硫酸羟胺及亚硝酸钠对高碳钢表面锌系磷化涂层的组织和摩擦性能的影响

研究了在锌系磷化液中添加环保型促进剂-硫酸羟胺与常规促进剂-亚硝酸钠以便在高碳钢表面形成锌系磷化涂层．用X射线衍射分析了磷化涂层的相结构的变化,结果发现,形成的磷化膜主要由Zn₃Fe(PO₄)₂·4H₂O(H膜)和Zn₂Fe(PO₄)₂·4H₂O(P膜)组 成．运用扫描电镜分析了磷化涂层的显微组织与磷化时间之间的变化规律．四球摩擦实验结果表明,与亚硝酸钠相比,在锌系磷化液中添加硫酸羟胺能有效降低润滑后的磷化涂层的摩擦系数．     

Tribological properties of heat-treated electroless Ni-P coatings on AZ91 alloy

Influence of heat treatment regime on adhesion and wear resistance of Ni-P electroless coating on AZ91 magnesium alloy is investigated in this work. The pretreated substrate was plated using a bath containing nickel sulphate, sodium hypophosphite and sodium acetate as main constituents. The coated samples were heat treated at 400-450 °C for 1-8 h. Adhesion of coating was estimated from the scratch test with an initial load of 8.80 N. Wear resistance was studied using the pin-on-disc method. It was found that there is no significant dependence of the coating wear resistance on heat treatment regime, as the formation of Al-Ni intermetallic sub-layers that reduce coating adhesion is limited to regions where Al₁₇Mg₁₂ phase is present in the substrate. Moreover, the coating shows good sliding properties due to the formation of oxide glazes in the wear track.     

Electroless deposition of Ni-W-P coating on AZ91D magnesium alloy

Ternary Ni-W-P alloy coating was deposited directly on AZ91D magnesium alloy by using an alkaline-citrate-based baths. Nickel sulfate and sodium tungstate were used as metal ion sources, respectively, and sodium hypophosphite was used as a reducing agent. The pH value of the electroless bath was tailored for magnesium alloy. The coating was characterized for its structure, morphology, microhardness and the corrosion properties. SEM observation showed the presence of dense and coarse nodules in the ternary coating. EDS analysis showed that the content of tungsten in the Ni-W-P alloy was 4.5 wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution revealed that the ternary Ni-W-P coating exhibited good corrosion resistance properties in protecting the AZ91D magnesium alloy.     

Studies of the porosity in electroless nickel deposits on magnesium alloy

In the present paper, the porosity of the plating coating was evaluated by the combination of corrodkote and filter paper, the effects of the plating solution on the porosity were investigated, and the properties of the porous coatings were studied through scanning electron microscopy (SEM) and electrochemical potentiodynamic polarization. The results show that the eriothrome black T indicator used as an indicator of the coating porosity for coatings on magnesium alloy is more effective than magneson indicator and sodium alizarinesulfonate indicator. The porosity in electroless nickel deposits on magnesium alloy was well evaluated by the combination of corrodkote and filter paper. It is revealed that the pores exist on both grain surface and grain boundaries. An affecting trend of the plating bath parameters on the coating porosity was obtained.     

Bioactive calcium phosphate coating formed on micro-arc oxidized magnesium by chemical deposition

In order to improve the bioactivity of the micro-arc oxidized magnesium, a calcium phosphate coating was formed on the surface of micro-arc oxidized magnesium using a chemical method. The microstructures of the substrate and the calcium phosphate coating before and after the simulated body fluids (SBF) incubation were characterized by X-ray diffraction, Fourier-transformed infrared spectroscopy and scanning electron microscopy. The results showed that the calcified coating was composed of calcium deficient hydroxyapatite (HA) and dicalcium phosphate dihydrate (DCPD). After SBF incubation, some new apatite formation on the calcified coating surface from SBF could be found. The corrosion behaviours of the samples in SBF were also investigated by potentiodynamic polarization curves and immersion tests. The results showed that calcium phosphate coating increased the corrosion potential, and decreased the hydrogen gas release.     

The effect of deposition temperature on the surface coverage and morphology of iron-phosphate coatings on low carbon steel

The influence of deposition temperature and concentration of NaNO₂ in the phosphating bath on the surface morphology and coverage of iron-phosphate coatings on low carbon steel was investigated. The phosphate coatings were chemically deposited on steel from phosphate bath at different temperatures (30-70 °C) and with the addition of different amounts of accelerator, NaNO₂ (0.1, 0.5 and 1.0 g dm⁻³). The morphology of phosphate coatings was investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The composition of iron-phosphate coatings was determined using energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). Surface coverage was evaluated by the voltammetric anodic dissolution (VAD) technique.It was shown that the increase in temperature of the NaNO₂-free phosphating bath up to 70 °C caused an increase in surface coverage. The addition of NaNO₂ in the phosphating bath significantly increased the surface coverage of phosphate coatings deposited at temperatures lower than 50 °C. The phosphate crystals were of laminated and needle-like structures for deposits obtained at temperatures lower than 50 °C, while at higher temperatures needle-like structure was transformed to laminated structure. The increase in NaNO₂ concentration in the phosphating bath from 0.1 to 1.0 g dm⁻³ did not significantly increase the surface coverage, but decreased the crystals size, consequently favouring the phosphate nucleation and better packing of the crystals.     

The rate of electroless deposition of a four-component Ni-W-P-ZrO2 composite coating from a glycine bath

Four-component Ni-W-P-ZrO₂ composite coatings were electroless deposited. A bath containing aminoacetic acid as the agent complexing nickel ions, and sodium tungstate(VI) as the source of tungstate was used. It has been determined that as the bath's pH increases (from 5 to 6) so does the rate of coating deposition while the phosphorus content in the coating decreases. Both an increase in the aminoacetic acid concentration and an increase in the sodium tungstate cause a reduction in the rate of deposition of the Ni-W-P-ZrO₂ coating. Changes in the concentration of the two components in the bath result in a change in the composition of the coatings. When the concentration of the components is too high the bath loses its stability and a sediment precipitates itself. The ZrO₂ content in the coating depends most on the amount of this powder in the suspension.     

The effect of pH and role of Ni in zinc phosphating of 2024-Al alloy: Part I: Macroscopic studies with XPS and SEM

Coatings formed on 2024-T3 aluminum alloy were studied by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) after dipping in zinc phosphating (ZPO) baths at different acidities, for different lengths of time, and with or without Ni²⁺ additive. The overall objective was to learn more about the role of Ni²⁺ on the ZPO coating mechanism, particularly since this additive is believed to improve corrosion protection for the Al alloy. Secondary phosphates dominate the coatings when the Ni-containing solution is adjusted to starting pH values of either 3 or 5, while tertiary phosphate is predominant at pH 4. AlF₃ precipitates during the early stages of the coating process. Ni²⁺ has two main roles in the mechanism. First, the rate of increase in local solution pH is retarded by the slower kinetics of reactions involving Ni²⁺ compared to Zn²⁺, leading to thinner ZPO coatings when Ni²⁺ is present in the coating solution. Second, most Ni²⁺ deposition occurs during the later stages of the coating process, by nickel phosphate deposition and/or by formation of a Ni-rich oxide.     

Surface modification of magnesium aluminum hydroxide nanoparticles with poly(methyl methacrylate) via one-pot in situ polymerization

Hydrophobic magnesium aluminum hydroxide composite particles (PMMA-MAH) were obtained by means of grafting poly(methyl methacrylate) (PMMA) onto the surface of magnesium aluminum hydroxide(MAH) nanoparticles after a novel type of phosphate coupling agent (DN-27) modification. The introduction of functional double bonds was firstly conducted on the surface of nanoparticles by DN-27 modification, followed by one-pot in situ polymerization on the particles surface using methyl methacrylate (MMA) as monomer, azoisobutyronitrile (AIBN) as initiator and sodium dodecyl sulfate (SDS) as stabilizer to graft PMMA on the surface of DN-27-modified MAH particles. The obtained composite particles were characterized by field-emission scanning electron microscope (FESEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD). The results show that the organic macromolecule PMMA could be successfully grafted on the surface of DN-27-modified MAH nanoparticles and the thermal stability of the PMMA-MAH composite particles had been improved. Compared with unmodified blank MAH sample, the product obtained with this method possesses better hydrophobic properties such as a higher water contact angle of 108° and a well dispersion.     

Low-phosporous nickel-coated carbon microcoils: Controlling microstructure through an electroless plating process

Carbon microcoils (CMCs) have been coated with a nickel-phosphorus (Ni-P) film using an electroless plating process, with sodium hypophosphite as a reducing agent in an alkaline bath. CMC composites have potential applications as microwave absorption materials. The morphology, elemental composition and phases in the coating layer of the CMCs and Ni-coated CMCs were investigated by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD), respectively. The effects of process parameters such as pH, temperature and coating time of the plating bath on the phosphorus content and deposition rate of the electroless Ni-P coating were studied. The results revealed that a continuous, uniform and low-phosphorous nickel coating was deposited on the surface of the CMCs for 20 min at pH 9.0, plating bath temperature 70 °C. The as-deposited coatings with approximately 4.5 wt.% phosphorus were found to consist of a mix of nano- and microcrystalline phases. The mean particle size of Ni-P nanoparticles on the outer surface of the CMCs was around 11.9 nm. The deposition rate was found to moderately increase with increasing pH, whereas, the phosphorous content of the deposit exhibited a significant decrease. Moreover, the material of the coating underwent a phase transition between an amorphous and a crystalline structure. The thickness of the deposit and the deposition rate may be controlled through careful variation of the coating time and plating bath temperature.     

Simplistic surface active agents mediated morphological tweaking of CdS thin films for photoelectrochemical solar cell performance

This study reports on the formation of cadmium sulfide (CdS) nanostructures with controlled morphology synthesized via a simple chemical route in surface active agent environment. The effect of organic surface active agents (surfactants) as sodium dodecyl sulfate (SDS), polyethylene glycol (PEG) and cetyltrimethylammonium bromide (CTAB) on structural, morphological, optical and photoelectrochemical properties of CdS thin films have been studied. Our results reveal that the organic surfactants play key roles in tweaking the surface morphology. A compact spongy ball like morphology was observed for the CdS samples grown without organic surfactants. The cauliflower's with nanopetals from the CTAB, whereas crowded star fish like morphology is observed in PEG-mediated growth. Water hyacinth like morphology is tweaked using SDS. Considering the importance of these nanostructures, the growth mechanism has been discussed in details. Additionally, the samples are photoelectrochemically (PEC) active and having a compact surface with a nanoporous structure twig helps in improved photoelectrochemical performance compared to that of CdS deposits from surfactant free solution. This is a simplistic way to tune the morphology using surfactants, which can be applied to other energy conversion applications.     

Characterization of calcium containing plasma electrolytic oxidation coatings on AM50 magnesium alloy

An attempt was made to produce calcium containing plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy using an alkaline electrolyte. This study was performed in three alkaline electrolytes containing calcium hydroxide and sodium phosphate with three different mass ratios viz., 1:2.5, 1:5 and 1:7.5. All the three coatings produced were found to contain Ca and P in appreciable amounts. The concentration of P was found to be higher in the coatings obtained in the electrolytes with higher concentration of phosphate ions. Even though all the three coatings were found to be constituted with magnesium oxide and magnesium phosphate phases, X-ray diffraction analyses revealed that the phase composition was influenced by the phosphate ion concentration/conductivity of the electrolyte. Further, the PEO coating obtained in the 1:7.5 ratio electrolyte was found to contain di-calcium phosphate (monetite) and calcium peroxide phases, which were absent in the other two coatings. Potentiodynamic polarization studies performed in 0.1 M NaCl solution showed that the coatings obtained from the 1:5 ratio electrolyte possessed a superior corrosion resistance, which is attributed to the combined effect of thickness, compactness and phase/chemical composition of this coating.     

Studies on influence of zinc immersion and fluoride on nickel electroplating on magnesium alloy AZ91D

The effect of zinc immersion and the role of fluoride in nickel plating bath were mainly investigated in nickel electroplating on magnesium alloy AZ91D. The state of zinc immersion, the composition of zinc film and the role of fluoride in nickel plating bath were explored from the curves of open circuit potential (OCP) and potentiodynamic polarization, the images of scanning electron microscopy (SEM) and the patterns of energy dispersive X-ray (EDX). Results show that the optimum zinc film mixing small amount of Mg(OH)₂ and MgF₂ is obtained by zinc immersion for 30-90 s. The corrosion potential of magnesium alloy substrate attached zinc film will be increased in nickel plating bath and the quantity of MgF₂ sandwiched between magnesium alloy substrate and nickel coating will be reduced, which contributed to produce nickel coating with good performance. Fluoride in nickel plating bath serves as an activator of nickel anodic dissolution and corrosion inhibitor of magnesium alloy substrate. 1.0-1.5 mol dm⁻³ of F⁻ is the optimum concentration range for dissolving nickel anode and protecting magnesium alloy substrate from over-corrosion in nickel plating bath. The nickel coating with good adhesion and high corrosion resistance on magnesium alloy AZ91D is obtained by the developed process of nickel electroplating. This nickel layer can be used as the rendering coating for further plating on magnesium alloys.     

E-glass fibers coated with nickel phosphorous by electroless deposition technique

The nickel phosphorous catalyst coating was studied on the E-glass fiber by electroless deposition using sodium hypophosphite as a reducing agent in alkaline medium. The effects of deposition time, deposition temperature, pH of the solution, and amount of stabilizer used in the solution on the coating efficiency were investigated by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential thermal analysis (DTA). The XRD indicates the presence of amorphous and crystalline phases of Ni and nickel–phosphorous (NiP). From TGA, it is evident that the NiP coating increases the thermal stability and magnetic properties of the glass fiber. The bath temperature of 80 °C, pH of 9 to 9.5, and stabilizer concentration of 25 g/l are optimum to get a good and uniform coating of NiP on glass fiber. Carbon nanotubes were successfully coated on NiP coated glass fiber at a temperature of 700 °C.     

Raman identification of corrosion products on automotive galvanized steel sheets

Iron oxides (haematite, maghemite, magnetite), (oxy)hydroxides (lepidocrocite), carbonates, as well as zinc carbonate and oxide, have been identified on corroded galvanized steel samples after corrosion accelerating tests in the laboratory and compared with those observed on samples taken from vehicles that have been in circulation for five years in severe weather conditions. Spectra recorded on the corroded parts are compared with synthesized compounds. (Hydroxy)carbonates are clearly evidenced on galvanized and phosphated steel sheets. Corrosion layers beneath the paint could be detected. White regions always correspond to a ZnO‐rich phase but maghemite (γ‐Fe₂O₃) and sometimes akaganite (β‐FeOOHCl) are observed at the centre (maroon) of very corroded spots. Maghemite is observed in strongly corroded regions. Goethite (α‐) and lepidocrocite (γ‐FeOOH) (and akaganite) are observed at the surface of less corroded regions of phosphate‐free galvanized steel and are absent for phosphate‐coated steel. Green rust is observed only on galvanized samples corroded in the laboratory. Copyright © 2008 John Wiley & Sons, Ltd.     

The effect of pH and role of Ni in zinc phosphating of 2024-Al alloy: Part II: Microscopic studies with SEM and SAM

Coatings formed on 2024-T3 aluminum alloy were studied by scanning electron microscopy (SEM) and scanning Auger microscopy (SAM) after dipping in zinc phosphating (ZPO) baths at different acidities, with or without the Ni²⁺ additive. The objective was to learn more about the ZPO coating mechanism on the different microstructural regions of 2024-T3. When the initial coating solution pH is 4 (optimal acidity), a slower etching rate at the Al-Cu-Fe-Mn intermetallic particle causes significant precipitation of ZnO, which differs from the coating on other regions of the surface where phosphate predominates. The larger crystals (∼μm dimension) on the matrix and the Al-Cu-Mg particle contain more phosphate compared to other areas on the surface. When Ni²⁺ is added to the coating solution, the Al-Cu-Mg particle is more thickly coated compared to when the Ni²⁺ is not present. The slower rate of precipitation when Ni²⁺ is present in the coating solution increases the exposure of the alloy substrate to the acidic environment, so allowing more dissolution of Mg and Al from the Al-Cu-Mg particle. This results in the particle becoming more cathodic in nature, and therefore more coating deposits at this location. Evidence from SAM supports the presence of NiAl₂O₄, hypothesized in Part I, forming at coating pores later in the process.     

Microstructural effects on the formation and degradation of zinc phosphate coatings on 2024-Al alloy

The formation of zinc phosphate (ZPO) coatings on 2024-T3 aluminum alloy was studied using scanning electron microscopy (SEM), scanning Auger microscopy (SAM) and X-ray photoelectron spectroscopy (XPS), with an emphasis on microstructural effects involving second-phase particles and the alloy matrix. Surface polishing results in an Al-Cu-Mg particle surface that contains metallic Cu as well as an overlayer of aluminum and magnesium oxide, while larger amounts of aluminum oxide are present on the Al-Cu-Fe-Mn particle and matrix. When dipped in an acidic ZPO coating solution, the oxide covering the Al-Cu-Mg particle is etched most easily, and metallic Cu near the surface makes that region most cathodic, allowing more coating deposition compared with the other regions. The oxides on the Al-Cu-Fe-Mn and matrix regions are similar, thereby confirming that the observed differences in ZPO coating characteristics at these two regions arise from their underlying electrochemical characteristics. Immersion of a coated 2024-Al sample in corrosive NaCl solution for extended periods indicates that the ZPO provides better protection to the second-phase particles than to the matrix.     

Influence of heat treatment on tribological properties of electroless Ni-P and Ni-P-Al2O3 coatings on Al-Si casting alloy

Evolution of tribological properties of electroless Ni-P and Ni-P-Al₂O₃ coating on an Al-10Si-0.3Mg casting alloy during heat treatment is investigated in this work. The pre-treated substrate was plated using a bath containing nickel hypophosphite, nickel lactate and lactic acid. For preparation of fiber-reinforced coating Al₂O₃ Saffil fibers pre-treated in demineralised water were used. The coated samples were heat treated at 400-550 °C/1-8 h. Tribological properties were studied using the pin-on-disc method. It is found that the best coating performance is obtained using optimal heat treatment regime (400 °C/1 h). Annealing at higher temperatures (450 °C and above) leads to the formation of intermetallic compounds that reduce the coating wear resistance. The reason is that the intermetallic phases adversely affect the coating adherence to the substrate. The analysis of wear tracks proves that abrasion is major wear mechanism, however due to the formed intermetallic sub-layers, partial coating delamination may occur during the pin-on-disc test on the samples annealed at 450 °C and above. It was found that fiber reinforcement reduces this scaling and increases wear resistance of coatings as compared to the non-reinforced Ni-P coatings.     

Ultrasonic irradiation and its application for improving the corrosion resistance of phosphate coatings on aluminum alloys

In this paper, ultrasonic irradiation was utilized for improving the corrosion resistance of phosphate coatings on aluminum alloys. The chemical composition and morphology of the coatings were analyzed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The effect of ultrasonic irradiation on the corrosion resistance of phosphate coatings was investigated by polarization curves and electrochemical impedance spectroscopy (EIS). Various effects of the addition of Nd₂O₃ in phosphating bath on the performance of the coatings were also investigated. Results show that the composition of phosphate coating were Zn₃(PO₄)₂ · 4H₂O(hopeite) and Zn crystals. The phosphate coatings became denser with fewer microscopic holes by utilizing ultrasonic irradiation treatment. The addition of Nd₂O₃ reduced the crystallinity of the coatings, with the additional result that the crystallites were increasingly nubby and spherical. The corrosion resistance of the coatings was also significantly improved by ultrasonic irradiation treatment; both the anodic and cathodic processes of corrosion taking place on the aluminum alloy substrate were suppressed consequently. In addition, the electrochemical impedance of the coatings was also increased by utilizing ultrasonic irradiation treatment compared with traditional treatment.     

Mineralization of surfactant functionalized multi-walled carbon nanotubes (MWNTs) to prepare hydroxyapatite/MWNTs nanohybrid

Multi-walled carbon nanotubes (MWNTs) were well dispersed in water and functionalized by adding surface active agent (i.e., sodium dodecyl sulfate, SDS). Subsequently, biomimetic mineralization was carried out on the SDS functionalized MWNTs by using an alternate soaking process (ASP) in the Ca/P solutions. As-prepared samples were characterized by transmission electron microscope, infrared spectrum and X-ray diffraction. The results show that nano-HA crystals were formed on the SDS functionalized MWNTs and the mineralized MWNTs remained a dispersing state. As-prepared HA-MWNTs nanohybrid combining the osteconductive property of HA and the excellent mechanical property of MWNTs will provide a promising material for bone tissue engineering.