Effect of Cu in electroless Ni–Cu–P coating on passivation process

Electroless Ni–P and Ni–Cu–P coatings were passivated by chromate conversion treatment respectively. The anticorrosive performances of passivated coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The passivated Ni–Cu–P coating exhibited a high corrosion resistance with the i_corr of 0.236 μA/cm,² while the value of passivated Ni–P coating was only 1.030 μA/cm,² indicating the passive film could improve the corrosion resistance of Ni–Cu–P coating to a significant extent. High‐resolution X‐ray photoelectron spectroscopy was used to determine the chemical states of elements detected in the passive film. Compared with passivated Ni–P coating, the passive film on Ni–Cu–P coating exhibited a higher ratio of Cr₂O₃ to Cr(OH)₃ with the value of 72:28, which was the main factor for passivated Ni–Cu–P coating showing excellent corrosion resistance. The effect of Cu in electroless Ni–Cu–P coating on passivation process was discussed by the contrast experiment. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrochemical Behavior of Dental Ni‐Cr Wirolloy Coated with Eco‐friendly Films in Artificial Saliva

The electrochemical corrosion behavior of the non‐precious Ni‐Cr Wirolloy, being used in dentistry, was investigated before and after applying of two types of eco‐friendly coatings, polyvinyl silsesquioxane (PVS) and nano‐hydroxyapatite (nHAP) separately in artificial saliva solution at 37 °C for 14 d of immersion. The study aimed to investigate the effectiveness of the introduced coating films in enhancing the corrosion resistance of the alloy, and in decreasing the leaching of the toxic Ni ions from the alloy into the environment. The electrochemical corrosion investigation methods used are; open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The evaluated results revealed that the electrochemically coated alloy with PVS. prepared at cathodic potential showed higher corrosion resistance and more stable film compared to that prepared by conventional dip‐coating method. At the same time, the nHAP electrochemically coated film provided the best anti‐corrosion properties over all examined time intervals. The obtained results were confirmed via surface analysis, which assured the formation of the prepared coatings on the alloy surface. Chemical analysis of the corrosion product/solutions showed that the effect of electrochemically deposited nHAP and PVS. polymer films in suppression of Ni ions leaching is similar and slightly higher than that of the chemically coated PVS. one; however, all of them are efficient in decreasing the leaching of the risky Ni ions into the solution.     

Characteristics of morphology,structure and composition of titanium surface under its modification by electrochemical polarization in phosphate‐alkaline solutions

The modification of titanium surface under electrochemical polarization (EP) in the phosphate‐alkaline solutions has been studied using the methods of X‐ray diffraction, electron probe microanalysis, atomic force microscopy, X‐ray photoelectron spectroscopy (XPS), cyclic voltammetry and spectroscopic ellipsometry. It is shown that the morphological parameters of the surface, e.g. roughness and stringiness, as well as its structural‐chemical characteristics, e.g. preferred orientation, size and habit of crystallites, titanium chemical forms, thickness and phase composition of oxide film are generally dependent on the polarization potential. The characteristics of titanium surface modified at low anodic potentials 500, 750 and 1000 mV and 10‐min polarization time have been measured. The processes of Ti surface dissolution and etching along grain boundaries are found to be most intensive at 750 mV. Under 500 mV, these processes are poorly developed yet, while at 1000 mV, the surface passivating film formation limits the previous processes. Despite relatively low polarization potentials (1 V), the surficial oxide films have sufficient thickness (up to ~20 nm) and a specific multilayer structure of variable composition and oxidation state of titanium. The data obtained allow to assert that EP represents an effective tool for morphological and a structural chemical modification of a titanium surface. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization and cytocompatibility of polydopamine on MAO‐HA coating supported on Mg‐Zn‐Ca alloy

Magnesium has been suggested as a potential biodegradable metal for the usage as orthopaedic implants. However, high degradation rate in physiological environment remains the biggest challenge, impeding wide clinical application of magnesium‐based biomaterials. In order to reduce its degradation rate and improve the biocompatibility, micro‐arc oxidation coating doped with HA particles (MAO‐HA) was applied as the inner coating, and polydopamine (PDA) film was synthesized by dopamine self‐polymerization as the outer coating. The microstructure evolution of the coating was characterized using scanning electron microscopy (SEM), atomic force microscope (AFM), X‐ray diffraction analyses (XRD), Fourier transform infrared spectroscopy (FT‐IR), and X‐ray photoelectron spectroscopy (XPS). The results showed that PDA film had covered the entire surface of MAO‐HA coating and the pore size of MAO‐HA coating decreased. The root mean square (RMS) roughness of PDA/MAO‐HA coatings was approximately 106.46 nm, which was closer to the optimum surface roughness for cellular attachment as compared with MAO‐HA coatings. Contact angle measurement indicated that the surface wettability had been transformed from hydrophobic to hydrophilic due to the introduction of PDA. The PDA/MAO‐HA coatings exhibited better corrosion resistance in vitro, with the self‐corrosion potential increasing by 150 mV and the corrosion current density decreasing from 2.09 × 10^?5 A/cm ² to 1.46 × 10^?6 A/cm ² . In hydrogen evolution tests, the corrosion rates of the samples coated with PDA/MAO‐HA and MAO‐HA were 4.40 and 5.95 mm/y, respectively. MTS assay test and cell‐surface interactions experiment demonstrated that PDA/MAO‐HA coatings exhibited good cellular compatibility and could promote the adhesion and proliferation of MC3T3‐E1 cells.     

石墨烯对镍钛形状记忆合金耐腐蚀性能的影响

利用化学气相沉积法在镍钛形状记忆合金表面原位生长出石墨烯,拟提高镍钛形状记忆合金的抗腐蚀性能。通过X射线光电子能谱、拉曼光谱与扫描电镜等手段对其表征,分析石墨烯修饰后的合金表面结构和形貌。在人工唾液环境中探究了石墨烯对镍钛形状记忆合金的腐蚀速率、细胞毒性和金属释放的影响。结果表明,石墨烯在金属基体和腐蚀介质之间可以起到物理屏蔽作用,可明显地降低金属基体发生腐蚀的速率,对镍钛合金具有较强的保护能力。     

Growth and characterization of ultrathin carbon films on electrodeposited Cu and Ni

Ultrathin carbon films were grown on different types of metallic substrates. Free‐standing foils of Cu and Ni were prepared by electroforming, and a pure Ni film was obtained by galvanic displacement on a Si wafer. Commercial foil of Ni 99.95% was used as a reference substrate. Carbon films were grown on these substrates by chemical vapour deposition in a CH₄‐H₂ atmosphere. Obtained films were characterized by Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and ultraviolet photoemission spectroscopy. The XPS at grazing collection angle was used to determine the thickness of carbon films. Depending on the deposition parameters, the films of graphene or graphite were obtained on the different substrates. The uniformity of graphene and its distribution over the sample area were investigated from Raman data, optical images, and XPS chemical maps. The presence of graphene or graphite in the films was determined from the Raman spectra and Auger peak of C KVV. For this purpose, the D parameter, which is a fingerprint of carbon allotropes, was determined from C KVV spectra acquired by using X‐rays and electron beam. A formation of an intermediate layer of metal hydroxide was revealed in the samples with graphene overlayer.     

The effect of nonmetallic element P in electroless Ni‐P coating on the passivation process during chemical conversion treatment

Pure Ni and electroless Ni‐P coating (ENPC) were passivated by a chemical conversion treatment. The passive films formed on pure Ni and ENPCs (with content of P 2.9, 7.2 and 11.7 at.% respectively) were analyzed by X‐ray photoelectron spectroscopy (XPS). High‐resolution XPS was also used to analyze the chemical states of the elements detected in the passive films. The results indicated that the detected Ni and P were in elemental states, and no compound with Ni and P element was detected in passive film, meaning that Ni and P did not participate in the formation of the passive film. The content of film‐forming reaction product in passive film increases with the content of element P in Ni‐P coating, suggesting that the nonmetallic P in Ni‐P coating played an important role in the formation of the passive film. The XPS results were used to analyze the formation mechanism of the passive film. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and performance of electroless Ni–P–TiCN composite coatings on Al substrate

Electroless Ni–P and Ni–P–TiCN composite coatings have been deposited successfully on Al substrates. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) techniques were applied to study the surface morphology and the chemical composition of the deposited films. Moreover, X‐ray diffraction (XRD) proved that Ni–P and Ni–P–TiCN deposits have amorphous structures. The properties of Ni–P–TiCN/Al composite films such as hardness, corrosion resistance and electrocatalytic activity were examined and compared with that of Ni–P/Al film. The results of hardness measurements reveal that the presence of TiCN particles with Ni–P matrix improves its hardness. Additionally, the performance against corrosion was examined using Tafel lines and electrochemical impedance spectroscopy techniques in both of 0.6 M NaCl and a mixture of 0.5 M H₂SO₄ with 2 ppm HF solutions. The results indicate that the incorporation of high dispersed TiCN particles into Ni–P matrix led to a positive shift of the corrosion potential and an increase in the corrosion resistance for all aluminum substrates after their coating with Ni–P–TiCN. In addition, Ni–P–TiCN/Al electrodes showed a higher electrochemical catalytic activity and stability toward methanol oxidation in 0.5 M NaOH solution compared with that of Ni–P/Al. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrochemical behavior of polypyrrole-coated AZ31 alloy modified by fluoride anions

The electrochemical polymerization of polypyrrole (Ppy) films on AZ31Mg alloys was carried out using cyclic voltammetery in 0.5 M sodium salicylate solution containing 0.25 M pyrrole and different concentration of sodium fluoride (NaF). Corrosion performance of the Ppy film was assessed by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in 3.5 % NaCl solution. It was observed that Ppy coatings doped in the presence of 100 ppm NaF provide the best corrosion protection for magnesium and the corrosion potential shifted about 290 mV toward nobler potentials and decrease the corrosion current density about one order of magnitude. The surface analysis of the coatings showed that the addition of F^? dopant anions led to an improvement in the smoothness, thickness, and adhesion quality of the synthesized Ppy coating on the Mg surface. The scanning electron microscopy (SEM) studies of the fluoride-doped Ppy films revealed that the synthesized coating has a closely packed globular structure which was composed of nanoparticles of Ppy.     

A Novel Functionalized Single‐Wall Carbon Nanotube Modified Electrode and Its Application in Determination of Dopamine and Uric Acid in the Presence of High Concentrations of Ascorbic Acid

Multilayer films of negatively charged single‐wall carbon nanotubes (SWCNTs) and positively charged cetylpyridinium bromide (CPB) have been deposited on a glassy carbon electrode (GCE) using layer‐by‐layer (LBL) technique. The assembled multilayer films have been investigated by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and quartz crystal microbalance (QCM) measurements. The voltammetric signal of dopamine (DA), uric acid (UA), and ascorbic acid (AA) could be observed well‐separated with the assembled SWCNTs/CPB multilayer films in pH 7.0 PBS. The oxidation peak potentials of DA, UA, and AA are centered at about 169 mV, 292 mV and ?10 mV on differential pulse voltammograms (DPVs), respectively. The peak‐to‐peak potential separation was 123 mV, 179 mV, and 302 mV for DA‐UA, DA‐AA, and UA‐AA in DPVs, respectively. This permits the simultaneous detection of DA and UA in the presence of AA.     

Reinforcement of phosphorylated graphene oxide on the anticorrosive properties of waterborne acrylate-epoxy resin coatings

Abstract

Phosphorylated graphene oxide (PedGO) was synthesized through the in-situ phosphate esterification method with urea as catalyst and then embed into waterborne acrylate-epoxy resin emulsion (AE) coating to modify the coating. The TEM and AFM indicated that phosphate was uniformly decorated on GO sheets, forming a large phosphorylated graphene oxide sheets. The PedGO improved the water vapor permeability and the coating adhesion strength after 30?days of immersion in 3.5% NaCl of AE coatings, respectively. Electrochemical impedance spectroscopy measurements (EIS) revealed that the PedGO-modified AE (PedGO/AE) was an outstanding barrier against corrosive media compared with AE or GO-modified AE (GO/AE). Scratch tests also showed that the corrosion-promotion effect of PedGO in AE was inhibited. The enhanced corrosion protection performance was observed because on the one hand the PedGO can greatly prolonged the diffusion pathway of corrosive media in the coating matrix; on the other hand the organic phosphate on the PedGO formed the passivation membrane with metal ions by chelation in the corrosion region, which can prevented the contact of corrosive medium and metal.     

Layer-by-layer stacked graphene nanocoatings by Marangoni self-assembly for corrosion protection of stainless steel

Graphene nanosheets are widely used in anti-corrosion polymeric coating as filler,owing to the excellent electrochemical inertness and barrier property.However,as the arrangement of graphene nanosheets is difficult to form a perfect layered structure,polymeric coating with graphene nanosheets usually needs micron-scale thickness to ensure the enhancement of corrosion protection.In this work,layer-by-layer stacked graphene nanocoatings were fabricated on stainless steel by self-assembly based on Marangoni effect.The anti-corrosion property of graphene coatings were studied through Tafel polarization curves,electrochemical impedance spectroscopy and accelerated corrosion test with extra applied voltage.The self corrosion current density of optimized three-layered graphene coated sample was one quarter of that of bare stainless steel.And the self corrosion potential of optimized sample is increased to-0.045 V.According to the results,graphene nanocoatings composed of layered nanosheets exhibits good anticorrosion property.Besides,the self-assembly method provide a promising approach to make layeredstructure coating for other researches about 2 D material nanosheets.     

Self-assembled graphene/azo polyelectrolyte multilayer film and its application in electrochemical energy storage device

Graphene/azo polyelectrolyte multilayer films were fabricated through electrostatic layer-by-layer (LbL) self-assembly, and their performance as electrochemical capacitor electrode was investigated. Cationic azo polyelectrolyte (QP4VP-co-PCN) was synthesized through radical polymerization, postpolymerization azo coupling reaction, and quaternization. Negatively charged graphene nanosheets were prepared by a chemically modified method. The LbL films were obtained by alternately dipping a piece of the pretreated substrates in the QP4VP-co-PCN and nanosheet solutions. The processes were repeated until the films with required numbers of bilayers were obtained. The self-assembly and multilayer surface morphology were characterized by UV-vis spectroscopy, AFM, SEM, and TEM. The performance of the LbL films as electrochemical capacitor electrode was estimated using cyclic voltammetry. Results show that the graphene nanosheets are densely packed in the multilayers and form random graphene network. The azo polyelectrolyte cohesively interacts with the nanosheets in the multilayer structure, which prevents agglomeration of graphene nanosheets. The sheet resistance of the LbL films decreases with the increase of the layer numbers and reaches the stationary value of 1.0 × 10(6) Ω/square for the film with 15 bilayers. At a scanning rate of 50 mV/s, the LbL film with 9 bilayers shows a gravimetric specific capacitance of 49 F/g in 1.0 M Na(2)SO(4) solution. The LbL films developed in this work could be a promising type of the electrode materials for electric energy storage devices.     

Novel flame retardant paint based on Co(II) and Ni(II) metal complexes as new additives for surface coating applications

The study is focused on the synthesis of a new Co(II) and Ni(II) metal complexes, which is synthesized by the reaction of the isatin 4‐aminoantipyrine Schiff base ligand with selected divalent Co(II) and Ni(II) ions and their possible applications as flame retardant additives in paint formulations for surface coating application. The prepared metal complexes were characterized using a combination of Fourier transform infrared, elemental analysis, proton nuclear magnetic resonance, ¹³C‐NMR spectra, and mass spectroscopy. The prepared Schiff base ligand metal complexes were physically added to alkyd paint formulation to give coating formulations at a laboratory scale and then applied onto plywood and steel panels using a brush. The ignitability and oxygen index values obtained indicated that the paint which contained the prepared Co(II) and Ni(II) metal complexes as additives exhibited very good flame retardant. The physical and mechanical characteristics of the coatings were studied in order to estimate any disadvantages due to the incorporation of the additives. It was discovered that the added substances did not impact the hardness, flexibility, and adhesion of the prepared coating films. The gloss of the paint formulation film was improved due to the incorporation of the aromatic ring into the formulation and the level of the oil percent.     

Synthesis of graphene oxide nanosheet: A novel glucose sensor based on nickel-graphene oxide composite film

The graphene oxide (GO) nanosheets were produced by chemical conversion of graphite, and were characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR). An electrochemical sensor based on Ni/graphene (GR) composite film was developed by incorporating Ni²⁺ into the graphene oxide film modified glassy carbon electrode (Ni/GO/GCE) through the electrostatic interactions with negatively charged graphene oxide. The Ni²⁺/graphene modified glassy carbon electrode (Ni/GR/GCE) was prepared by cyclic voltammetric scanning of Ni/GO/GCE in the potential range from ?1.5 to 0.2 V at 50 mV s^?1 for 5 cycles. The electrochemical activity of Ni/GR/GCE was illustrated in 0.10 M NaOH using cyclic voltammetry. The Ni/GR/GCE exhibits the characteristic of improved reversibility and enhanced current responses of the Ni(III)/Ni(II) couple. The introduction of conductive graphene not only greatly facilitates the electron transfer of Ni²⁺, but also dramatically improves the long-term stability of the sensor by providing the electrostatic interactions. Ni/GR/GCE also shows good electrocatalytic activity toward the oxidation of glucose. The Ni/GR/GCE gives a good linear range over 10 to 2700 μM with a detection limit of 5 μM towards the determination of glucose by amperometry. This sensor keeps over 85% activity towards 0.1 mM glucose after being stored in air for a month, respectively. Furthermore, the modified sensor was successfully applied to the sensitive determination of glucose in blood samples.     

Improve Corrosion Resistance of Zircaloy by Copper–Graphene Nanocomposite Coatings

In this study, the corrosion behavior of Zircaloy was investigated in the presence and absence of copper–graphene nanocomposites coating. The coating was prepared employing Hummers’ and electrochemical reduction methods. The morphology of copper–graphene nanocomposites coating was studied using scanning electron microscopy (SEM). Corrosion behavior was investigated employing dynamic polarization and electrochemical impedance spectroscopy (EIS) tests in a solution containing lithium hydroxide (LiOH), boric acid (H₃BO₃), and deionized water. The results showed that corrosion resistance of Zircaloy increased with introduction of copper–graphene nanocomposites coatings. The lowest corrosion rate was attained in the Zircaloy with copper–graphene nanocomposites coating (corrosion rate: 0.040 mm/year). An approximately 20 times decrease in the corrosion rate was observed in the Zircaloy with copper–graphene nanocomposites coating when compared to the un-coated Zircaloy (corrosion rate: 0.831 mm/year).

     

Surface analysis and corrosion resistance of new nickel base thin film alloys

Electroless Zn–Ni–P thin films were deposited on low carbon steel from an alkaline non‐cyanide aqueous electrolyte. The newly developed ternary alloys structure and microstructure investigations were carried out via X‐ray diffraction and SEM. Chemical composition of the coatings was investigated via energy dispersive spectroscopy. Polarization tests were used to study the corrosion properties of the coatings in a 3.5 wt.% NaCl solution. The results confirmed the high corrosion resistance of Zn–Ni–P alloy plated steel sheet. The surface analysis of the thin film samples before and after corrosion was performed by XPS. The incorporation of Zn in Ni–P thin film is proven for all initial samples to be as a mixture of zinc and zinc oxide, while nickel exists in +2 and +3 oxidized states. A passive film of a mixture of oxide and hydroxide of zinc and nickel forms on the surface and prevents the Zn–Ni–P thin films from corrosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Corrosion behavior of electroless Ni–P/TiO2 nanocomposite coatings

Composite Ni–P/nano‐TiO₂ coatings were prepared by simultaneous electroless deposition of Ni–P and nano‐TiO₂ on a low carbon steel substrate. The deposition was carried out from stirred solutions containing suspended nano‐TiO₂ particles. The Ni–P and Ni–P/nano‐TiO₂ coatings before and after heat treatment were characterized by X‐ray diffraction, scanning electron microscopy and energy dispersive X‐ray spectroscopy. The micro‐structural morphologies of the coatings significantly varied with the nano‐TiO₂ content. The corrosion resistance of as‐plated and heat‐treated Ni–P and Ni–P/nano‐TiO₂ coatings was investigated by anodic polarization, Tafel plots and electrochemical impedance spectroscopic (EIS) studies in 3.5% NaCl solution. Ni–P/nano‐TiO₂ coating exhibited superior corrosion resistance over Ni–P coating. Copyright © 2015 John Wiley & Sons, Ltd.     

FeS膜的离子选择性对基体金属腐蚀的影响

本文采用动电位扫描法研究了Ａ３钢在油田污水中的腐蚀速度，以及Ｓ２－对腐蚀速度的影响，通过测膜电位曲线的方法，研究了ＦｅＳ膜的离子选择性，阐述了ＦｅＳ膜的离子选择性对基体金属腐蚀行为的影响。研究表明，金属表面的ＦｅＳ膜是一种双极结构膜，促进腐蚀。     

Fabrication of graphene with CuO islands by chemical vapor deposition

Graphene prepared on Cu foil by chemical vapor deposition was studied as a function of post growth cooling conditions. CuO islands embedded in the graphene film were discovered and studied by scanning electron microscopy, atomic force microscopy, and X-ray photoemission spectroscopy. It is shown that nanostructured holes can be formed within a graphene film by reduction using hydrogen cooling immediately after film growth. We also observe the formation of symmetrical oxide islands in these holes. This study provides an easy way to fabricate a graphene + CuO composite, and the method may be extended to other graphene based structures.