R.E. Salt Droplet test) the corrosion resistance of coatings containing cadmium is superior to that of corresponding coatings containing zinc.     

电弧喷涂锌涂层的酸雨腐蚀性能

热镀锌涂层因具有优越的耐腐蚀性、涂装性能等被广泛应用于工业生产众多领域,成为金属材料在户外工作环境下防腐蚀的有效措施之一。为研究热喷涂锌涂层在酸雨中的腐蚀行为,采用电弧喷涂技术在Q235碳素结构钢表面喷涂锌涂层,模拟酸雨腐蚀环境,在腐蚀液pH值改变的情况下,采用SEM,XRD,硬度测试及失重分析等手段,分析不同pH值溶液腐蚀后涂层的表面形貌和腐蚀产物,及试样的硬度变化和腐蚀速率情况。结果表明,锌涂层的表面腐蚀会随着模拟酸雨溶液pH值的降低而加重,其表面腐蚀产物逐渐增多,腐蚀产物的形貌由小块状逐渐变成羽针状和岛状,主要成分为Zn(OH)2,ZnSO4和Zn4SO4(OH)6·3H2O;涂层表面硬度最高为23.4 HV、最小腐蚀速率为0.21×10-4g/(m2·h),但当模拟酸雨溶液pH值由7降至2.8时,涂层表面硬度降低约12%,腐蚀速率约增大至最小值的26倍;模拟酸雨溶液pH值在5～2.8时,溶液对锌涂层的腐蚀比较严重。     

Microstructural characterization and hardness evaluation of HVOF sprayed Ni–5Al coatings on Ni- and Fe-based superalloys

HVOF sprayed Ni–5Al coatings on Ni- and Fe-based superalloy substrates were characterized to assess the microstructural features and strength in the as deposition condition for their applications in high-temperature corrosive environment of gas turbine. X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), and X-ray mapping analysis are used to characterize the Ni–5Al coatings. The dense coatings with less porosity and inclusions were produced using HVOF process. The deposited Ni–5Al coatings exhibited splat like layered morphologies due to deposition and resolidification of successive molten and semi molten powder particles. The hardness of coatings on three different superalloy substrates was measured and it was in the range of 210–272 Hv. The average bond strength and surface roughness of the as-sprayed coatings were 42.62 MPa and 9.22–9.45 μm, respectively. Diffusion of alloying elements from the substrate into the coating has occurred in all the three superalloy substrates as observed from the X-ray mapping analysis.     

The development of low-temperature hardening silicone ceramer coatings for the corrosion protection of metals

The process parameters for the formulation of two different hybrid ceramic-polymer (ceramer), barrier-type coatings for the corrosion protection of metals are discussed. The coating formulations were characterized in the liquid, gel, and solid phases using Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and Secondary Ion Mass Spectroscopy (SIMS), respectively. The coatings were applied to 6061-T6 aluminum alloy, hardened in ambient conditions, and analyzed with X-ray photoelectron spectroscopy (XPS). Thermal stability of the coatings was analyzed in inert and oxidative atmosphere using thermogravimertic analysis. The final surface morphology was studied using Scanning Electron Microscope (SEM) and Atomic Force Microscopy (AFM). The nanoindentation technique supported by SEM revealed the nanomechanical properties of the coatings. The effectiveness as a barrier-type coating was studied using electrochemical polarization experiments and immersion experiments in saline solution.     

Abrasive wear behaviour of laser clad and flame sprayed-melted NiCrBSi coatings

In this work, the influence of the processing conditions on the microstructure and abrasive wear behaviour of a NiCrBSi hardfacing alloy is analysed. The hardfacing alloy was applied in the form of coatings onto a mild steel substrate (Fe–0.15%C) by different techniques: laser cladding (LC) and flame spraying (FS) combined with surface flame melting (SFM). In both cases, the appropriate selection of the process parameters enabled high-quality, defect-free NiCrBSi coatings to be obtained. The microstructure of the coatings was analysed by scanning electron microscopy (SEM), with attached energy dispersive spectroscopy (EDS) microprobe, and by X-ray diffraction (XRD). Their tribological properties were evaluated by micro-scale ball cratering abrasive wear tests using different abrasives: diamond, SiC and WC. Microstructural characterisation showed that both coatings exhibit similar phases in their microstructure, but the phases present differ in morphology, size distribution and relative proportions from one coating to another. Wear tests showed that in three-body abrasive conditions, despite these microstructural differences, the wear behaviour is comparable for both coatings. Conversely, in two-body wear conditions with diamond particles as the abrasive, it was observed that the specific wear rate of the material is sensitive to microstructural changes. This fact is particularly apparent in LC coatings, in which the zones of the layers with higher proportions of very small hard particles present a lower wear resistance. These results indicate that it is important to have good microstructural control of this material, in order to obtain coatings with an optimized and homogeneous tribological behaviour.     

Influences of chromium and hafnium additions on the microstructures of β-nial coatings on superalloy substrates

In this study, Hf-doped and Cr/Hf-modified NiAl coatings were deposited onto René N5^® substrates via direct current magnetron sputtering. Microstructural analysis using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA) showed the as-deposited coatings to be single phase with B2 crystal structures. Post-deposition annealing at 1000 °C in an Ar + 5%H₂ atmosphere resulted in the formation of nanometer-sized precipitates along grain boundaries and within grain interiors. TEM analyses showed most of the precipitates to be β′-Ni₂AlHf. Three-dimensional atom probe tomography (3D-APT) also revealed the presence of α-Cr precipitates within the NiAlCrHf coatings after annealing. The results have been analyzed and discussed relative to previous research on sputter deposited NiAl–Hf coatings.     

Phase composition and in-vitro bioactivity of plasma sprayed calcia stabilized zirconia coatings

Zirconia coatings stabilized with different calcia content (12.8 mol%, 16 mol% and 30 mol%) were fabricated on titanium alloy substrates using atmospheric plasma spraying technology. The in-vitro bioactivity of coatings was evaluated by simulated body fluid (SBF) soaking test. The morphology and phase composition of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), micro Raman spectroscopy, energy dispersive spectrometry (EDS) and infrared spectroscopy (IR). The results showed that the apatite was formed on the surface of the calcia stabilized zirconia coatings soaked in SBF for 28 days and the formation ability of apatite decreased with the increase in calcia content of the coating. The bioactivity of zirconia coatings was thought to be related to the Zr-OH formed on their surfaces during the phase transformation in the presence of water. Osteoblast-like MG63 cells were cultured on the surfaces of the coatings to evaluate their cytocompatibility. Results showed that MG63 cell grew and proliferated well on all coating surfaces, indicating that plasma sprayed calcia stabilized ZrO₂ coatings were cytocompatible.     

A study on microstructure and properties of calcium phosphate coatings processed using ion beam assisted deposition on heated substrates

In this study a set of thin Hydroxyapatite (HA) [Ca₁₀(PO₄)₆(OH)₂] coatings was deposited on heated silicon and titanium substrates using Ion Beam Assisted Deposition (IBAD). The effects of substrate temperature and processing parameters on the microstructural properties and composition of the coatings are being studied. Analytical techniques include transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) with an energy dispersive X-ray spectroscopy (EDS), as well as scanning electron microscopy (SEM) with EDX, X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR). The current results indicate that as substrate temperature increases the Ca/P ratio of the coatings both on titanium and silicon substrates increases. The crystallinity of the coatings and the number of calcium phosphate compounds within the coating including HA also increases. STEM-EDS revealed an atomically diffused intermediate layer at the interface between the coating and substrate. XRD results along with TEM selected area diffraction (SAD) revealed that the coatings are composed of HA, other calcium phosphate, and calcium oxide compounds.     

埋弧堆焊TiC颗粒增强复合涂层的组织与性能

以TiFe粉、Cr粉、Ni粉、Fe粉、胶体石墨等为原料,利用合金粉粒埋弧堆焊技术在Q235钢表面原位反应合成TiC颗粒增强Fe基复合涂层。利用SEM,XRD和EDS等分析了涂层的显微组织,并在室温干滑动磨损条件下测试该涂层的耐磨性能。结果表明:利用合金粉粒埋弧堆焊技术,可以原位合成粒径在2μm以下、弥散分布的TiC颗粒。涂层组织由TiC颗粒、马氏体和奥氏体构成。涂层平均显微硬度达601HV0.2,约是碳钢基体的3倍。由于TiC颗粒和马氏体的抗磨损性能使涂层具有优异的耐磨性能,因此涂层磨损质量约是基体金属的1/10。埋弧堆焊双层涂层与单层涂层相比,马氏体含量减少,奥氏体和TiC含量增加,耐磨性更好。     

Plasma-sprayed YSZ coatings: Microstructural features and resistance to molten metals

Yttria Stabilized Zirconia (YSZ) coatings deposited by plasma spraying are widely used as thermal barriers onto metallic substrates, due to their attractive thermal properties and chemical inertia. In the present study, YSZ coatings were deposited onto steel substrates and their microstructure was investigated with X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The micro- and nano-scopic structural features were correlated to the performance of the coatings against corrosion by molten metals, which could simulate the industrial conditions of numerous applications. More precisely, in-scale porosity of the coatings and crystal parameters modifications were systematically examined and correlated to the corrosion behaviour in molten zinc, tin and aluminium baths for a 6 days testing period. The structural stability of the ceramic coating at high temperature, as well as the reactivity of the molten metal on the ceramic surface were preliminarily evaluated by thermogravimetric analysis and differential scanning calorimetry.     

Microstructural evaluation of tungsten carbide-cobalt coatings

Tungsten carbide-12 wt.% cobalt coatings were deposited using optimized high-energy plasma (HEP) and high-velocity oxygen fuel (HVOF) thermal spray techniques. The coatings were evaluated using transmission electron microscopy, differential thermal analysis, X-ray diffraction, and subjected to wear tests to relate the coating structure to wear performance. Coatings were evaluated in the assprayed condition, as well as after heat treatments in inert atmosphere. The results indicate that a substantial amount of amorphous matrix material is created during the thermal spray process. Carbon and tungsten, liberated through the dissociation of the WC, combine with cobalt present in the starting powder to form amorphous material on solidification. Differential thermal analysis revealed an exothermic reaction for both the HVOF and HEP coatings at approximately 853 and 860 °C, respectively, which did not occur for the powder. Post-coating heat treatment in an inert atmosphere resulted in the recrystallization of the amorphous material into Co₆W₆C and Co₂W₄C, which was dependent on the time and temperature of the heat treatment. Wear testing showed improvement in the wear performance for coatings that were subjected to the heat treatment. This was related to the recrystallization of the amorphous matrix into eta phase carbides. Editor’s Note: This paper was presented at the 4th National Thermal Spray Conference, Pittsburgh, 6-10 May, 1991. The proceedings of this conference will be published by ASM International. Dr. T.F. Bernecki is the Editor of these proceedings.