Hydrogen-induced cracking of pure titanium in sulphuric acid and hydrochloric acid solutions using constant load method

The hydrogen-induced cracking (HIC) of the commercial pure titanium (Ti) has been investigated as functions of applied stress and test temperature in sulphuric acid and hydrochloric acid solutions by using a constant load method. From the results obtained, HIC was hydrogen embrittlement (HE) related to the fracture of hydride. We have also found that the steady state elongation rate obtained from corrosion elongation curve becomes a relevant parameter for predicting time to failure and a criterion to assess whether HIC takes place or not. A parameter, t_sst_f⁻¹ was also found to become an indicator to assess whether HE takes place or not. Furthermore, it was deduced that HIC was qualitatively explained in terms of hydride formation and a localized deformation, which was basically based on a hydride formation-rupture event at crack tips.     

Evaluation of hydrogen absorption behaviour during acid etching for surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys

The hydrogen absorption behaviour during acid etching for the surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys has been investigated on the basis of the surface morphology, electrochemical behaviour and hydrogen thermal desorption analysis. To simulate the conventional acid etching for the improvement of the biocompatibility of Ti alloys, the specimens are immersed in 1 M HCl, 1 M H₂SO₄ or 0.5 M HCl + 0.5 M H₂SO₄ aqueous solution at 60 °C. Upon immersion, commercial pure Ti absorbs substantial amounts of hydrogen irrespective of the type of solution. In H₂SO₄ or HCl + H₂SO₄ solutions, the hydrogen absorption occurs for a short time (10 min). For Ti-6Al-4V alloy, no hydrogen absorption is observed in HCl solution, whereas hydrogen absorption occurs in other solutions. For Ni-Ti superelastic alloy, the amount of absorbed hydrogen is large, resulting in the pronounced degradation of the mechanical properties of the alloy even for an immersion time of 10 min, irrespective of the type of solution. The hydrogen absorption behaviour is not necessarily consistent with the morphologies of the surface subjected to corrosion and the shift of the corrosion potential. The hydrogen thermal desorption behaviour of commercial pure Ti and Ni-Ti superelastic alloy are sensitively changed by acid etching conditions. The present results suggest that the evaluation of hydrogen absorption is needed for each condition of acid etching, and that the conventional acid etching often leads to hydrogen embrittlement.     

Corrosion resistance properties of plasma nitrided Ti-6Al-4V alloy in nitric acid solutions

The corrosion resistance of plasma nitrided Ti-6Al-4V titanium alloy in nitric acid solutions was investigated using polarisation curves, cyclic voltammetry, XRD analysis and surface microhardness. For comparison, untreated alloy samples were tested under the same conditions. While the untreated alloy shows a passive behaviour, the compound layer obtained by glow-discharge nitriding treatment, which is composed of an outer TiN and an inner Ti₂N layer, shows a high electrochemical inertia; however, if the polarisation potential is higher than a threshold or the period of immersion in high oxidising acid solution is sufficiently long, then the compound surface layer will be attacked and removed with corrosion rate higher than in the case of the untreated Ti-6Al-4V alloy. The corrosion resistance of Ti₂N layer results higher in comparison with that of TiN layer.     

Hydrogen absorption monitoring of sputter-deposited Ti film in seawater

Hydrogen absorption in Ti film sputter-deposited on glass plate immersed in sodium chloride solution of seawater concentration was monitored using resistometry. Increase in electric resistance due to increase in hydrogen content or growth of hydride in Ti during cathodic polarization was evaluated. A monitoring system was developed in which a couple of Ti films were used to reduce influence of temperature-fluctuation on resistance; one was used as a working electrode exposed to electrolyte solution and another was used as a reference resistance with silicon sealant coating. Two films were connected electrically in series, and applied by constant AC to measure resistance of the working electrode as relative value against the reference resistance. Increase in resistance during cathodic polarization at −0.8 V_RHE was observed after some induction period. Scratching test during cathodic polarization did not provide major effect on hydrogen absorption.     

A resistometric study of the passive film on an evaporated iron electrode

Cathodic reduction mechanisms of the passive film formed on an evaporated iron electrode in a neutral solution were studied by chronopotentiometry, colorimetric analysis and measurement of the electrical conductance of the film electrode (resistometry). By galvanostatic cathodic reduction, the outer γ-Fe₂O₃ layer was reduced to ferrous ion and dissolved with nearly 100% current efficiency without showing any change in the conductance of the film. The inner magnetite layer was partly reduced to metallic iron and the residual part was dissolved as ferrous ion. The latter reaction was predominant in low pH. From the increase in conductance in the initial part of cathodic reduction, it was concluded that adsorbed oxygen fortified the passivity by lowering the conductance of the passive film.     

Dealloying behaviour of Cu-20Zr alloy in hydrochloric acid solution

The dealloying of the duplex-phase Cu-20Zr cast alloys and corresponding sputtered Cu-20Zr films (wt.%) in hydrochloric acid solution was investigated using electrochemical, chemical and surface analysis techniques. Results show that the dissolution mechanisms for the cast alloy and the films were strongly depended on the electrochemical activities of Zr and Cu in each phase in 0.1 mol/l HCl solution. When the potential was between the redox potentials of Cu/Cl⁻/CuCl_s and Zr/Zr⁴⁺, the dissolution is attributed to the selective removal of Zr atoms in the cast alloy and the sputtered films; when the potential was higher than the redox potential of Cu/Cl⁻/CuCl_s, Cu and Zr atoms in the samples dissolved simultaneously. In duplex-phase cast alloy, of Zr in the different phases in the alloy, Zr in the zirconium-rich phase was in preference to dissolve owing to its high electrochemical activities. Namely the selective phase attach firstly happens in the cast alloy. The study of the corrosion characteristic of sputtered films showed that Cu atoms reacted with Cl⁻ ions in the solution and formed the corrosion product of Cu(I) and Cu(II) complex ions, which restrained the dissolution of Cu atoms.     

The growth mechanism of CO2 corrosion product films

Carbon steel usually has high corrosion rate in water with dissolved CO₂ however the steel surface can be covered by protective corrosion product film. Therefore the carbon steel can be widely used in oil and gas industry. This paper discusses the structure, electrochemistry performances, initiation and growth of protective corrosion product films. A duplex layer structure of FeCO₃ films was found by electrochemical impedance spectrum (EIS). The physical and chemical situations of solution near carbon steel surface were investigated by ultraviolet spectrophotometry and chronopotentiometry. According to crystallography the growth mechanisms of protective CO₂ corrosion product films were discussed.     

Open circuit potential transients and electrochemical quartz crystal microgravimetry measurements of dissolution of copper in acidic sulfate solutions

It is demonstrated that open circuit potential transients measurements are able to give the realistic and fast information on the rate of metal corrosion. The results of the studies of the rate of copper corrosion in naturally aerated unstirred acidic sulfate solutions obtained by this method are close to the results of electrochemical quartz crystal microgravimetry measurements. It was found that within the concentration range CuSO₄: 0.001-0.01 M, H₂SO₄: 0.005-0.5 M, independently of whether 0.1 M K₂SO₄ is present in the solution or not, the rate of corrosion of thin (about several tens monolayers) and fresh deposits of copper does not depend on the solution composition and is limited by the transport of the dissolved oxygen. The rate of corrosion of such deposits sometimes exceeds the rate of corrosion of compact copper samples.     

Effect of magnesium hydride on the corrosion behavior of an AZ91 magnesium alloy in sodium chloride solution

The effect of magnesium hydride on the corrosion behavior of an as-cast AZ91 alloy in 3.5 wt.% NaCl solution was investigated using gas collection method and potentiostatic test. The Pourbaix diagram of Mg–H₂O system was built using thermodynamic calculation. It was possible that magnesium hydride could form in the whole pH range in theory. The experimental results showed that at cathodic region, magnesium hydride formed on surface, which was the controlling process for the corrosion behavior of AZ91 alloy; at anodic region and free corrosion potential, magnesium hydride model and partially protective film model, monovalent magnesium ion model and particle undermining model were responsible for the corrosion process of AZ91 alloy.     

Crack tip chemistry and electrochemistry of environmental cracks in AA 7050

The role of the crack environment in establishing environment-assisted crack (EAC) propagation in AA 7050 alloys is elucidated. A suite of mini-electrodes provided real-time in situ measurements of the crack potential, pH, and chloride concentration during stage II cracking in a chromate-chloride electrolyte under electrochemical control. For material aged to an EAC-susceptible condition, crack growth during an incubation period is characterized by tip polarization to near the applied electrode potential (E_App) and bulk-like chemistry near the crack tip. In contrast, establishment of high-rate crack growth coincided with the development of an acidic, high chloride concentration tip environment and tip depolarization. During steady state high rate crack growth, the tip potential was ∼−0.85V_SCE; near-tip potential gradients were ∼1 V/cm. Large ohmic potential drop within fast-growing cracks is indicative of net anodic current in the near tip region and increased mass transport resistance within the crack due to solid corrosion products and/or hydrogen bubble formation. Microinjection of a corrosion-inhibiting or corrosion-promoting solution at the tip suppresses or prompts, respectively, the transition from incubation to high-rate cracking, highlighting the intimate dependence of the crack growth kinetics on the local chemistry. The exceptional EAC resistance of over-aged AA 7050 is intrinsic; injection of an acidic aluminum chloride solution at the tip of a crack of this material while polarized to a high E_App failed to induce brittle crack advance.     

Effect of cobalt on the corrosion resistance of low alloy steel in sulfuric acid solution

This study examines the effect of cobalt addition on the corrosion resistance of low alloy steel in a 10 wt.% sulfuric acid solution at room temperature. All specimens show passive behaviors over the potential range, 0.5–1.55 V_SCE, and the passive current density decreased with increasing Co addition. The Co-containing steels also show higher polarization resistance and lower corrosion rate. The beneficial effect of Co is attributed to the formation of a uniform and continuous rust layer due to an interaction between Co and other elements such as Fe, O and S.     

Passivity: enabler of our metals based civilisation

Abstract

The origin of passivity, as viewed from the Point Defect Model, is presented in terms of the phase space analysis of the rate law for the growth of passive films. It is shown that passivity is due to the formation of a metastable oxide and hence, the occurrence of passivity is a kinetic phenomenon, in which the rate of film growth of the oxide at the metal/barrier layer interface into the metal at zero barrier layer thickness must exceed the rate of barrier layer dissolution at the barrier layer/solution (bl/s) interface, in order for the barrier layer to exist. If this relationship does not hold, the barrier layer disappears and the surface becomes depassivated. Depassivation is illustrated with respect to transpassive dissolution, acid depassivation, pitting corrosion, flow assisted corrosion, impingement attack, resistive depassivation and other phenomena. The theory also leads to the development of Kinetic Stability Diagrams (KSDs), in which the potential for depassivation is plotted against pH to define regions of depassivation and passivation, so that regions in potential versus pH space can be defined within which passive films may exist as protective, metastable entities. The author offers these diagrams as kinetically inspired alternatives to the classical Pourbaix diagrams. One form of depassivation that occurs at highly localised regions on a metal surface is pitting corrosion. The theory for pitting is now highly developed and certain aspects of the subject are reviewed here. It is argued that the theory of pitting is sufficiently well established that the deterministic prediction of pitting damage is practical, in many systems. The theory is illustrated here with respect to the pitting of Type 403 stainless steel (SS), which is used extensively for the manufacture of low pressure steam turbines in steam cycle systems for the generation of electrical power.     

Mechanism of dissolution of a Cu-13Sn alloy in low aggressive conditions

Corrosion of a synthetic Cu-13Sn alloy with a dendritic structure was investigated in a low aggressive medium (0.01 M Na₂SO₄ aqueous solution). The corrosion rate was accelerated through anodic polarization of the alloy in a potential range close to the open-circuit potential. The composition of the corrosion layer was followed as a function of the polarization time, using scanning electron microscopy and energy dispersive spectrometry methods. The results clearly showed that bronze corrosion in these experimental conditions proceeds by decuprification. Selective copper dissolution leads to corrosion layers enriched in tin compounds. It was concluded that bronze is partially passivated through the presence of a tin oxide layer, which slows down copper dissolution rate, compared to pure copper.     

Effect of nickel alloying on crevice corrosion resistance of stainless steels

The crevice corrosion behaviour of stainless steels containing 25 mass% Cr, 3 mass% Mo and various amounts of Ni was investigated in natural seawater. The results showed that ferritic steels containing nickel were more resistant to corrosion than both ferritic steels without nickel and austenitic steels. The superiority of the Ni bearing ferritic steel over the other steels was in close agreement with the depassivation pH of those steels in acidic chloride solutions. The results showed that the addition of Ni to ferritic steel was effective in decreasing the depassivation pH and the dissolution rate in acidic chloride solutions at crevices.     

Inhibition treatment of the corrosion of lead artefacts in atmospheric conditions and by acetic acid vapour: use of sodium decanoate

The efficiency of linear sodium decanoate, CH₃(CH₂)₈COONa (noted NaC₁₀), as corrosion inhibitor of lead was determined by electrochemical techniques in two corrosive mediums: ASTM D1384 standard water and acetic acid-enriched solutions. Best results were obtained with 0.05 mol l⁻¹ of NaC₁₀ solution. In these conditions, the inhibition efficiency can be estimated of 99.9%. The corrosion inhibition effect was confirmed by cyclic atmospheric tests in a climatic chamber in two different conditions: water saturated vapour, and acid acetic enriched vapour simulating the atmosphere in the wooden displays in museums. Surface analyses by SEM and X-ray diffraction indicate that the metal protection is due to the formation of a protective layer mainly composed of lead decanoate Pb(C₁₀)₂ (metallic soap). This inhibition treatment was applied on objects of metallic cultural heritage: gallo-roman sarcophagus in lead. Electrochemical methods confirm the efficiency of treatment on archaeological materials. In conclusion, this inhibitor treatment seems to be very promising against the atmospheric corrosion and the corrosion by organic acid vapour in museums.     

Electrochemical behaviour of high nitrogen stainless steel in acidic solutions

The electrochemical behaviour of high nitrogen stainless steel in acidic solutions was studied by potentiodynamic polarization, EIS, Mott-Schottky and XPS. The passive film formed in neutral NaCl solution was very stable, but the stability of the film decreased with the addition of H₂SO₄ into the solution. The passive film formed in acidic Na₂SO₄ has a superior protective ability than that in acidic NaCl solution. The stability of the film formed in tested solution decreased with increase of applied potentials. The film formed on steel surface was of n-type semiconductor. Chloride penetration mechanism was proposed for the observed passive film breakdown.     

Al/Ti扩散层形成的扩散溶解机制

分别在铝组元熔点之下和之上对Al/Ti镶嵌式扩散偶进行退火热处理,形成固-固和固-液扩散偶.利用光学显微镜、扫描电子显微镜和电子探针显微分析仪观察和分析Al/Ti固-固和固-液扩散层的形态和结构,并对其形成微观机理进行了研究.结果表明,Al/Ti固-固扩散层由一层TiAl₃构成;固-液扩散层由TiAl₃单相层与TiAl₃和Al(Ti)固溶体双相层两层构成,双相层TiAl₃和Al(Ti)固溶体的形态自铝向钛呈现规律性变化.Al/Ti固-固TiAl₃扩散层和固-液TiAl₃单相层的形成都是铝扩散溶解到钛中形成以钛为溶剂的Al-Ti固溶体结晶形成的;而Al/Ti固-液TiAl₃和Al(Ti)固溶体双相层是钛先溶解再扩散到液态铝中形成的Al-Ti液溶体结晶形成的.铝液中Ti原子浓度自铝向钛逐渐升高,导致了双相层TiAl₃和Al(Ti)固溶体形态的规律性变化.     

Influence of pH on the passivation behavior of 254SMO stainless steel in 3.5% NaCl solution

The potentiodynamic polarization measurement of 254SMO stainless steel (UNS 31254) was conducted in 3.5% NaCl solutions with pH ranging from 0.1 to 5. The results indicated that this stainless steel offered excellent pitting corrosion resistance in corrosive environments. Further, it also exhibited various features on the polarization curves in different pH solutions. The electrochemical constant-potential passivation treatment performed at different pH followed by XPS analysis revealed that the primary constituents of the outermost layer of the passive films formed in the weak (pH 5) and strong (pH 0.8) acid solutions are iron oxides and Cr₂O₃ and Cr(OH)₃, respectively. Molybdenum oxides, primarily in the six-valence state, existed in the outermost layer of the passive film. Only very weak signals corresponding to that of nickel oxides were detected in the film formed in the weak acid (pH 5) solution. The ICP-MS analyses indicated selective dissolution of a significant amount of Fe and a few Mo and Ni ions during the passivation treatment in the strong acid (pH 0.8) solution. No Cr dissolution was observed; this indicated that the Cr in the film is relatively stable. XPS depth profiling results showed that a similar bilayer-structured film was formed in both the solutions (pH 0.8 and 5); the outer layer of this film is primarily composed of Cr(OH)₃ and Mo(VI), and the inner layer, Cr₂O₃ and Mo(IV). The results of the examinations of passive film formations and dissolution by XPS and ICP-MS were consistent with the polarization curves.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

The inhibition activity of ascorbic acid towards corrosion of steel in alkaline media containing chloride ions

The activity of ascorbic acid towards steel corrosion in saturated Ca(OH)₂ solution containing chloride ions was investigated in this study. Concentration and time dependence of the protective properties of the passive film were acquired by electrochemical impedance spectroscopy. The best inhibitive performance, i.e. the longest pitting initiation time was obtained in the presence of 10⁻³ M ascorbic acid, while both lower and higher concentrations showed shortening of the pitting-free period. The overall behaviour of ascorbic acid was attributed to its ability to form chelates of various solubility having various metal/ligand ratios and oxidation states of the chelated iron. The assumption of ascorbic acid assisted reductive dissolution of the passive layer at higher inhibitor concentrations was confirmed by cyclic voltammetry and ATR FTIR spectroscopy. It is proposed that the overall inhibitive effect at lower concentrations is due to the formation of insoluble surface chelates and the effective blocking of the Cl⁻ adsorption at the surface of passive film. A pronounced inhibitive effect observed after the pitting had initiated was ascribed to the formation of a resistive film at the pitted area.