Comparison of repassivation kinetics of stainless steels in chloride solution

Using a rapid scratching electrode technique, the repassivation kinetics of type 304, 316, 444, and 2205 stainless steels (SS) were investigated in a chloride solution. The value of cBV in a log i(t) versus 1/q(t) plot as an effective measure of the repassivation rate was used to compare the reapssivation behaviors among the alloys. During repassivation, lower values of cBV for SS corresponded with faster repassivation rates with the formation of a more protective passive film. In a comparison of repassivation rates based on the alloy’s cBV values, the best repassivation behavior was shown by 2205 SS, followed by 444 SS and 316 SS. However, 304 SS exhibited an inflection point in the log i(t) versus 1/q(t) curve, suggesting that dissolution by localized corrosion rather than SCC may occur in the alloy under given conditions.     

Effects of PbO on the repassivation kinetics of alloy 690

Effects of PbO on the repassivation kinetics of alloy 690 were examined to elucidate the reason why the alloy, otherwise immune, is susceptible to stress corrosion cracking (SCC) in high temperature water contaminated with a small amount of Pb compounds. The repassivation kinetics of the alloy was analyzed in terms of the current density i(t) flowing from the scratch as a function of the charge density q(t) that has flowed from the scratch. During the repassivation on the scratched surface of the alloy, passive film initially nucleated and grew according to the place exchange model in which log i(t) is linearly proportional to q(t), and then grew according to the high-field ion conduction model in which log i(t) is linearly proportional to 1/q(t) with a slope of cBV, a parameter of repassivation rate. The higher the cBV, the slower is the repassivation rate of an alloy. The cBV of alloy 690 was increased significantly in water with PbO compared with that in water without PbO, suggesting that the PbO decreased the repassivation rate of the alloy, and hence reduced the resistance to SCC. The decrease in repassivation rate of the alloy resulted from both Pb-induced Cr dissolution and an incorporation of Pb compounds into the passive film during repassivation.     

Repassivation behaviour of 316L stainless steels using new type of abrading electrode technique

Abstract

In this paper, a novel electrode abrading technique is designed to improve the conventional methods. By employing the new depassivation method, 316L stainless steel has been tested in 0.05M H₂SO₄ solution with and without chloride ion. The repassivation kinetics has been analysed in terms of the current density flowing through the abraded surface bare metal surfaces. The results are described by the linear relationship of log i(t) versus log t. At potentials within the passive region, the passive film grew according to the high field ion conduction model in which log i(t) is linearly proportional to 1/q(t). The repassivation process was analysed in three stages according to different kinetics. The effect of applied potential and chloride ion concentration on repassivation kinetics was also discussed, and the change of calculated film thickness is more sensitive to applied potential than chloride ion concentration.     

Corrosion characteristics of zinc–zirconium alloy in c-SBF and its biocompatibility in vitro/in vivo

Zinc-based metals have attracted attention as biodegradable implant materials for medical applications. New alloying systems are still being tried. In this study, three kinds of extruded zinc–zirconium alloys (R1, R2, and R3) were prepared, and two of the most important performance of corrosion characteristics and biocompatibility in vitro/in vivo were carefully examined. We found that zirconium content did not linearly influence the corrosion behavior. Zirconium improved the zinc–zirconium alloy corrosion potential, but the strengthening effect was weakened due to the ZrZn ₂₂ phase, leading to microgalvanic corrosion. The alloy with zirconium content of 0.8% (R2) showed high corrosion resistance and minimum initial corrosion rate in the corrected simulated body fluid. R2 alloy also exhibited favorable cytocompatibility and biological histocompatibility.     

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.     

Corrosion behavior of under‐, peak‐, and over‐aged 6063 alloy: A comparative study

The mechanical property of age‐hardenable Al‐alloys is governed by the state of ageing, which determines the microstructure and consequently, their corrosion behavior which is a vital aspect for a number of applications. This article presents a comparative assessment of corrosion behavior of under‐, peak‐ and over‐aged Al‐Mg‐Si alloy. Corrosion characteristics have been determined via immersion tests in 0.1 M ortho‐phosphoric acid solution and intergranular corrosion (IGC) tests. Corroded surfaces are examined by field emission scanning electron micrographs‐energy dispersive spectroscopy and 3D optical profilometer. The obtained results reveal that the corrosion rate at a specific immersion time as well as the depth of IGC increases in the order for under‐, peak‐, and over‐aged states. Irrespective of the state of ageing, corrosion loss increases linearly but the rate of corrosion decreases rapidly with increasing immersion time. The dominant mode of corrosion in under‐aged alloy is identified as localized pitting, while peak‐aged is highly susceptible to IGC in contrast extensive pitting corrosion is observed for over‐aged alloy. The observed differences in corrosion behavior are explained considering characteristics of precipitates. Formation of β (Mg₂Si) in case of over‐aged alloy and presence of inclusions like AlFeMnSi particles are found to accelerate pitting corrosion.     

Oxidation Behavior of Nanocrystalline Al Alloys Containing 5 and 10 at.% Ti

The oxidation behavior of mechanically alloyed(MA) Al-Ti alloys containing 5 and 10 at.% Ti wereinvestigated at 500-600°C under 1 atm of oxygen. Ateach temperature, alloys oxidized linearly during the initial stage and later followed the parabolicrate law. During the initial stage, the oxidation ratesof nanocrystalline (50 nm) Al-Ti alloys were fasterthan those of conventional (200 nm) alloys. It is suggested that more grain boundaries innanocrystalline alloys provide more nucleation sites foroxides, so that the oxide scales grew faster as denseprotective layers. During the parabolic stage, the nanocrystalline alloys had greater oxidationresistance than conventional alloys because of the denseprotective layer. Oxide scales on both alloys consistedof a mixture of -Al₂O₃ andTiO₂ in the outer layer and-Al₂O₃ near the alloy as aprotective layer.     

Comparative study of stress corrosion cracking susceptibility of Fe18Cr10Mn- and Fe18Cr10Mn1Ni-based high nitrogen stainless steels

The stress corrosion cracking (SCC) behavior of Fe18Cr10Mn1Ni(0.3–0.8)N alloys was investigated in aqueous NaCl environment by using slow strain rate test method, and the results were compared to those of Ni-free counterparts. The addition of N tended to improve the SCC resistance of Fe18Cr10Mn- and Fe18Cr10Mn1Ni-based alloys. The alloying Ni magnified the beneficial effect of N on the SCC susceptibility and, eventually, the Fe18Cr10Mn0.8N alloy was immune to SCC in 2 M NaCl solution at 50 °C. The SCC behavior of the present alloys was found to be closely related to the repassivation tendency and the resistance to pitting corrosion.     

Corrosion of tin alloys in sulfuric and nitric acids

To obtain a fundamental understanding of the corrosion behavior of lead-free solder, the corrosion behavior of tin-based eutectic alloys in sulfuric and nitric acids saturated with oxygen was investigated. The presence of bismuth in a Sn-Bi alloy (43Sn-57Bi (wt.%)) slightly accelerated the preferential dissolution of tin instead of dissolving itself in 0.05 M H₂SO₄ and greatly accelerated, in 0.1 M HNO₃ compared with that of pure tin. In both acids, dissolution of both tin and zinc from a Sn-Zn alloy (91Sn-9Zn (wt.%)) occurred depending on the ratio of composition, and dissolution of tin from a Sn-Ag alloy (96.5Sn-3.5Ag (wt.%)) was accelerated. Dipping tests in H₂SO₄ and HNO₃ of pH 4 showed that dissolution of only zinc and lead occurred, suggesting that the tin-based alloys investigated in this study are preferable to substitutes for lead solders in terms of corrosion resistance.     

Effect of Copper and Zirconium Addition on Properties of Fe-Co-Si-B-Nb Bulk Metallic Glasses

In this research work, iron-based bulk metallic glasses (BMGs) have been fabricated, characterized and compared with Fe-Si alloy. BMG alloys of composition ((Fe_0.6Co_0.4)_0.75B_0.20Si_0.05)₉₆Nb₄) were synthesized by suction casting technique using chilled copper die. Effect of copper and zirconium addition on magnetic, mechanical, thermal and electrochemical behavior of ((Fe_0.6Co_0.4)_0.75B_0.20Si_0.05)₉₆Nb₄ BMGs was investigated. Furthermore, effect of annealing on nano-crystallization and subsequently on magnetic and mechanical behavior was also analyzed. Amorphousness of structure was evidenced by XRD analysis and microscopic visualization, whereas nano-crystallization behavior was identified by peak broadening of XRD patterns. Magnetic properties, measured by vibrating sample magnetometer, were found to be improved for as-cast BMG alloys by copper addition and further enhanced by nano-crystallization after annealing. Mechanical properties were observed to be increased by zirconium addition while slightly declined by copper addition. Potentiodynamic polarization analysis manifested the positive role of zirconium in enhancing corrosion resistance of BMGs in acidic, basic and brine mediums. Moreover, mechanical properties and corrosion analysis results affirmed the superiority of BMG alloys over Fe-Si alloy.     

Influence of minor additions on the emissivity of the oxide scale of FeCrAlY alloys during resistance heating

Chromium aluminum yttrium (FeCrAlY) alloys owe their low oxidation rate to the formation of a slow growing α‐alumina scale. For material used for heating elements not only the life time and the behavior of the resistance during the life time is of relevance, but also the emission coefficient of the oxide scale. The power density J_S produced by resistance heating of strip with 50 µm thickness and about 5–6 mm width at 1050 °C is approximately equal to the radiant flux density, which is according to Stefan–Boltzmann's law proportional to the total emission coefficient ε_g. Resistance heating tests were performed on samples made from FeCrAlY alloys with different zirconium and carbon content. The “high zirconium” containing FeCrAlY alloys (zirconium > about 0.10%) have a higher power density/emissivity than the “low zirconium” alloys. In parallel with this, all samples with higher power density/emissivity have internal oxidation and therefore a “rough” metal–oxide interface. Thus, one cause for the increase of the emissivity of the scale could be this rough metal–oxide interface; other causes could be a higher amount of zirconium incorporated into the scale, more pores and/or different grain structure in the scale. Additionally the carbon content influences the appearance of a higher emissivity and the internal oxidation.     

Electrochemical Behavior Assessment of As-Cast Mg-Y-RE-Zr Alloy in Phosphate Buffer Solutions (X Na<Subscript>3</Subscript>PO<Subscript>4</Subscript> + Y Na<Subscript>2</Subscript>HPO<Subscript>4</Subscript>) Using Electrochemical Impedance Spectroscopy and Mott–Schottky Techniques

In the present study, electrochemical behavior of as-cast Mg-Y-RE-Zr alloy (RE: rare-earth alloying elements) was investigated using electrochemical tests in phosphate buffer solutions (X Na₃PO₄?+?Y Na₂HPO₄). X-ray diffraction techniques and Scanning electron microscopy equipped with energy dispersive x-ray spectroscopy were used to investigate the microstructure and phases of the experimental alloy. Different electrochemical tests such as potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS) and Mott–Schottky (M–S) analysis were carried out in order to study the electrochemical behavior of the experimental alloy in phosphate buffer solutions. The PDP curves and EIS measurements indicated that the passive behavior of the as-cast Mg-Y-RE-Zr alloy in phosphate buffer solutions was weakened by an increase in the pH, which is related to formation of an imperfect and less protective passive layer on the alloy surface. The presence of the insoluble zirconium particles along with high number of intermetallic phases of RE elements mainly Mg₂₄Y₅ in the magnesium matrix can deteriorate the corrosion performance of the alloy by disrupting the protective passive layer that is formed at pH values over 11. These insoluble zirconium particles embedded in the matrix can detrimentally influence the passivation. The M–S analysis revealed that the formed passive layers on Mg-Y-RE-Zr alloy behaved as an n-type semiconductor. An increase in donor concentration accompanying solutions of higher alkalinity is thought to result in the formation of a less resistive passive layer.     

Corrosion properties of nickel free austenitic stainless steels in 0·5M H2SO4 and 0·5M H2SO4 plus 0·4M NaCl

Abstract

The corrosion behaviour of four nickel free austenitic stainless steels were investigated in 0·5M H₂SO₄ and 0·5M H₂SO₄ plus 0·4M NaCl solutions by means of potentiodynamic and potentiostatic anodic polarisation testing. The performances of the nickel free alloys are compared to those of an experimental intermediate nickel alloy (4%Ni) and a standard AISI 304 steel grade. Once passivity was reached all alloys displayed similar current densities i _p in 0·5M H₂SO₄, independent from alloying. Mo and Cu were shown to be beneficial in decreasing the active dissolution currents and i _crit values. The commercial AISI 304 steel displayed superior resistance to pit initiation during potentiodynamic testing, and AISI 304 steel displayed the highest E _pit value of all alloys tested. When tested potentiostatically the N and Mo alloyed nickel free alloys showed excellent resistance to pit initiation and growth. The dominant effect of N was associated with repassivation of incipient pits, while Mo appeared to act at an earlier stage, suppressing initiation.     

Effect of temperature on corrosion and semiconducting properties of oxide films formed on M5 zirconium alloy

Nuclear fuel cladding for pressurised water reactors is commonly manufactured with zirconium alloys. The M5 alloy is a relatively new cladding material for in-reactor used with enhanced performance compared to traditional zircaloys. In this work, the influence of temperature on the corrosion resistance and semiconducting properties of the passive film formed on the M5 alloy in a borate buffer solution has been evaluated. The electrochemical behaviour of the zirconium alloy was assessed by potentiodynamic polarisation tests, electrochemical impedance spectroscopy and Mott–Schottky plots. The results indicated that the corrosion resistance of the M5 alloy decreased with temperature due to the formation of a less stable and more defective passive film. The Mott–Schottky approach used in combination with polarisation tests and impedance measurements was effective to reveal the protective state of the passive film on the M5 alloy.     

用循环极化曲线研究Al和铝合金的点蚀行为

通过循环极化确定纯Al和Al-7Zn-0.1Sn-0.015Ga (质量分数,%) 合金在3.5%NaCl溶液中的自腐蚀电位E_corr、点蚀电位E_pit、点蚀转变电位E_ptp和保护电位E_rp,并通过Al和铝合金在这些特征电位的点蚀形貌研究了它们的点蚀行为及点蚀扩展机理。结果表明：在点蚀电位时开始出现点蚀坑,随着电位升高点蚀坑迅速向横向和纵向扩展直至保护电位;纯Al的点蚀坑为窄而深的方形点蚀形貌,蚀坑内部为粗糙的结晶状结构,且表面出现明显的丝状腐蚀。Al-7Zn-0.1Sn-0.015Ga合金的点蚀形貌为宽而浅的圆形腐蚀坑,蚀坑内部比较光滑,且丝状腐蚀消失。合金元素能明显活化合金,降低点蚀坑深度,改善其腐蚀形貌。     

The oxidation of Fe-Cr alloys containing an oxide dispersion or reactive metal additions

The oxidation of an iron-16% chromium alloy containing a dispersion of yttria particles and of iron-16 to 18% chromium alloys containing small additions of yttrium or zirconium has been studied at 1100 and 1200°C in 100 Torr oxygen. The yttria-containing alloy exhibited the excellent oxidation resistance usually associated with oxide-dispersion-containing alloys, having a thin, adherent, virtually iron-free scale which resisted the breakaway rapid oxidation behavior commonly found in Fe-Cr alloys in this composition range. Of the alloying additions intended to form a fine oxide dispersion during oxidation, only zirconium affected the oxidation behavior in a beneficial way, the scale on the yttrium-containing alloy being possibly less protective than that on the equivalent binary alloy.Supported by Battelle, Columbus Laboratories, Columbus, Ohio.     

Microstructure characterization and effect of extrusion temperature on biodegradation behavior of Mg-5Zn-1Y-xCa alloy

Microstructure and biodegradation behavior of as-cast and hot extruded Mg-5Zn-1Y alloy containing different amounts of calcium (0.0%, 0.1%, 0.5%, and 1.0%, mass fraction) were explored. The extrusion process was conducted at three different temperatures of 300, 330, and 370 °C. Chemical composition, phase constitution, microstructure, and biodegradation behavior of the alloys were investigated. The macro- and micro-scopic examination revealed that the addition of Ca refines the grain structure and forms an intermetallic phase, Ca₂Mg₆Zn₃. The hot extrusion process resulted in breaking the intermetallic phases into fine particles routed to the extrusion direction. Moreover, dynamic recrystallization happened in almost all alloys, and more bimodal microstructure was formed in the alloys when the alloys were extruded at 370 °C. Polarization curves showed no passive region, which indicated that active polarization dominated in the alloys; therefore, grain refining through Ca addition and dynamic recrystallization over hot extrusion operation increased biodegradation rate. The results show that the as-cast Mg-5Zn-1Y-0.1Ca alloy provides the highest corrosion resistance, and the extruded Mg-5Zn-1Y-0.5Ca alloy at 300 °C shows the lowest biodegradation rate among the extruded alloys. Therefore, hot extrusion does not always improve the biodegradation behavior of magnesium alloys.     

Corrosion behavior of Cu–Al–Be shape memory alloys with different compositions and microstructures

The corrosion behavior of Cu–Al–Be shape memory alloys with different microstructures and Be content in a 3.5% NaCl solution was studied by weight loss, cyclic anodic polarization and chronoamperometric measurements. The beryllium has a beneficial effect in β alloys. A pitting potential of −100 mV/SCE was found by anodic polarization tests for all the studied alloys, corresponding to the formation of pits produced by severe dealuminization. Samples with precipitates were more susceptible to pit formation. The corrosion behavior is strongly affected by the alloy microstructural conditions, and the β samples present higher pitting resistance and repassivation ability.     

Effect of Immersion Time on Corrosion Behavior of Single-Phase Alloy and Nanocomposite Bismuth Telluride-Based Thermoelectrics in NaCl Solution

The corrosiveness of bismuth telluride-based thermoelectric materials (n-type single-phase alloy and a nanocomposite with MoS₂ nanoinclusions), in 0.1 molar solution of sodium chloride (NaCl), was investigated. The electrochemical impedance spectroscopy curves obtained after 1, 24, 48 and 72 h immersion time revealed the enhancement of the corrosion resistance of the nanocomposite specimen in a 0.1 molar NaCl solution in comparison with the single-phase bismuth telluride-based alloys, and the passivity increased by immersion time up to 72 h. The nanocomposite sample with submicron grains provided suitable nucleation sites for passive film nucleation that led to higher protective behavior.     

Role of nitrogen on the corrosion behavior of austenitic stainless steels

The role of nitrogen in the mechanisms of localized corrosion resistance and repassivation were electrochemically investigated using a nitrogen-bearing austenitic stainless (SUS316L) steel in 0.1 and 0.5 M Na₂SO₄ solutions and a 3.5% NaCl solution. Almost 100% of the nitrogen compounds dissolved into the bulk solution after crevice corrosion were transformed into NH₃. That is, the mole amount of ammonia in the solution was approximately equivalent to the mole amount of nitrogen dissolved in the steel. This suggests that NH₄⁺ consuming H⁺ in the pit controlled the local decrease of pH and promoted the repassivation. NO₃-N and NO₂-N were not detected by chemical analyses in the high potential and thermodynamically stable zone as NO₃⁻ in the potential-pH diagram. The repassivation in nitrogen-bearing SUS316L steel in a 0.1 M Na₂SO₄ solution was studied using the scratching electrode technique, which measured the partially destroyed passivation films on the steel. This technique showed that nitrogen dissolved in the steel has a strong repassivation capacity.