Process and performance of hot dip zinc coatings containing ZnO and Ni-P under layers as barrier protection

A new coating system of under layer for hot dip zinc coating was explored as an effective coating for steel especially for application in relatively high aggressive environments. The influence of different barrier layers formed prior to hot dip galvanization was investigated to optimize high performance protective galvanic coatings. The deposition of ZnO and Ni-P inner layers and characteristics of hotdip zinc coatings were explored in this study. The coating morphology was characterized by scanning electron microscope (SEM) analysis. The hot dip zinc coatings containing under layer showed substantial improvement in their properties such as good adhesion, and high hardness. In addition, a decrease in the thickness of the coating layer and an enhancement of the corrosion resistance were found. Open circuit potential (OCP) of different galvanized layers in different corrosive media viz. 5% NaCl and 0.5 M H₂SO₄ solutions at 25 ± 1 °C was measured as a function of time. A nobler OCP was exhibited for samples treated with ZnO and Ni than sample of pure Zn; this indicates a dissolution process followed by passivation due to the surface oxide formation. The high negative OCP can be attributed to the better alloying reaction between Zn and Fe and to the sacrificial nature of the top pure zinc layer.     

The role of the spray pyrolysed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> barrier layer in achieving high efficiency solar cells on flexible steel substrates

Thin film chalcopyrite solar cells grown on light-weight, flexible steel substrates are poised to enter the photovoltaic market. To guarantee good solar cell performance, the diffusion of iron from the steel into the CIGSe absorber material must be hindered during layer deposition. A barrier layer is thus required to isolate the solar module from the metal substrate, both electronically and chemically. Ideally the barrier layer would be deposited by a cheap roll-to-roll process suitable to coat flexible steel substrates. Aluminium oxide deposited by spray pyrolysis matches the criteria. The coating is homogeneous over rough substrates allowing comparatively thin barrier layers to be utilized. In this article, solar cell results are presented contrasting the device performance made with a barrier layer to that without a barrier layer. Secondary Ion Mass spectrometry (SIMS) measurements show that the spray pyrolysed barrier layer diminishes iron diffusion to the chalcopyrite absorber layer. The role of sodium, imperative for the growth of high efficiency chalcopyrite solar cells, and how it interacts with Al₂O₃ is discussed.     

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.     

Dissolution behaviour of the barrier layer of porous oxide films on aluminum formed in phosphoric acid studied by a re-anodizing technique

Chemical dissolution of the barrier layer of porous oxide films formed on aluminum foil (99.5% purity) in the 4% phosphoric acid after immersion in 2 mol dm⁻³ sulphuric acid at 50 °C has been studied. The barrier layer thickness before and after dissolution was determined using a re-anodizing technique. A digital voltmeter with a computer system was used to record the change in the anode potential with re-anodizing time. It has been found that the barrier layer material may consist of two or three regions according to the dissolution rate. The barrier oxide contains two layers at 35 V: the outer layer with the highest dissolution rate and the inner layer with low dissolution rate. The barrier oxide contains three layers at 40 V and above it: the outer layer with high dissolution rate, the middle layer with the highest dissolution rate and the inner layer with low dissolution rate. It has been shown that there is a dependence of the dissolution rate on the surface charge of anodic oxide film. Annealing of porous alumina films for 1 h at 200 °C leads to disappearance of layers with different dissolution rates in the barrier oxide. We explained this phenomenon by the absence of the space charge in the barrier oxide of such films.     

Analysis of chemical dissolution of the barrier layer of porous oxide on aluminum thin films using a re-anodizing technique

Chemical dissolution of the barrier layer of porous oxide formed on thin aluminum films (99.9% purity) in the 4% oxalic acid after immersion in 2 mol dm⁻³ sulphuric acid at 50 °C has been studied. The barrier layer thickness before and after dissolution was calculated using a re-anodizing technique. It has been shown that above 57 V the change in the growth mechanism of porous alumina films takes place. As a result, the change in the amount of regions in the barrier oxide with different dissolution rates is observed. The barrier oxide contains two layers at 50 V: the outer layer with the highest dissolution rate and the inner layer with a low dissolution rate. Above 60 V the barrier oxide contains three layers: the outer layer with a high dissolution rate, the middle layer with the highest dissolution rate and the inner layer with a low dissolution rate. We suggest that the formation of the outer layer of barrier oxide with a high dissolution rate is linked with the injection of protons or H₃O⁺ ions from the electrolyte into the oxide film at the anodizing voltages above 57 V.     

Study on the deterioration process of bipolar coating using electrochemical impedance spectroscopy

A bipolar coating, which is composed of inner layer epoxy with nano SiO₂ modified by cetyltrimethylammonium bromide (CTAB) (containing positive fixed charge) and outer layer epoxy with nano SiO₂ modified by sodium dodecylbenzenesulfonate (SDBS) (containing negative charge), was prepared in this paper. Its deterioration process after exposure to 5% KCl solution was also studied by EIS measurement and SEM observation. The results indicate that the impedance module of the bipolar coating is about 1E+9 ohm after a longer time immersion period. The bipolar coating has a better anti-corrosion capacity than that of epoxy coating. The cation-selective outer layer in bipolar coating inhibits the aggressive anion, such as Cl⁻ ion, passing through the outer coating. Similarly, the anion-selective inner layer inhibits the metal cation passing through the inner coating. Thus the bipolar coating can protect the metal substrate from corrosion effectively. The p-n junction of bipolar coating, which has great charge storage ability, is the key factor in the anti-corrosion capacity of bipolar coating.     

Analysis of the interface between a pulsed laser deposited calcium phosphate coating and a titanium alloy substrate

Calcium phosphate coatings deposited on titanium alloy are intended to add a bioactive surface to medical implants. This work presents the characterisation of the interface between Ti-6Al-4V and a crystalline calcium phosphate coating obtained by pulsed laser deposition, with a KrF excimer laser, at 575 °C and under a 45 Pa water-vapour atmosphere. The coating–substrate system was studied by secondary-ion mass spectrometry, scanning electron microscopy, X-ray diffractometry, Raman spectroscopy and X-ray photoelectron spectroscopy. The results show that the deposition process promotes the interdiffusion of substrate elements into the coating and coating elements into the substrate oxide layer. Thus, a graded layer of mixed calcium phosphate and amorphous titanium oxide is formed. For the substrate, a hydroxyapatite coating acts more as a barrier for oxygen incoming from a gas than as an oxygen source during deposition. Moreover, oxygen diffusion into the substrate occurs. Thus, the content of oxygen of this oxide layer diminishes with depth. When the oxygen concentration is low enough it is incorporated in solid solution in the titanium alloy . PACS 81.15.Fg; 68.55.-a; 87.68.+z     

Atmospheric corrosion in the Gulf of México

The corrosion products on steels exposed at two sites in Campeche, México and one site at Kure Beach, USA, have been investigated to determine the extent to which different marine conditions and exposure times control the oxide formation. The corroded coupons were analyzed by Mössbauer, Raman and infrared spectroscopy as well as X‐ray diffraction, in order to completely identify the oxides and map their location in the corrosion coating. The coating compositions were determined by Mössbauer spectroscopy using a new parameter, the relative recoilless fraction (F-value) which gives the atomic fraction of iron in each oxide phase from the Mössbauer sub‐spectral areas. For short exposure times, less than three months, an amorphous oxyhydroxide was detected after which a predominance of lepidocrocite (γ-FeOOH), and akaganeite (β-FeOOH) were observed in the corrosion coatings with the fraction of the later phase increasing at sites with higher atmospheric chloride concentrations. The analysis also showed that small clusters of magnetite (Fe₃O₄), and maghemite (γ(Fe₂O₃), were seen in the micro-Raman spectra but were not always identified by Mössbauer spectroscopy. For longer exposure times, goethite (α-FeOOH), was also identified but little or no β-FeOOH was observed. It was determined by the Raman analysis that the corrosion products generally consisted of inner and outer layers. The protective layer, which acted as a barrier to slow further corrosion, consisted of the α-FeOOH and nano-sized γ-Fe₂O₃ phases and corresponded to the inner layer close to the steel substrate. The outer layer was formed from high γ-FeOOH and low α-FeOOH concentrations.     

Preparation of a novel Ni/Co-based alloy gradient coating on surface of the crystallizer copper alloy by laser

A high wear-resistant gradient coating made of Ni/Co-based alloys on the surface of a Cu alloy substrate was synthesized using a YAG laser induced in situ reaction method. The coating consists of three layers: the first is a Ni-based alloy layer, the second and third are Co-based alloy layers. The microhardness increases gradually from 98 HV in the Cu alloy substrate to the highest level of 876 HV in the third layer. The main phase of the Co-based alloy layer is CoCr₂(Ni,O)₄, coexisting with the Fe₁₃Mo₂B₅, Cr(Co(Mo, and FeCr_0.29Ni_0.16C_0.06 phases. Wear tests indicate that the gradient coating has good bond strength and wear properties with a wear coefficient of 0.31 (0.50 for the Cu alloy substrate). Also, the wear loss of the coating is only 0.01 g after it has been abraded for 60 min, which is only one fifth of that of the Cu alloy of the crystallizer. Wear tests of the gradient coating reveal good adhesive friction and wear properties when sliding against steel under dry conditions. This novel technique may have good application to make an advanced coating on the surface of the Cu alloy crystallizer in a continuous casting process.     

Development of phosphate inter layered hydroxyapatite coating for stainless steel implants

As zinc phosphate acts as a versatile material for potential biomedical applications, it was modified into a thin layer coating for orthopaedic applications in the present study. A unique layering system consisting of pure substrate (316L SS), thick Fe-Zn alloy layers, thin ZnP layer on which a hydroxyapatite (HA) layer, was developed and studied. The composition, surface morphology and corrosion resistance characteristics of the layering system was evaluated. The stability of the multi-layered coating system consisting of ZnP inter layer, was evaluated by subjecting to different extent of dissolution in aggressive physiological media followed by allowing for re-growth in simulated body fluid (SBF). The coating system revealed good stability.     

Study of the composition and properties of protective layers formed by the ion-beam-assisted deposition of cadmium,zinc, and aluminum onto steel surfaces

Layers formed by the ion-beam-assisted deposition of cadmium, zinc, and aluminum onto the surface of carbon and stainless steels to protect aluminum and its alloys from corrosion in the case of their contact with steel parts are investigated. The protective layers are created via ion-beam-assisted deposition, in which metal deposition and mixing of the deposited layer with the substrate surface (this process is implemented by accelerated (U = 5 kV) ions of the same metal) occurs, respectively, from a neutral vapor fraction and the vacuum arc plasma of a pulsed electric-arc ion source. The morphology and composition of the generated surface layers are studied by means of scanning electron microscopy, electron-probe microanalysis, and Rutherford backscattering spectrometry. The layer composition is revealed to include atoms of the deposited metal, the substrate material, oxygen, and carbon. The layer thickness varies from ~50 to 80 nm, and the deposited metal content of the layers is ~(1.0–3.5) × 10¹⁷ atom/cm². Corrosion tests of the aluminum and its alloy in contact with the materials under study confirm the efficiency of the ion-beam modification of steel surfaces.     

Study on the deterioration process of a chromium-free conversion coating on AZ91D magnesium alloy in NaCl solution

The morphology of a chromium-free conversion coating for AZ91D magnesium alloy was observed with an Atomic Force Microscopy. The results showed the uniform conversion coating has a relatively smooth appearance with shallow valleys. The EDX results indicated that the compositions of the coating were mainly compounds of Mg, Al, Mn, P, Ca and O. The XRD result showed that the coating contained amorphous materials and a small quantity of crystalline compound. The pitting product of the coating in NaCl water solution mainly composed of Mg, Cl, Mn, P, Ca and O. The corrosion behavior of the samples in NaCl solution was also studied by electrochemical impedance spectroscopy (EIS), which was characterized by one capacitive loop and one inductive loop. Based upon study on both a mathematical model for Faradic admittance of coating in NaCl solution and EIS, it could be considered that the inductive loop was caused by the adsorption of Cl anion and the appearance of pitting corrosion. A degradation mechanism of the coating in NaCl solution is set forth: dissolution velocity of the Cl⁻ adsorption regions of the coating is higher than those non-adsorption regions, for Cl⁻ anions are selective adsorption at some regions of coating surface. When the adsorption regions of coating layer are penetrated by dissolution, the pitting comes into being. The degradation mechanism of conversion coating and the mathematical model are consistent with the EIS results, polarization measurement results and coating's corrosion test results.     

Growth of Ga-doped ZnO films with ZnO buffer layer by sputtering at room temperature

Gallium-doped zinc oxide films have been grown on glass substrates with and without ZnO buffer layers by r.f. magnetron sputtering at room temperature. In this approach, the grey relational Taguchi method analysis is adopted to solve the coating process with multiple deposition qualities. Optimal coating parameters can then be determined by using the gray relational grade as a performance index. The GZO coating parameters (r.f. power, sputtering pressure, O₂/(Ar+O₂) flow-rate ratios, and deposition time) are optimized, by taking into account the multiple performance characteristics (structural, morphological, deposition rate, electrical resistivity, and optical transmittance). The results indicate that with the grey relational Taguchi method, the electrical resistivity of GZO films is reduced from 9.23×10⁻³ to 5.77×10⁻³ Ω cm and optical transmittance increases from 79.42% to 82.95%, respectively. The ZnO buffer layer can reduce the electrical resistivity of GZO films from 5.77×10⁻³ to 2.38×10⁻³ Ω cm. It can be anticipated that room temperature deposition enables film deposition onto polymeric substrates for flexible optoelectronic devices.     

CEMS study of oxide layers formed on stainless steel (SUS304 and SUS316)

Stainless steel (SUS304 and SUS316) was chemically treated and heated at various temperatures, and the oxide films formed on the surface were analyzed by conversion electron Mössbauer spectrometry (CEMS). Three magnetic components of iron species were detected in the top oxide layers of stainless steels heated below 600°C and the fine particles of iron oxides were initially produced in the inner oxide layers of the samples heated at temperatures higher than 700°C. Only paramagnetic iron species were detected in the oxide layers of the stainless steels prepared by chemical treatment.     

Photocatalytic degradation of methylene blue in water solution by multilayer TiO2 coating on HDPE

A multilayer photocatalytic TiO₂ coating on a high-density polyethylene (HDPE) disk was found to degrade aqueous methylene blue in a batch reactor study. The TiO₂ coating was fabricated by a low-temperature method using polyurethane resin (PU) as a barrier layer for HDPE and as a binding agent for two TiO₂ layers. Adequate adhesion between the HDPE substrate and PU barrier in aqueous environment was ensured with an oxygen plasma treatment.The photocatalytic effect of immersed TiO₂ coating on the degradation of methylene blue in aqueous solution was monitored by UV–vis spectrometry as a function of UV-illumination time. Samples were allowed to adsorb methylene blue in the dark for 1 h before the UV-degradation experiments were started. The percentages of methylene blue degraded during 6 h UV illumination (λ = 365 nm) varied from 80% to 92%. The degradation followed pseudo-first order reaction kinetics, and the observed rate constants (k_obs) were between 0.27 and 0.43 h⁻¹.     

57Fe Mössbauer spectroscopic analysis of a welding wire's coating

The coating layer of a steel welding wire has been removed and studied by⁵⁷Fe Mössbauer spectroscopy at different temperatures and at 5 K in an applied magnetic field of 60 koe. The subspectrum of the metallic phase is typical for a low-carbon steel. The coating phase cannot be identified as any known modification of iron oxide or oxyhydroxide. The spectral features rather suggest that it consists of an amorphous ferric material similar to a ferric gel.     

Mössbauer and XRD study of Al-Sn linished steel bimetal alloy

Aluminium alloy free CS1 type steel (0.06 wt% C, 0.45 wt% Mn) and samples of cold roll bonded steel bimetal alloys (MAS15 and MAS16) were fabricated and investigated by X-ray diffraction (XRD), ⁵⁷Fe conversion electron Mössbauer spectroscopy (CEMS) at room temperature. XRD has revealed only the existence of the alpha iron solid solution (steel) phase in the steel only sample, while identified steel and metallic Al and Sn constituent phases in the bimetallic alloys. ⁵⁷Fe Mössbauer spectroscopy revealed the presence of 4 % secondary iron-bearing phase attributed mainly to iron oxide/ oxyhydroxides (ferrihydrite) besides the steel matrix on the surface of the steel sample. A significant difference between the occurrences of the secondary phase of differently prepared bimetal alloys found in their ⁵⁷Fe CEM spectra allowed to identify the main phase of debris as different iron oxide/ oxyhydroxides.     

Oxidation of the (100) surface of a NiFe alloy

The initial stages of oxidation of the (100) surface of a single crystal alloy specimen of approximate atomic composition Ni 59, Fe 41 (at%) have been studied by Auger spectroscopy and electron diffraction techniques. The clean alloy surface shows only a slight iron enrichment over the temperature range of the oxidation studies (373–873 K). Oxidation studies were performed over the O₂ pressure range 5 × 10^?9 to 1 × 10^?6 Torr. Within these experimental conditions the rate of oxygen uptake was found to be linear in pressure and essentially independent of temperature. LEED studies showed that a chemisorbed c(2 × 2) structure preceded the formation of surface oxides. The interaction of oxygen with the surface induced a marked segregation of iron and this was particularly pronounced at elevated temperatures. Chemical shifts were observed in the low energy Ni and Fe Auger spectra during oxidation; these were similar to those previously observed in separate studies of the oxidation of pure Ni and of pure Fe. At the higher temperatures the initial oxide layer grew epitaxially apparently as a (111) cubic oxide on the (100) substrate. The Ni to Fe concentration ratio in oxides several layers thick was found to depend on the temperature of the reaction; at higher temperatures the oxide were more Fe-rich. The Fe to Ni ratio in oxides produced at lower temperatures could be increased by annealing. At large O₂ exposures (about 5000 L) a transition was observed in the structure of the oxide layer.     

CLAM钢表面Fe-Al合金渗层的制备

FeAl/Al2O3阻氚涂层具有高阻氚因子、耐腐蚀和耐高温等优良性能,是ITER首选的阻氚涂层.Fe-Al合金渗层对Al2O3膜层的形成质量有重要的影响.本文采用了AlCl3-EMIC离子液体电镀法在CLAM钢表面镀铝,然后利用热处理使Al与基体相互扩散制备Fe-Al合金渗层.采用X射线衍射仪、扫描电子显微镜和能量散射谱仪研究了热处理时间和温度对渗层组织结构的影响.结果表明:渗层厚度随着热处理温度和时间的提升而增大,试样表面逐渐由富铝相向贫铝相转化.在不同热处理条件下获得的渗层与CLAM钢基体结合紧密,无孔洞等缺陷.热处理时间一定时,热处理温度对渗层生长速率的影响符合Arrhenius关系,拟合计算出CLAM钢的渗铝Arrhenius活化能为78.48 kJ/mol.在640℃和760℃时,渗层中金属间化合物的生长受晶界扩散速率与体扩散速率的共同影响.在综合考虑合理的渗层厚度、表面Fe-Al合金相、热处理成本的情况下,较优的热处理工艺为700℃/10 h.     

Influence of nanometer scale film structure of ZDDP tribofilm on Its mechanical properties: A computational chemistry study

We investigated the influence of a nanometer scale film structure of a tribofilm generated from zinc dialkyldithiophosphate (ZDDP) anti-wear additive on its mechanical properties using a combined molecular dynamics (MD) and finite element (FE) method. The frictional behavior of an interface between a native iron oxide layer on steel surface and zinc metaphosphate - regarded as a model material of ZDDP tribofilm - was firstly studied using the MD method. The results showed that the iron atoms in the oxide layer diffused into the phosphate layer during the friction process. The zinc atoms in the phosphate layer also diffused into the oxide layer. Significant interdiffusion of iron and zinc atoms was observed with increasing simulation time. Thus, metallic phosphate with a gradient composition of iron and zinc atoms was formed on the phosphate/oxide interface. We then constructed an axisymmetric nanoindentation simulation model from the MD-derived structures at a certain simulation time and carried out a FE calculation. As a result, we found that the rubbed ZDDP tribofilm, including the phosphate with the gradient composition of metallic atoms, showed larger contact stiffness and hardness. The combined MD/FE simulation indicates that the tribofilm becomes stiffer and harder due to the interdiffusion of iron and zinc atoms on the tribofilm/oxide interface. We have found that the gradient composition formation in ZDDP tribofilm during friction process influences on its mechanical properties.