Chrome Plating from Sulfate–Oxalate Cr(III) Baths. Structure, Composition, and Corrosion Behavior1

The studies on chrome-plating from sulfate–oxalate Cr(III) baths are generalized. It is shown that the metal is deposited from the mentioned baths at a current efficiency over 40% and forms deposits of any thickness. Chrome-plating may be carried out in the cells with undivided cathodic and anodic compartments, which reduces the current efficiency to 25–30%. The reflectivity and color of the deposits do not differ from those of the deposits from standard chrome-plating baths based on Cr(VI). Special attention is paid to the studies of the corrosion and electrochemical behavior of deposited layers. Steady-state polarization curves in a 0.5 M H₂SO₄indicate that the studied chromium deposits exhibit no active-dissolution range. The free corrosion–potential is shifted in the positive direction compared with coatings deposited from standard chrome-plating baths and falls into the passivity range. According to XPS method, the passive film is about several nanometers thick and, along with oxide compounds of chromium, includes its carbides formed during the electroplating.     

Corrosion of metals and alloys in molten glasses. Part 1: glass electrochemical properties and pure metal (Fe, Co, Ni, Cr) behaviours

Corrosion of pure metals Fe, Ni, Co, Cr in molten glass was studied at 1050 °C by electrochemical techniques and thickness losses measurements. These two techniques are in good agreement. The electrochemical apparatus was used to determine the formal potential of some redox couples, to identify the corrosion reactions and to evaluate the corrosion rates.Among tested metals, only chromium is a passivable material. The passivation is due to the formation of a chromium oxide (Cr₂O₃) protective layer at the glass/metal interface. Then superalloys used in molten glass must contain a high chromium level to resist to corrosion.     

The effects of immersion time on morphology and electrochemical properties of the Cr(III)-based conversion coatings on zinc coated steel surface

The main purpose of this paper is to develop a dynamic and non-destructive method to quantify and correlate the microstructure changes of the Cr(III) layer by electrochemical techniques. The open circuit potential (OCP) analysis reveals the nucleation growth mechanisms of the Cr(III) layer and the dissolution phenomena of Zn. In addition, the effects of immersion time to the corrosion behavior of Cr(III)-based conversion coatings (TCCCs) on electrogalvanized steel were studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in a 3.5% NaCl solution. Furthermore, surface morphology of the Cr(III) coatings under different immersion times was examined using both a scanning electron microscope and an atomic force microscope.From the potentiodynamic polarization experiment, the corrosion current density (I_corr) of the specimen with immersion time of 60 s was found appreciably small, representing the inheritance of the best anticorrosion performance. Additionally, the corrosion resistance of the Cr(III)-coating for the specimens obtained between 30 s and 60 s is two order higher than those of the untreated specimen from the EIS experiments. Results show that the quality of Cr(III)-based conversion coatings was strongly influenced by the immersion time of Cr(III) solution. And the optimal immersion time is recommended in the range of 30–60 s.     

Chromium electrodeposition from Cr(III) aqueous solutions

The aim of this work is to study an alternative plating process to obtain chromium coatings through electrodeposition from baths containing trivalent chromium, as aqueous solutions of Cr (III) are significantly less dangerous, in terms of human health and environmental impact, as compared to the traditional Cr (VI) baths employed for this purpose. In order to overcome problems regarding the reduction of Cr (III) in aqueous solution, two approaches were followed: i) the possibility of co-depositing chromium along with a second metal, which could help the process of discharge of Cr³⁺ on the substrate; ii) the use of a specific ligand for the Cr³⁺ ion, which can generate easily reducible complexes at the metal-solution interphase. Both approaches led to interesting results: in particular, the co-deposition enabled us to obtain NiCr alloy with a high percentage of chromium, and the deposition using specific complexing agents allowed optimal bath compositions to be developed both for decorative and hard chromium plating.     

Nanocrystalline zinc–nickel alloy deposition using pulse electrodeposition (ped) technique

Abstract

Zinc–nickel alloy was electrodeposited on stainless steel using pulse current deposition (PED) from a chloride–sulphate bath. Duty cycles were varied between 10 and 80% and frequency was changed from 10 to 100 Hz. The deposit characteristics were analysed using SEM, XRD and AFM and the results are presented in this paper. The corrosion resistance of zinc–nickel alloy deposited from direct current deposition (DCD) has been compared with that of the deposit obtained by pulse current using the electrochemical impedance spectroscopy method.     

Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.     

Prohesion and outdoors tests on corrosion products developed over painted galvanized steel sheets with and without Cr(VI) species

Galvanized steel sheets pre-treated with a new product and then painted with a polyester topcoat without primer were submitted to Prohesion G-85 test (PT) and to outdoor marine exposure test (OT). The new product that replaces standard inorganic chromium pre-treatment + primer consists in a water based resin which applied directly to the properly cleaned metal substrate is then dried in place. This scheme sets aside Cr(VI) compounds which cause severe damages on human health.Goethite, lepidocrocite, magnetite, akaganeite and silicates were found in OT samples coinciding with the usual corrosion products obtained for conventional painting schemes (with Cr(VI)).Surprisingly in PT samples greigite was detected, showing that the new painting scheme is susceptible to microbiological corrosion. Goethite, lepidocrocite, pyrite, magnetite and akaganeite were also found.This study allows the conclusion that in the PT the corrosion mechanism is different from that in the OT for the analyzed samples and should not be used to predict the performance of this kind of outdoor exposed materials.     

Oxidation of green rust suspensions containing different chromium ion species

The oxidation of hydrosulphate green rust (GR2(SO₄²⁻)) suspension containing different chromium ion species was investigated by X-ray diffraction, X-ray absorption spectroscopy and transmission electron microscopy. The pH, oxidation-reduction potential and amount of dissolved oxygen in aqueous solutions were measured during the reactions. The results show that the addition of Cr(III)₂(SO₄)₃ solution suppresses the transformation of GR2(SO₄²⁻) into iron oxyhydroxides and oxides in aqueous solution, while the addition of Na₂Cr(VI)O₄ solution promotes the transformation of GR2(SO₄²⁻) in which Cr(VI) is reduced to Cr(III); α-FeOOH particles were refined by the addition of the chromium ions.     

Characteristics of Zinc Corrosion and Formation of Conversion Films on the Zinc Surface in Acidic Solutions of Cr(III) Compounds

The influence of the components of an acidic solution: Cr(III) nitrate-malonic acid-Co(II) salt and treatment conditions on zinc dissolution and formation of Chromate films as well as on their decorative and protective properties have been studied using the analytical, XPS, structural and accelerated corrosion test methods. An organic acid is the main component, which has an essential influence on zinc dissolution and formation of Chromate films as well as their decorative and protective properties. The influence of organic acid is directly related with the state of the Cr³⁺ ions in chromating solution. When the Cr³⁺ ions are in the form of hexaaquaions, the organic acid increases the quantities of the zinc dissolved and the Cr(III) deposited on the zinc surface (especially at 60°C). It also predetermines the formation of a thick, porous Chromate film with large cracks at 60°C. Its decorative and protective properties are rather poor. When Cr³⁺ ions are in the form of a complex with organic acid, the quantities of the zinc dissolved and the Cr(III) deposited on the zinc surface significantly decrease and thinner Chromate films with an even surface, good decorative appearance and high corrosion resistance are formed Decorative blue-bright Cr(VI)-free films with a slight iridescent tint, obtained in solution, containing Cr(III) nitrate (0.2), malonic acid (0.3) and Co(II) nitrate (0.02) mol dm^?3, at p H 1.6-2.0 at room temperature over 30–60 s, possess corrosion resistance (192–240 h in a salt spray chamber) similar to that of iridescent Chromate films, obtained in acidic Cr(VI) solution.     

Dry sliding tribological behaviour of bilayer Cr/Cr coatings obtained in sulphate Cr(III) baths

This study was intended to investigate the properties of Cr/Cr bilayer coatings. These coatings were deposited on a copper substrate by the DC electrodeposition method from Cr(III) sulphate baths with additions of formate-urea or glycine as complexing agents. Examination of the surface morphology of Cr coatings with SEM has shown that both single and bilayer Cr coatings obtained in the Cr(III) bath with formate-urea, and those obtained in the Cr(III) bath with glycine are cracked. It has been determined that the surface microhardness (HV) of bilayer Cr coatings obtained in the Cr(III) bath with glycine is higher compared with that of single-layer Cr coatings. Wear testing of the coatings was undertaken against an Al₂O₃ ball counterface (6?mm diameter) at 1N load. The results indicate that the friction coefficients (COF) of bilayer Cr/Cr coatings obtained in the Cr(III) bath with formate-urea increased from 0.2 to 0.5 compared with that of single-layer Cr coatings, while their wear resistance deteriorated. However, bilayer Cr/Cr coatings obtained in the Cr(III) bath with glycine exhibit wear resistance close to that of single coatings with COF equal to 0.05.     

Adsorption of XSD-296 resin for Cr（Ⅵ）

The adsorption properties of XSD-296 for Cr（Ⅵ） were studied by using chemical analysis and infrared spectrometry. Experimental results show that XSD-296 resin has a good adsorption ability for Cr（Ⅵ） at pH=2.6 in the HAc-NaAc medium. The statically saturated adsorption capacity is 235 mg/g resin. The apparent activation energy of adsorption reaction, Ea, is 16.73 kJ/mol, and the thermodynamic parameters are △H=11.62 kJ/mol, △G298 K=-4.13 kJ/mol. The adsorption behavior of resin for Cr（Ⅵ） is in accordance with Freundlich adsorption isotherm. Cr（Ⅵ ） adsorbed on resin can be eluted by 5%NaCl-5%NaOH or 5%NH4Cl-5%NH3-H2O quantitatively. Infrared spectra and adsorption mechanism show that the functional group of resin coordinates with Cr（Ⅵ） to form co-ordination compound. The coordination molar ratio of the functional group of resin to Cr（Ⅵ） is 1：1.     

Influence of SiC + WC addition to Cr(VI) bath on corrosion behaviour of coatings in sulphate solution

Abstract

Cr–WC–SiC coatings were deposited from Cr(VI) baths containing a mixture of both WC and SiC particles in the ratio of 1 : 1. X-ray photoelectron spectroscopy data indicated relatively low percentages of both WC (about 2˙68–2˙85 at.-% of W4f) and SiC (0˙16–0˙45 at.-% of Si2p) particles in the top layers of the Cr–WC–SiC coatings. However, these particles have some effect on the morphology and corrosion properties of the Cr coating. Protective properties of the coatings obtained were studied at different exposure times of samples in sulphate solution (pH=2˙8), using the electrochemical impedance spectroscopy method (EIS). Equivalent circuits, based on the electrophysical model describing the electrochemical corrosion at the coated surface, were proposed. The simulation of EIS data with the proposed equivalent circuit models made it possible to reveal the details of the corrosion processes occurring at coated systems (steel/Cr–WC–SiC coatings) immersed in the sulphate solution. Based on EIS data, diffusion in the coating was found to be a significantly controlling factor in the corrosion process for the system under investigation. The electrochemical impedance spectroscopy tests indicated a better corrosion resistance of Cr–WC–SiC coating than that of Cr. Analysis of the EIS data suggests that the enhanced corrosion resistance of Cr–WC–SiC coating was due to the microstructural features of these coatings, presumably containing smaller pores than Cr coating.     

Investigation on carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water

The carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water is studied by potentiodynamic curve and electrochemical impedance spectroscopy (EIS); the micro-structure and composition of the corrosion scale formed at high-temperature and high-pressure are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that 13Cr stainless steel is in passive state in the stratum water, the passive current density increases and the passive potential region decreases with increasing temperature. The corrosion scale formed at high-temperature and high-pressure is mainly composed of iron/chromium oxides and a little amount of FeCO₃.     

Kinetics and mechanism of chromium electrodeposition from methanesulfonate solutions of Cr(III) salts

Kinetics and mechanism of the chromium electrodeposition process in methanesulfonate and sulfate solutions of Cr(III) ions have been investigated. The electroreduction of Cr(III) complex ions is shown to proceed stepwise with the formation of relatively stable intermediates—Cr(II) compounds. Chromium is established to be deposited via the discharge of Cr(II) hydroxocomplexes in these electrochemical systems. Some differences in electrodeposition behavior of methanesulfonate and sulfate trivalent chromium electrolytes are associated with the differences in their buffering capacity.     

Thermal stability behaviors of Cr(N,O)/CrN double-layered coatings by TGA/DTA analysis

In this study, Cr(N,O)/CrN double-layered coatings were synthesized using the cathodic arc deposition (CAD) process. CrN film was first deposited onto a substrate as an interlayer to ensure better adhesion, and Cr(N,O) film was subsequently deposited on top of the CrN layer as the surface layer. Variation in the Cr(N,O) coating composition was achieved through changing the O₂/N₂ flow ratio during the last stage of processing. Phase structure, chemical composition, and morphology of the resulting coatings were analyzed and observed using the X-ray diffractometer, Auger electron spectrometer and SEM. In addition, oxidation behavior of the coatings was investigated using TGA/DTA methods. The tests were carried out by increasing temperature up to 1000 °C in ambient air. With the introduction of oxygen gas during the CAD process, a superficial layer was produced in the Cr(N,O) constituent containing CrN and Cr₂O₃ phases. The formation of the oxide phase attributed to the reaction of chromium and oxygen was more favorable than that of chromium and nitrogen. The results also showed that Cr(N,O)/CrN double-layered coatings exhibited superior oxidation resistance at elevated temperature than that of CrN single-layer coated specimen (870 °C vs. 750 °C).     

Corrosion behavior of Cr/Cu-coated Mg alloy (AZ91D) in 0.1 M H2SO4 with different concentrations of NaCl

An electroplating process was proposed for obtaining a protective Cr/Cu deposit on the two-phase Mg alloy AZ91D. The corrosion behavior of Cu-covered and Cr/Cu-covered AZ91D specimens was studied electrochemically in 0.1 M H₂SO₄ with different NaCl concentrations. Experimental results showed that the corrosion resistance of an AZ91D specimen improved significantly after Cr/Cu electrodeposition. The corrosion resistance of Cr/Cu-covered AZ91D decreased with increasing NaCl concentration in 0.1 M H₂SO₄ solution. After immersion in a 0.1 M H₂SO₄ with a NaCl-content above 3.5 wt.%, the surface of Cr/Cu-covered AZ91D suffered a few blisters. Cracks through the Cr deposit provided active pathways for corrosion of the Cu and the AZ91D substrate. Formation of blisters on the Cr/Cu-covered AZ91D surface was confirmed based on the results of an open-circuit potential test, which detected an obvious potential drop from noble to active potentials.     

High temperature oxidation of a (Cr2N−Mo2S3)/Cr double-layered coating deposited on steel by D.C. magnetron sputtering

A coating consisting of (Cr₂N−Mo₂S₃) overlay coating and an underlying Cr coating was deposited on a steel substrate by D.C. magnetron sputtering. The oxidation characteristics of the deposited double-layered coating were studied at temperatures ranging from 400 to 900 °C in air. The oxidation product was primarily Cr₂O₃. The unreacted coating beneath the oxide scale had some dissolved oxygen, sulfur, and iron. Oxidation of the coating occurred via complex routes such as the outward diffusion of chromium and nitrogen from Cr₂N and iron from the substrate, and the inward transport of oxygen from air, chromium from Cr₂N, and S from Mo₂S₃. This counter diffusion of various ions occurred easily via fine crystallites that constituted the coating, which had some solubility of S, O, and Fe.     

Influence of electrodeposition potential,TiO2 nanoparticles and chromium (III) inhibitor addition on the corrosion protection performance of organosilane coating on aluminium

In this work, the anticorrosion properties of phenyl trimethoxysilane (PTMS) films coated on aluminium 5000 series alloys were studied. PTMS films were deposited at various cathodic potentials. The optimum electrodeposition potential was found to be ?0.8?V vs. SCE. The coatings were also modified by different amounts of nano-TiO₂. In order to introduce corrosion inhibition and a self-repair property of the PTMS film, the addition of chromium (III) corrosion inhibitor in the presence of nano-TiO₂ was studied. The anticorrosion performance of coatings was investigated in a 3.5 wt.% NaCl solution. At optimum deposition potential, the ‘critical’ nano-TiO₂ and Cr(III) contents were both observed, under which the obtained PTMS coatings show the highest anticorrosion performance. The surface morphologies of PTMS coatings were examined by scanning electron microscopy. The results showed that the coatings deposited at ?0.8?V vs. SCE, from 20?ppm of nano-TiO₂ and 0.003 M Cr(III) inhibitor present uniform and compact morphologies.     

Towards improved integrated properties in FeCrPCB bulk metallic glasses by Cr addition

Fe-based soft-magnetic metallic glasses (MGs) of Fe_80−xCr_xP₉C₉B₂ (x = 0, 2, 5, 8 and 16 at.%) with high glass-forming ability (GFA), good soft-magnetic properties and high corrosion resistance are fabricated. With the addition of Cr to FePC-based alloys, the GFA and saturation magnetization (M_s) slightly decrease while the corrosion resistance effectively increases. The Fe–Cr–P–C–B BMGs exhibit good GFA and fully glassy rods can be produced up to 1.8 and 1.5 mm in diameter for the 2 and 5 at.% Cr added alloys, respectively. The alloys with 2 and 5 at.% Cr addition also show good soft-magnetic properties featured by high M_s of 1.16 and 1.04 T, low coercivity of 2.7 and 2.2 A/m, respectively. Besides, the corrosion behavior of the alloys was studied by immersion tests and potentiodynamic polarization measurements. It was found that the addition of Cr efficiently enhances the corrosion resistance of Fe–Cr–P–C–B alloys and the glassy alloy with 5 at.% Cr addition exhibits better corrosion resistance in comparison with the stainless steel SUS304 in 3 mass% NaCl solution. The combination of large GFA, good soft-magnetic properties, high corrosion resistance as well as low cost makes the Fe–Cr–P–C–B alloys as promising soft-magnetic and anti-corrosive materials for industrial applications.     

The influence of chromium content on the electrochemical behavior of weathering steels

To investigate the influence of chromium content on corrosion characteristics of weathering steels, the electrochemical measurements were performed on the steels containing 0–9% Cr (wt.%) in NaHSO₃ aqueous solution. The results indicated that the open circuit potential of these steels shifted to the positive direction remarkably, because the additions of Cr improved the passivation capability of the steels. The corrosion current density of the steels containing more than 7% Cr (wt.%) decreased significantly after pre-rusted treatment, implying the corrosion resistance could be enhanced by the formation of protective goethite rust layer.