Impedance spectroscopy studies of electroless Ni–P matrix,Ni–W–P,Ni–P–ZrO2, and Ni–W–P–ZrO2 coatings exposed to 3.5% NaCl solution

Ni–P matrix, ternary Ni–W–P and Ni–P–ZrO₂ coatings, and quaternary Ni–W–P–ZrO₂ coatings were deposited using electroless method from a glycine bath. Their corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS) for various immersion times in a 3.5% NaCl solution. From among the investigated coatings, the ternary Ni–W–P coatings show the highest resistance to corrosion in the first hour of exposure to the 3.5% NaCl medium. An addition of ZrO₂ adversely affects the performance of both the Ni–P coatings and the Ni–W–P coatings. For all the coatings, including the ones containing tungsten, a marked decrease in pore resistance (R_por) over time is observed. This means that their corrosion resistance and capacity to protect the substrate decline. On the other hand, after 24 h immersion in the 3.5% NaCl solution the Ni–W–P coating shows the highest low‐frequency impedance modulus (|Z|_{f = 0.01 Hz}). As regards corrosion resistance, the Ni–P coatings and the Ni–W–P coatings perform best.     

热处理对不锈钢表面化学镀Ni-Cr-P合金镀层结构及性能的影响

采用化学镀工艺在不锈钢表面获得了Ni-Cr-P合金镀层。研究了Ni-Cr-P非晶态合金膜随热处理温度升高,其结构以及显微硬度和耐蚀性的变化规律,并对变化的原因进行了分析。结果表明,镀态Ni-Cr-P为非晶态镀层,200℃热处理开始晶化,到400℃时Ni3P晶化比较完全,800℃时Ni3P完全分解,生成含Ni、Cr、Fe的合金膜的Cr2Ni3和FeNi2P相。其显微硬度随热处理温度升高而升高,500～600℃之间显微硬度略有下降,600～700℃又随着热处理温度的升高而略有升高,700℃后显微硬度略有下降;合金膜的耐腐性在热处理温度200～400℃间变化较小,500℃热处理后其耐腐蚀性下降厉害,600～700℃随着热处理温度的升高其耐腐蚀性又略有升高,800℃后由于Ni3P的分解其耐腐蚀性又急剧下降。     

Corrosion of alloys and their diffusion aluminide coatings by KCl:K2SO4 deposits at 650 °C in air

P91 ferritic‐martensitic steel, 17Cr–13Ni and alloy 800 austenitic stainless steels and Inconel 617 alloy have been aluminised to form Fe₂Al₅, (Fe,Ni)Al and Ni₂Al₃ aluminide coatings. These alloys and their corresponding coatings were subjected to corrosion in air by 50:50 mol/mol K₂SO₄/KCl deposits at 650 °C for 300 h. With the exception of the Inconel 617 alloy, significant metal losses (>180 µm) were recorded. These losses were planar for P91 alloy but involved internal corrosion for the two austenitic steels. The (Fe,Ni)Al and NiAl coatings on the austenitic steels and the Inconel 617 alloy were significantly corroded via intergranular and internal chloridation–sulphidation–oxidation. In contrast, the Fe₂Al₅ coating on the P91 alloy coating was virtually unattacked. For the alloys, the relative extents of corrosion damage can be explained in terms of the stability and volatility of metal chlorides formed. For the coatings, STEM/EDS analyses enable clear linkages to be made between the presence and number of Cr‐rich particles on coating grain boundaries and the corrosion damage observed for the coatings.     

Effects of rare earth cerium addition on the synthesis and corrosion resistance of electroless Ni–PTFE–P coating

Electroless Ni–PTFE–P coatings have been successfully deposited on the surface of mild steel shaft from plating baths containing various concentrations of rare earth metal cerium (RE Ce). Surface morphology, Ce fraction, and thickness of the coatings were characterized by scanning electron microscope, inductively coupled plasma optical emission spectrometry, and reflection optical microscope, respectively. Salt spray test was used to determine the corrosion resistance of the coating. Results revealed that structure, compactness, and deposition rate of the Ni–PTFE–P coatings were increased significantly by addition of a small amount of RE Ce (10–20 ppm) to the plating bath. Electroless Ni–PTFE–P coating deposited from plating baths with 20 ppm Ce shows the highest corrosion resistance, owing to its high compactness and thickness. Deposition rate and corrosion resistance of the Ni–PTFE–P coating were deteriorated greatly as concentration of RE Ce in the plating baths exceeds 100 ppm.     

Corrosion resistance of Zn–Ni/Ni and Ni/Zn–Ni compositionally modulated multilayer coating

Zn–Ni/Ni and Ni/Zn–Ni compositionally modulated multilayer (CMM) coatings were prepared by dual‐bath technique. The effects of layers number and sublayers order were studied. Specially, the effect of different sublayers thickness ratios with the same multilayer period (λ) on the corrosion resistance of the CMM coatings was investigated in detail. Results showed that the corrosion resistance of Ni/Zn–Ni (Zn–Ni alloy sublayer as the top layer) CMM coating was better than that of Zn–Ni/Ni (Ni sublayer as the top layer) CMM coating. The 6‐layer CMM coating with the layer thickness ratio of Ni/Zn–Ni = 0.8:1.2 (λ = 2 µm) has the best corrosion resistance.     

Nanocrystalline electroless nickel poly-alloy deposition: incorporation of W and Mo

Autocatalytic quaternary Ni–W–Mo–P films were prepared using alkaline citrate based baths and compared with binary Ni–P and ternary Ni–W–P, Ni–Mo–P coatings. Energy dispersive X-ray analysis showed that the binary Ni–P deposit contained 12·2 wt-%P. Codeposition of tungsten in Ni–P matrix resulted in ternary Ni–W–P with 4·1 wt-%P and 5·2 wt-%W. Incorporation of molybdenum led to a ternary Ni–Mo–P deposit containing 4·1 wt-%Mo and 11·2 wt-%P. Presence of both sodium tungstate and sodium molybdate in the basic bath resulted in a quaternary coating with 3·6 wt-%W, 6·7 wt-%Mo and 2·5 wt-%P. X-ray diffraction patterns of all the deposits revealed a single peak for Ni (1 1 1). The quaternary alloy exhibited a sharper peak showing the more crystalline nature of the deposit. Field emission scanning electron microscopy studies of the deposits showed the presence of smooth nodules for ternary deposits, but coarse and well defined nodules for quaternary deposits. Phase transformation behaviour of the ternary Ni–W–P deposit revealed a single exothermic peak at 440°C. However, ternary Ni–Mo–P deposit exhibited a split type high temperature peak at 397 and 461°C and the quaternary Ni–W–Mo–P deposit showed a single high temperature peak at 485°C. Microhardness measurements showed that the quaternary Ni–W–Mo–P deposit exhibited increased hardness of 920 HV(50 gf) when heat treated for 1 h at 400°C.     

TC4钛合金表面化学镀Ni-P合金耐磨层研究

利用化学镀方法在TC4钛合金表面成功制备结合力良好的Ni-P合金耐磨层,研究了提高镀层结合力的方法,结合SEM、XRD、EDS等现代物理分析方法分析了不同温度热处理后镀层的组织结构,从而建立不同热处理温度、镀层结构与镀层硬度和耐磨性能的关系。结果表明:二次浸锌活化方法和热处理能显著提高镀层与基体的结合强度,经600℃热处理后镀层结合力达到35N。基材的硬度HV为3780MPa,磨损量为9.6mg,镀态镀层的硬度HV为5760MPa、磨损量为7.7mg。随着热处理温度升高Ni3P相增多,该相的弥散分布使镀层硬度增加,最高硬度HV达到9790MPa,但400℃后硬度降低,这是由于Ni3P相随着热处理温度的继续升高而发生偏聚,使弥散强化程度下降;镀层的磨损量随着热处理温度的升高而减小,说明耐磨性能随着热处理温度的升高而增强,600℃热处理后,虽然镀层晶粒长大、粗化及镀层硬度降低,但此时镀层晶格的完整性最佳,镀层塑性和韧性提高,所以耐磨性能最好。     

Investigation of the surface properties of heat treated electroless Ni–P coating

Electroless nickel phosphorus (Ni–P) coatings were synthesised from an acid chloride electrolyte. The synthesised coatings were heat treated at different temperatures, and the surfaces of the heat treated coating were characterised using scanning electron microscopy and X-ray diffraction. Adhesion, wettability, hardness and corrosion behaviour of the coatings were measured. The surface morphology showed the formation of a nano crystalline nickel matrix under heat treated condition. X-ray diffraction analysis of the heat treated samples revealed the recrystallisation of nickel and formation of Ni₃P phase in the coatings. The wettabilty study showed that the as-deposited Ni–P coating is hydrophobic and wettability increases to a maximum of 70.8° contact angle for heat treated temperature of 400°C due to nano crystalline formation. The Rockwell C adhesion test revealed the presence of micro cracks with increase in heat treatment temperature, however the failure is within the acceptability limit. The micro hardness of the Ni–P coating increased with increase in heat treatment temperature. Corrosion potential of the Ni–P coating shifted to a positive potential under heat treated conditions owing to oxidation and precipitation of Ni₃P phase. Decreased corrosion rate and corrosion current density (7.37–0.21?µA?cm^?2) is attributed to heat treatment at 400°C.     

Erosion–corrosion characteristic of nano‐particulates reinforced Ni–Cr–Mo–Cu surface alloying layer in acidic flow and acidic slurry flow

In order to improve the corrosion and erosion–corrosion resistance of 316L stainless steel in engineering application, two kinds of composite alloying layers were prepared by a duplex treatment, consisting of Ni/nano‐SiC and Ni/nano‐SiO₂ predeposited by brush plating, respectively, and a subsequent surface alloying with Ni–Cr–Mo–Cu by double glow process. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were performed on the two kinds of composite alloying layer using 10 wt% HCl solution to assess the corrosion behavior. Erosion–corrosion tests were carried out by erosion–corrosion test rig in acidic flow and acidic slurry flow for test time of 20 h at four different rotational speeds. Results of electrochemical tests indicated that the corrosion resistance of composite alloying layer with brush plating Ni/nano‐SiO₂ particles interlayer approximated to that of single Ni‐based alloying layer, whereas the corrosion resistance of the composite alloying layer with brush plating Ni/nano‐SiC particles interlayer was apparently inferior to that of Ni‐based alloying layer in 10 wt% HCl solution at static state. Under the conditions of acidic flow and acidic slurry flow, the mass losses of tested samples increased with increase in the time of erosion–corrosion tests and the rotational speeds of samples. The mass losses of composite alloying layer with brush plating Ni/nano‐SiO₂ particles interlayer were lower than that of single Ni‐based alloying layer at all rotational speeds, except at 1.88 m/s in acidic flow. The mass losses of composite alloying layer with brush plating Ni/nano‐SiC particles interlayer were higher than that of single Ni‐based alloying layer at all rotational speeds, but were obviously lower than that of AISI 316L stainless steel. The influences of second phase on the corrosion and erosion–corrosion of the two kinds of composite alloying layer were discussed in this paper.     

Corrosion characteristics of electroless Ni–P coating in sulfur‐bearing solution

The corrosion behaviors of electroless Ni–P coatings deposited on carbon steel in sulfur‐bearing solutions were investigated by weight gain test and scanning electron microscopy. The results indicate that the corrosion rate of electroless Ni–P coating was directly related to the sulfur content, immersion time, and test temperature. The corrosion rate increased with the prolonged immersion time. Increasing the temperature can markedly increase the corrosion rate of electroless Ni–P coating. The electroless Ni–P coating had a better corrosion resistance than 316L stainless steel against Cl^? corrosion in sulfur‐bearing solution.     

The effect of TiO2 nanoparticle codeposition on microstructure and corrosion resistance of electroless Ni?P coating

Ni? P? TiO₂ nanocomposite coatings with various contents of TiO₂ nanoparticles were synthesized by adding TiO₂ nanoparticles to Ni? P electroless plating solution. The effects of pH and anionic surfactant sodium dodecyl sulfate (SDS) on the chemical composition of Ni, P, and TiO₂ in the coatings were investigated. Scanning electron microscope (SEM), energy dispersive spectrometer (EDX), and X‐ray diffractometer (XRD) were used to characterize the morphology, composition, and crystal structure of deposited coatings, respectively. The hardness of nanocomposite coatings was improved greatly compared to Ni? P coating especially after heat treatment. After heat treatment at 400 °C for 1 h, an increase in microhardness was observed for heat‐treated Ni? P coatings. The hardness was increased from 805 to 1050 Hv for Ni? P? TiO₂ coating deposited at 9 g/LTiO₂ concentration in the bath. The corrosion resistance of Ni? P? TiO₂ coating was significantly increased compared to Ni? P coatings by incorporation of TiO₂ nanoparticle.     

Investigations on role of HVOF sprayed Co and Ni based coatings to combat hot corrosion

Abstract

This paper aims to investigate the hot corrosion resistance of high velocity oxy-fuel (HVOF) sprayed cobalt based (Stellite-6) and nickel based (Ni–20Cr) coatings deposited on the superalloy Superni-718 (Ni–19Cr–18˙5Fe–5˙13Ta–3˙05Mo–0˙9Ti–0˙5AI–0˙18Mn–0˙18Si–0˙15Cu–0˙04C) in the Na₂SO₄–60%V₂O₅ salt environment at 900°C under cyclic conditions. The X-ray diffractometry, scanning electron microscopy/energy dispersive analysis and electron probe microanalyser techniques were used to study the corrosion products with respect to their morphology, phase composition and element concentration. The thermogravimetric technique was used to establish the kinetics of corrosion. The bare alloy underwent severe hot corrosion attack. The Ni–20Cr coating shows excellent hot corrosion resistance with negligible spallation, whereas Stellite-6 coating reveals less hot corrosion resistance and more spallation. The hot corrosion resistance of Ni–20Cr coating has been attributed to the formation of oxides of chromium, nickel and spinel of nickel chromium. The oxides of silicon, chromium, cobalt and spinels of cobalt–chromium and nickel–chromium have contributed for hot corrosion resistance of Stellite-6 coatings.     

Influence of regulated modification of nitride layer by oxygen on the electrochemical behavior of Ti–6Al–4V alloy in the Ringer's solution

The corrosion behavior of oxynitrided Ti–6Al–4V alloy was investigated in the Ringer's solution (simulated body fluid) at a temperature of 37°C. The oxynitriding of the alloy was carried out by leaking controlled oxygen‐containing medium into the reaction chamber at the final stage of the nitride formation. It was determined that oxynitriding improved corrosion resistance of Ti–6Al–4V alloy as it provided lower corrosion current density by 1.3–1.5 times and higher corrosion potential. In this paper, we analyzed that the resistance of the double layer had increased with the increase of the oxygen content in titanium oxynitride. Its value was higher compared with untreated alloy, indicating higher corrosion resistance of the oxynitrided one.     

PROPERTIES OF ELECTRODEPOSITED AMORPHOUS Ni-W-P-SiC COMPOSITE COATINGS

ＰＲＯＰＥＲＴＩＥＳＯＦＥＬＥＣＴＲＯＤＥＰＯＳＩＴＥＤＡＭＯＲＰＨＯＵＳＮｉ－Ｗ－Ｐ－ＳｉＣＣＯＭＰＯＳＩＴＥＣＯＡＴＩＮＧＳＧＵＯＺｈｏｎｇｃｈｅｎｇ;ＬＩＵＨｏｎｇｋａｎｇ;ＷＡＮＧＺｈｉｙｉｎ;ＷＡＮＧＭｉｎ（ＤｅｐａｒｔｍｅｎｔｏｆＭｅｔａ...     

Synthesis and passivation behavior of electroless Ni–P‐CNT composite coating

Carbon nanotubes (CNTs) have high chemical stability, unique hollow nanotube structure, and are believed to be ideal materials for fabricating composites. In this study, Ni–P and Ni–P‐CNT composite coatings were fabricated by electroless plating. Scanning electron microscopy was used to characterize the coatings. The corrosion behavior of Ni–P and Ni–P‐CNT coated samples were evaluated by polarization curves and electrochemical impedance spectroscopy in 3.5 wt% NaCl and 0.1 M H₂SO₄ aqueous solutions at room temperature. The results indicated that incorporation of CNTs in the coating significantly increased corrosion resistance. The role of CNTs in improvement of corrosion resistance of the coating was also discussed.     

Corrosion behavior of nickel alloys in wet hydrofluoric acid

Wet hydrofluoric acid at concentrations below approximately 60% is highly corrosive to glass, reactive metals, carbon steel and stainless steels. Nickel alloys offer moderate corrosion resistance over a wide range of acid concentration and temperature. The corrosion behavior of eleven commercial alloys was quantified through laboratory testing. Variables that were studied included testing time, acid concentration, temperature, vapor and liquid phases and the presence of residual stresses. Results show that the corrosion rate of a Ni‐Cu and a Ni‐Cr‐Mo‐Cu alloy increased with the acid concentration and the temperature. However, both for increasing acid concentration and temperature, the corrosion rate of the Ni‐Cu alloy increased faster than the corrosion rate of the Ni‐Cr‐Mo‐Cu alloy, especially in the vapor phase. Even in unstressed coupons, nickel alloys showed internal penetration in presence of wet HF; the mode of this internal penetration varied from alloy to alloy. Considering all the studied variables that influence corrosion, the highest ranked material for wet HF service was a Ni‐Cr‐Mo‐Cu alloy.     

Effects of the Zr and Mo contents on the electrochemical corrosion behavior of Ti–22Nb alloy

Ti–22Nb–xZr and Ti–22Nb–xMo (x = 0, 2, 4, 6, in atom percent) were prepared by an arc melting method. The alloys were solution‐treated at 1073 K for 1.8 ks followed by quenching them into ice water, and the electrochemical corrosion behavior in a 0.9% NaCl solution at 25 °C and neutral pH range of the solution‐treated alloys was evaluated by using electrochemical impedance spectroscopy, polarization curves and an equivalent circuit analysis. It was found that the microstructure of the solution‐treated Ti–22Nb alloy mainly contains β phase with small amount of α″ phase, and the addition of Zr or Mo to a Ti–22Nb alloy is efficient to stabilize the β phase. The resulting impedance parameters and passive current densities indicated that the corrosion resistance of the Ti–22Nb alloy was promoted significantly with the addition of Zr and Mo.     

Corrosion characteristics of the wrought Ni‐Cr‐Mo alloys

This paper concerns the wrought, nickel‐chromium‐molybdenum (Ni‐Cr‐Mo) alloys, a family of materials with a long history of use in the chemical process industries. Their attributes include resistance to the halogen acids and resistance to pitting, crevice attack, and stress corrosion cracking in hot, halide salt solutions. The purpose of this paper is to characterize the performance of the Ni‐Cr‐Mo alloys in several key chemicals, using iso‐corrosion diagrams. These indicate the expected corrosion rates over wide ranges of concentration and temperature. Furthermore, the differences between individual Ni‐Cr‐Mo alloys, and their behavior relative to the stainless steels are defined. The data indicate benefits of both a high chromium content and a copper addition, as used in Hastelloy® C‐2000® alloy.     

Electrodeposition of high corrosion resistant Ni–Sn–P alloy coatings from an ionic liquid based on choline chloride

With the objective of obtaining corrosion resistant coatings, ternary Ni–Sn–P alloy coatings were electrodeposited from a deep eutectic solvent and their composition, morphology and corrosion resistance were investigated as a function of electrodeposition potential. A comparison was made with a Ni–P binary alloy coating electrodeposited under similar conditions. Cyclic voltammetry, energy dispersive analysis of X-rays, potentiodynamic polarisation, open circuit potential-time and electrochemical impedance spectroscopy techniques were used for studying the electrodeposition behaviour, chemical composition and coatings corrosion performances, respectively. The chemical compositions of the ternary Ni–Sn–P alloy films contained about 4.4–10.3?wt-% Sn, 7.2–8.1?wt-% P and Ni (balance). X-ray diffraction patterns of the ternary Ni–Sn–P deposits revealed a single and broad peak, becoming wide with an increase in Sn content, showing that the structures of all the deposits were nanocrystalline or amorphous. Corrosion tests showed that ternary Ni–Sn–P alloy coatings exhibited considerably better barrier corrosion resistance than binary Ni–P coatings, and their corrosion resistance improved with an increase in Sn content.     

化学沉积 Ni-Mo-P 和 Ni-P 镀层退火晶化组织及耐蚀性

目的研究化学沉积Ni-4.11%Mo-6.50%P和Ni-9.19%P合金镀层退火晶化转变特征,通过定量表征镀层的晶化程度、晶粒尺寸及结晶相的质量分数,建立显微组织与耐蚀性的关联。方法采用XRD衍射技术和Jade软件分析,定量表征镀层的晶化组织特征,由SEM/EDS测试确定镀层的成分及表面形貌,通过浸泡腐蚀实验及金相显微观察,对比两种镀层的耐蚀性。结果 Ni-Mo-P镀层在低于400℃退火时,只有Ni相结晶;在≥400℃退火时,发生Ni3P晶化反应,同时伴有Ni-Mo固溶体的形成,600℃时的晶化程度为88.13%。相比之下,Ni-P镀层中Ni3P相开始析出的温度降至300℃,600℃时的晶化程度达到91%。在相同温度进行热处理时,Ni-Mo-P镀层晶粒尺寸小于Ni-P镀层。在发生Ni3P晶化反应的温度下,两种镀层中Ni3P的晶粒尺寸总是大于Ni相。在0.5 mol/L的H2SO4中,对于Ni-Mo-P镀层,除300℃外,其他温度下的热处理均能显著改善其耐蚀性;而对于Ni-P镀层,镀态下具有最好的耐蚀性能。在10%的HCl溶液中,退火温度为600℃时,Ni-Mo-P镀层的耐点蚀性能更好;而Ni-P合金则相反,镀态及低温200℃退火后的耐点蚀性能最好。结论 Mo的共沉积提高了Ni-Mo-P镀层Ni3P的析出温度,降低了镀层的晶化程度及晶粒尺寸;与Ni-P镀层相比,高温退火的Ni-Mo-P镀层表现出了优异的耐点蚀性能,但耐硫酸均匀腐蚀的性能较差。