Deposition of zinc–zinc phosphate composite coatings on steel by cathodic electrochemical treatment

The present work aims at the development of an energy-efficient and eco-friendly approach for the deposition of zinc phosphate coatings on steel. The study describes the possibility of preparing zinc–zinc phosphate composite coatings by cathodic electrochemical treatment using dilute phosphoric acid as an electrolyte and zinc as an anode. The methodology enables the preparation of coatings with different proportions of zinc and zinc phosphate by suitably varying the applied current density, pH, and treatment time. Adhesion of the coating on mild steel and adhesion of paint film on the phosphate coating were found to be good. The surface morphology of the coatings exhibited platelet-type features and small white crystals (agglomerated at some places) which represented zinc and zinc phosphate, respectively. An increase in current density (from 20 to 50 mA/cm²) increased the size of the zinc crystals, and coatings prepared at 40 and 50 mA/cm² resembled that of electrodeposited zinc. Since the proportions of zinc and zinc phosphate could be varied with applied current density, pH, and treatment time, it would be possible to use this methodology to prepare coatings that would offer different degrees of corrosion protection.     

Electrophoretic deposition of bioactive wollastonite and porcelain–wollastonite coatings on 316L stainless steel

Wollastonite and porcelain–wollastonite coatings on stainless steel were obtained by electrophoretic deposition using acetone as dispersive medium. A direct electric current of 800 V for 3 min was used for obtaining the single wollastonite coating. A well-sintered layer was observed after heat treatment at 1050 °C for 1 h in air. The two-layer coating was obtained by depositing dental porcelain at 400 V for 30 s followed by the deposition of wollastonite at 400 V for 3 min. After forming the two layers, this complex coating was heat treated at 800 °C for 5 min. Under these conditions, strong bonds of both the interface wollastonite–porcelain and that of porcelain–metallic substrate were observed. The in vitro bioactivity assessment of the coatings was performed by immersing the deposited substrates in simulated body fluid (SBF) for 21 days. All the materials showed to be highly bioactive through the formation of a homogeneous apatite layer.     

Ni–Zn–P alloy deposition from sulfate bath: inhibitory effect of zinc

Electroless Ni–Zn–P alloy deposition from a sulphate bath, containing sodium hypophosphite as reducer, was investigated. To increase the plating rate, the deposition parameters were optimized. The effect of process parameters (T, pH and [Zn²⁺]) on the plating rate and deposit composition was examined and it was found that the presence of zinc in the bath has an inhibitory effect on the alloy deposition. As a consequence, the percentage of zinc in the electroless Ni–Zn–P alloys never reaches high values. Using cyclic voltammetry the electrodeposition mechanism of Ni–Zn–P alloys was investigated. It was observed that the zinc deposition inhibits the nickel discharge and, as a consequence, its catalytic activity on hypophosphite oxidation. It was also found that increase in temperature or pH leads to the deposition of nickel rich alloys.     

Structure and properties of electrodeposited Ni–Co–YZA composite coatings

The aim is to develop an economical composite coating with high thermal stability. Ni–Co alloys are found to possess better thermal, physical and mechanical properties compared to Ni. Also, oxide particles as distributed phase can impart better thermal stability. Hence, particulates of composite Yttria stabilised zirconia, a commonly used high temperature material and alumina (YZA) were reinforced in various Ni–Co alloy matrices through electrodeposition. The influence of YZA on the microhardness, tribology and corrosion behaviour of Ni–Co alloys with Co contents of 0 wt.%, 17 wt.%, 38 wt.% and 85 wt.% was evaluated. Optical and Scanning Electron Microscopy (SEM) confirmed the presence of YZA particles and Energy Dispersive X-ray Analysis (EDX) revealed the composition. Tribology testing showed that composite containing 38 wt.% Co displayed better wear resistance. It was found from the immersion corrosion studies that Ni–17Co–YZA coating displayed improved corrosion resistance. Thermal stability studies showed that Ni–85Co–YZA coating retained its microhardness at temperatures of 600 °C. Thus, these coatings can be tailored for various applications by varying the cobalt content.     

Effect of titania particles preparation on the properties of Ni–TiO2 electrodeposited composite coatings

In this paper, the effect of titania particles preparation on the properties of Ni–TiO₂ electrocomposite coatings has been addressed. Titania particles were prepared by precipitation method using titanium tetrachloride as the precursor. The titanyl hydroxide precipitate was subjected to two different calcinations temperatures (400 and 900 °C) to obtain anatase and rutile titania particles. These particles along with commercial anatase titania particles were separately dispersed in nickel sulfamate bath and electrodeposited under identical electroplating conditions to obtain composite coatings. The electrodeposited coatings were evaluated for their microhardness, wettability, corrosion resistance, and tribological behavior. The variation of microhardness with current density exhibited a similar trend for all the three composite coatings. The composite coating containing anatase titania particles exhibited higher microhardness and improved wear resistance. However, the corrosion resistance of the composite coating containing commercial titania powder was superior to that of plain nickel, Ni–TiO₂ composite coatings containing anatase and rutile titania particles. The poor corrosion resistance of these composite coatings was attributed to the higher surface roughness of the coatings. This problem was alleviated by incorporating ball-milled titania powders. The composite coatings with higher surface roughness were modified with a low surface energy material like fluoroalkyl silane to impart hydrophobic and superhydrophobic properties to the coatings. Among these coatings, Ni–TiO₂–9C coating exhibited the highest water contact angle of 157°.     

Influence of a Zwitterionic Surfactant on the Surface Properties of Electroless Ni–P Coating on Mild Steel

3-(N,N-Dimethyl myristyl-ammonio) propane sulfonate zwitterionic surfactant (C14-SB) which possessed both positive and negative charges was evaluated in the electroless Ni–P coating process. It was observed that the deposition rate, morphology and microhardness of the deposits were enhanced by the addition of C14-SB surfactant. The excess attractive forces from the negative head of C14-SB were strong enough to draw metallic nickel particles towards the substrate. Ni particles attempting to deposit on the electrolyte container were eliminated by the repulsive force from the positive head of the surfactant monomers. Thus, the deposition rate of the coating process was improved. The surfactant at its critical micelle concentration (CMC) doubles the deposition rate when compared to the substrate without surfactant. In addition, the microhardness of the deposit at the surfactant CMC increased by 62 %. The corrosion rate of the substrate without surfactant was 7.15 mpy, while it was 3.97 mpy for the substrate deposited with C14-SB zwitterionic surfactant at the CMC.     

Electroless deposited Ni–Re–P, Ni–W–P and Ni–Re–W–P alloys

Coatings of electroless Ni–W–P, Ni–Re–P and Ni–W–Re–P alloys were plated in alkaline citrate baths containing amino alcohols, but not free ammonia ions. The reference Ni–P alloy was used as an intermediate layer in the sandwich: Ni–Me–P/Ni–P/substrate. An extremely homogeneous thickness distribution of all alloy components was found by applying scanning Auger electron spectroscopy (SAES(. The inclusion of refractory metals at the expense of nickel and without substantial change in phosphorus content was established. A non-oxidized state of the codeposited Re and W in Ni–W–P, Ni–Re–P and Ni–W–Re–P alloys was determined by means of X-ray photoelectron spectroscopy examination, as well as by SAES profiles, revealing the absence of oxygen throughout the coatings. All alloy films are amorphous and paramagnetic.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Deposition of alumina coatings on monocrystalline diamonds by sol–gel techniques

Machining of steel or iron-based alloys with diamond tools leads to rapid tool failure — probably due to chemical wear. The use of monocrystalline diamond tools has, up to now, been obligatory for precision machining. Coating the diamonds with a thin but hard and chemically inert alumina film may overcome the problem. Alumina coatings were deposited by sol–gel techniques. It was shown that a very thin TiN intermediate layer, deposited by reactive sputtering, results in a good adhesion of the alumina coatings to the monocrystalline diamonds. The microstructure of the coatings was characterized by field-emission scanning electron microscopy (FE-SEM) and by transmission electron microscopy (TEM). The deposited coatings showed a nanocrystalline, dense microstructure. The hardness of the coatings was investigated by ultramicrohardness measurements (UMH).     

Pulse current electrodeposition and corrosion properties of Ni–W alloy coatings

Ni–W alloy coatings were prepared on a mild steel substrate by means of pulse current (PC) and compared to the coatings electrodeposited by direct current (DC). In particular the study dealt with the influence of the frequency using pulse current on the surface morphology while maintaining a constant duty cycle. A constant charge for DC and PC electrodeposition of Ni–W alloy coatings was used. The morphology of the coatings was explored by scanning electron microscopy and the composition of the coatings was analysed by X-ray powder diffraction and energy dispersive X-ray analysis. Corrosion resistance of Ni–W alloy coatings was investigated by potentiodynamic polarization in a chloride medium. The corrosion products were analysed by Raman spectroscopy. It was found that the temperature of the electrolysis affects current efficiency of the DC and PC electrodeposition. The frequency of pulse electrodeposition alters the morphology of the Ni–W alloy coatings. There was evidence of the positive influence of increased tungstate concentration in the electrolyte on corrosion resistance of the Ni–W alloy coatings.     

Electrochemical studies of Zn–Ni alloy coatings from acid chloride bath

The electrodeposition of Zn–Ni alloy from chloride bath was carried out in presence of condensation product (CP) formed between vanillin and hexamine. The investigation of electrodeposition and nucleation process was carried out on glassy carbon electrode using cyclic voltammetric and chronoamperometric techniques. During the anodic scan of cyclic voltammetry, three anodic peaks were observed corresponding to the dissolution of zinc and nickel from different phases of Zn–Ni alloy. The model of Scharifker and Hills was used to analyze the current transients and it revealed that Zn–Ni electrocrystallization process in the presence of CP, under the studied conditions, is governed by three-dimensional nucleation process controlled by diffusion. In presence of CP, the results indicated that nucleation process changes from progressive to instantaneous when the deposition potential becomes more negative. The phase structure and surface morphology of the deposits were characterized by means of X-ray diffraction analysis and Scanning electron microscopy, respectively.     

Surface microstructure and corrosion resistance of electrodeposited ternary Zn–Ni–Co alloy

The electroplating of ternary Zn–Ni–Co alloy, the influence of cobalt codeposition on crystal orientation, surface topography and corrosion resistance were investigated and contrasted with the characteristics of Zn–Ni electrodeposits. It was found that the Zn–Ni–Co alloy showed better corrosion resistance, in 3% sodium chloride, in comparison with Zn–Ni alloy electroplated under similar conditions. The best corrosion resistance was observed for ternary deposits having 11.24% Ni and 6.52% Co. The crystal orientation and surface topography were characterized by means of X-ray diffraction analysis and scanning electron microscopy, respectively.     

Effect of heat treatment on electroless ternary nickel–cobalt–phosphorus alloy

Ternary Ni–Co–P and binary Ni–P alloy coatings were deposited on mild steel panels from an alkaline bath in the presence and absence of cobalt sulfate using an electroless process. The effects of heat treatment on surface topography and crystal orientation of Ni–Co(11.17%)–P(3.49%) alloy coatings were studied in contrast to that of Ni–P ones. It was found that the as plated Ni–Co–P alloy is a supersaturated solid solution of P and Co dissolved in a microcrystalline Ni matrix with 111 preferred direction. Heat treatment induces structural changes. The formation of Ni₃P phase precipitates and recrystallization of nickel occur when the sample is treated at > 400 °C for one hour. It is observed that the Ni diffraction lines of treated Ni–Co–P alloy at > 400 °C are shifted to lower angles as compared to those of treated Ni–P or as plated Ni–Co–P alloys. The surface topography of Ni–Co–P alloy also changes with heat treatment temperature. The surface topography and crystal orientation were characterized by means of scanning electron microscopy and X-ray diffraction, respectively. The hardness and corrosion resistance, in 5 wt % NaCl solution, of heat treated Ni–Co–P samples were studied.     

Study of the mechanical and structural properties of Zn–Ni–Co ternary alloy electroplating

Ternary zinc–nickel–cobalt alloys were electrodeposited on steel substrates from sulfate bath by direct current. Microstructural and mechanical properties of Zn–Ni–Co ternary alloy coatings were investigated and contrasted with the characteristics of Zn–Ni and Zn–Co alloy coatings. It was found that the obtained Zn–Ni–Co alloy exhibited more preferred surface morphology and mechanical properties as compared to the other alloy coatings electroplated at the same conditions. X-ray diffraction studies showed that the deposits of Zn–Ni–Co alloy coatings consisted of Zn, ZnNi₃, and ZnCo₁₃ phases. The structure, surface morphology, and surface topography of the deposited alloys were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray microanalysis (EDS), and atomic force microscopy (AFM). In addition, hardness, elasticity modulus, and adhesion strength of coated alloys were measured with dynamic ultra-microhardness (DUH) and Scratch tester.     

Electroless deposition of Ni–B, Co–B and Ni–Co–B alloys using dimethylamineborane as a reducing agent

Fundamental aspects of electroless Ni–B, Co–B and Ni–Co–B alloys have been systematically examined. The composition, crystal structure and deposition rate of the alloys were determined as a function of the concentration of reducing agent (dimethylamineborane) and complexing agents (tartrate, citrate, malonate and succinic acid), bath pH and Ni2+/Co2+ ratio. Changes in the deposition rate and metallurgical features of the alloys induced by the change in plating parameters are discussed, based on electrochemical polarization data and the formation enthalpy of the nickel and cobalt borides.     

Electrochemical characterization of Ni–P and Ni–Co–P amorphous alloy deposits obtained by electrodeposition

Ni–P and Ni–Co–P amorphous alloy deposits were obtained by electrodeposition at 80 °C on carbon steel substrates. The influence of the electrolyte Co²⁺ concentration and of applied current density was investigated. The corrosion behaviour of amorphous and crystalline deposits was evaluated by polarization curves and electrochemical impedance spectroscopy in NaCl 0.1 M solution at room temperature. Impedances were measured for samples under total immersion (free potential against time) and for polarized samples in predefined regions of the polarization curves. It was found that the alloy deposit composition is highly affected by the composition of the electrolyte but displays no significant dependence on applied current density. The results showed that the presence of Co on Ni–P amorphous alloys improves the deposit performance in the studied corrosive medium. It was also verified that the amorphous structure provides higher corrosion resistance to both Ni–P and Ni–Co–P alloys.     

Young's modulus and adhesion coefficient of amorphous Ni–P coatings on a metal substrate

In the present paper the Young's modulus and adhesion coefficient of amorphous Ni–P coatings obtained from aqueous solutions were determined. The measurements were carried out using a vibrating reed apparatus. In the temperature range 550–590 K, crystallization of Ni and formation of nickel phosphide Ni₃P were observed. The Young's modulus of Ni–P amorphous layers on stainless steel at room temperature was found to be about 112 GPa. The adhesion coefficient γ of the examined layers depends on the layer thickness a _f and strongly decreases for a _f > 8 μm. This dependence corresponds to the change of the relative adhesion coefficient of about 40% for 8 μm < a _f < 15 μm. It was also shown that the adhesion coefficient does not depend on the temperature, at least in the range 300–550 K.     

Electro-deposition and characterizations of nickel coatings on the carbon–polythene composite

Nickel coating on the carbon–polythene composite plate was prepared by electrodeposition in a nickel sulfate solution in this work. The morphology and cross-sectional microstructure of the nickel coating were examined by scanning electron microscope (SEM) and optical microscope (OM), respectively. The influence of bath temperature on the nickel deposition rate was investigated experimentally. The adhesion between the coating and the substrate was evaluated by the pull-off test. The corrosion behavior of the coating in an aqueous solution of NaCl was studied by electrochemical methods. The results showed that the nickel electrodeposition rate could reach up to 0.68 μm min⁻¹ on average under conditions of cathodic current density of 20 mA cm⁻² and bath temperature of 60 °C. It was confirmed that increasing the bath temperature up to 50 °C had a positive effect on the nickel deposit rate, while an adverse effect was observed beyond 60 °C. The adhesion strength between the nickel coating and the substrate can be more than 2.3 MPa. The corrosion potential of the bright coating in the NaCl solution was more positive than that of the dull coating, and the anodic dissolution rate of the bright coating was also far lower at the same polarization potential compared with the dull coating.     

Characterization and adhesion strength study of detonation-sprayed MoB–CoCr alloy coatings on 2Cr13 stainless steel substrate

A novel MoB–CoCr alloy coating was deposited onto stainless steel (2Cr13) substrate using a detonation gun (D-gun) spraying technique. Microstructures of the powder and coating were investigated by X-ray diffraction (XRD), scanning election microscopy (SEM), and transmission electron microscopy (TEM), and a quantitative determination of the adhesion strength of the coating was calculated by combination of modified four-point bending (4PB) test and finite element analysis (FEA) simulation. The results show that the coating mainly consists of ternary transition metal boride matrix phases (CoMo₂B₂, MoCoB) and binary borides (MoB and CrB). Nanocrystalline grains with a size of 50–100 nm were observed in the coating. The average energy release rate and phase angle are 191.2 J m⁻² and 41.7o, respectively, which show strong bond strength compared to other reported values.