Effect of cations on stress corrosion cracking: Ag-40Cd alloy in silver ion aqueous solutions containing a variety of foreign cations

Uhlig showed that cupric ions accelerated the stress corrosion cracking (SCC) of α-brass in ammoniacal solutions. When adding foreign metal cations (cadmium, zinc, cobalt and nickel) to the solutions, it was found that only the copper ion had an effect on the fracture time. The aim of the present work was to study if this is a more general phenomenon in SCC. To that purpose, a Ag-40Cd (at/o) alloy was strained in silver nitrate aqueous solutions containing a variety of foreign metal cations, at the equilibrium potential of the reaction: Ag⁺ + e⁻ = Ag. SCC was found in all cases. Silver ions specifically accelerated the crack propagation rate and the addition of foreign cations showed no significant effect on the phenomenon. Most of the cracks found were intergranular, and the specific effect of the cations could be explained through the surface mobility SCC mechanism.     

Effect of common water contaminants on the corrosion of aluminium alloys in ethylene glycol-water solution

The effects of common water contaminants of chloride (Cl⁻), cupric (Cu²⁺) and ferric (Fe³⁺) ions, in four different mixture combination of Fe³⁺ + Cu²⁺, Cl⁻ + Fe³⁺, Cl⁻ + Cu²⁺ and Cl⁻ + Fe³⁺ + Cu²⁺, were examined on the corrosion behaviour of aluminium alloys in ethylene glycol-water solution, using mass loss technique. The highest material losses were recorded for the two alloys in ethylene glycol solution containing the combination of the chloride and the two heavy metal ions. The corrosivity of the solution in the presence of the combination of ions was in the order of Cl⁻ + Fe³⁺ + Cu²⁺ > Cl⁻ + Cu²⁺ > Cl⁻ + Fe³⁺ > Fe³⁺ + Cu²⁺. The results gave first-order kinetics with respect to aluminium in ethylene glycol solution-ion systems. Alloy 3SR exhibits maximum corrosion in all the solutions. It is concluded that the two commercial alloys in the solution polluted with all the three ions would not be able to survive for reasonable period of time without corrosion inhibitor.     

Modification of hard alloy by the action of high power ion beams

Phase composition, sizes of coherent scattering regions, hardness and friction coefficient of WC-TiC-Co hard alloy and “(Ti,Cr)N coating-on-alloy” system treated by high power ion beams (HPIB) are studied. HPIB treatment was carried out with power densities from 4 to 16 J/cm². The effect of HPIB pretreatment (4 J/cm²) before deposition procedure was studied. HPIB action with energy densities of 8-16 J/cm² on hard alloy results in partial fusion of tungsten and titanium carbides. The hardness of surface layer increases by two times and wear resistance improves. HPIB action on “coating-on-alloy” system leads to coarsening of (Ti,Cr)N crystallites, partial decomposition of (Ti,Cr)N and precipitation of chromium phase. Preliminary HPIB treatment (4 J/cm²) followed by HPIB impact (16 J/cm²) provides best effect on wear-resistance of (Ti,Cr)N solid solution on hard alloy.     

Anodic oxidation and dielectric behaviour of aluminium-niobium alloys

The anodizing behaviour of sputtering-deposited Al-Nb alloys, containing 21, 31 and 44 at.% niobium, has been examined in 0.1 M ammonium pentaborate electrolyte with interest in the composition and the dielectric properties of the anodic oxides. RBS and TEM revealed amorphous oxides, containing units of Nb₂O₅ and Al₂O₃ in proportion to the alloy composition. Xenon marker experiments indicated their growth through migration of the Nb⁵⁺, Al³⁺ and O²⁻ species, with cation transport numbers, in the range 0.31-0.35, and formation ratios, in the range 1.35-1.64 nm V⁻¹, intermediate between those of anodic alumina and anodic niobia. Al³⁺ ions migrate slightly faster than Nb⁵⁺ ions, promoting a thin alumina layer at the film surface, although this layer is penetrated by fingers of the underlying niobium-containing oxide of relatively reduced ionic resistivity. The incorporation of units of Nb₂O₅ into anodic alumina increases the dielectric constant from about 9 to the range 11-22 for the investigated alloys.     

Synergistic corrosion inhibition study of Armco iron in sodium chloride by piperidin-1-yl-phosphonic acid-Zn system

Electrochemical techniques, weight loss method and surface analysis were used to study the synergistic inhibition offered by Zn²⁺ and piperidin-1-yl-phosphonic acid (PPA) to the corrosion of Armco iron in 3% chloride solution. It is observed that the combination between PPA and Zn²⁺ shows excellent inhibition efficiency. The potentiodynamic polarization curves reveal that 5 × 10⁻³ mol l⁻¹ of PPA has only 76.7% inhibition efficiency whereas the mixture containing 5 × 10⁻³ mol l⁻¹ PPA -20%Zn²⁺ has 90.2% inhibition efficiency. This suggests that a synergistic effect exists between Zn²⁺ and PPA. The Fourier transform infrared (FTIR) spectrum of the film formed on iron indicates phosphonates zinc salt formation. A suitable mechanism of corrosion inhibition is proposed based on the results obtained. The surface film analysis showed that in the absence of Zn²⁺, the protective film consists of Fe²⁺-PPA complex formed on the anodic sites of the metal surface, whereas in the presence of Zn²⁺, the protective film consists of Fe²⁺-PPA complex and Zn(OH)₂.     

Effect of cations on corrosion of zinc and carbon steel covered with chloride deposits under atmospheric conditions

The effect of sodium, calcium, and magnesium chlorides deposited on zinc and carbon steel surfaces was studied under atmospheric conditions. The cations strongly affected the corrosion rate of zinc, whereas they had a significantly lower impact on the corrosion of carbon steel. The corrosivity of cations of chloride salts for zinc increased in order of Mg²⁺ < Ca²⁺ < Na⁺. The higher corrosion resistance of zinc treated with calcium and magnesium chlorides was connected to prevention of formation of hydrozincite during zinc exposure in wet air. It was observed that zinc weight loss and the carbonate to simonkolleite ratio in corrosion products were correlating. The principal protective effect of bivalent cations can be seen in the decrease of pH of the surface electrolyte, which was caused by hydrolysis of such cations and subsequent formation of simonkolleite that blocked the cathodic sites.     

Influence of oxygen ion irradiation on the corrosion aspects of Ti-5%Ta-2%Nb alloy and oxide coated titanium

The corrosion resistance of Ti-5%Ta-2%Nb alloy and DOCTOR (double oxide coating on titanium for reconditioning) coated titanium by O⁵⁺ ion irradiation were compared and investigated for their corrosion behaviour. O⁵⁺ ion irradiations were carried out at a dose rate of 1 × 10¹⁷, 1 × 10¹⁸ and 1 × 10¹⁹ ions/m² at 116 MeV. The surface properties and corrosion resistance were evaluated by using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), glancing-angle X-ray diffraction (GXRD) and electrochemical testing methods. The results of electrochemical investigations in 11.5 N HNO₃ indicated that the open circuit potential (OCP) of DOCTOR coated titanium is nobler than Ti-5%Ta-2%Nb alloy. The potentiodynamic polarization study of Ti-5%Ta-2%Nb alloy and DOCTOR coated specimen indicated decrease in passive current density with increase in ion doses (1 × 10¹⁷ to 1 × 10¹⁹ ions/m²) indicating decrease in anodic dissolution. Nyquist arc behaviour in the electrochemical impedance study substantiated the enhancement in oxide layer stability by O⁵⁺ ion irradiation. AFM results revealed that the DOCTOR coated Ti surface was dense without gross voids, and the surface roughness decreased by O⁵⁺ ion irradiation, but increased after corrosion test. EDX and GXRD patterns of DOCTOR coated Ti sample indicated that the coating was mainly composed of rutile TiO₂. Based on the above results, the O⁵⁺ ion irradiation effect on corrosion behavior of Ti-5%Ta-2%Nb alloy and DOCTOR coated titanium are discussed in this paper.     

AE response of α-brass during stress corrosion crack propagation

The present work was aimed at characterizing the acoustic emission (AE) response of α-brass during SCC propagation. For that purpose, slow strain rate tensile tests (SSRT) under potentiostatic control were performed in a 1 M NaNO₂ solution and in Mattsson’s solution. The differences between the AE signals generated by transgranular and intergranular stress corrosion cracking (SCC) were analysed. Results show that the AE activity during the propagation of TGSCC is various orders of magnitude higher than the AE activity during the IGSCC propagation. However, the mean amplitude and rise time of the AE signals registered during the propagation of TGSCC are similar to the AE parameters of the signals registered during the propagation of IGSCC. The measured AE activity was associated with the mechanical tearing of the metallic ligaments left behind by the propagating crack.     

In situ gravimetry of nickel thin film during potentiodynamic polarization in acidic and alkaline sulfate solutions

The passivation process of nickel thin films during potentiodynamic polarization in acidic and alkaline sulfate solutions was analyzed by an electrochemical quartz crystal microbalance (EQCM) to separate the partial current density of nickel dissolution through the passive film, i_Ni²⁺, and the partial current density of film growth, i_O^2-. The values of i_Ni²⁺ and i_O^2- during potentiodynamic polarization (20 mV s⁻¹) in the passive potential region could be separated by comparing the mass change rate and net polarization current as a function of electrode potential. It is found that i_Ni²⁺ is larger than i_O^2- in pH 3.0, 0.5 M sulfate solution, while the situation reverses in pH 12, 0.5 M sulfate solution. The sulfate concentration dependences of i_Ni²⁺ and i_O^2- in pH 3.0, sulfate solution were significant as compared to those in pH 12, sulfate solution.     

Effect of underpotential deposition of lead on polarization behavior of nickel in acidic perchlorate solutions at room temperature

The effect of Pb²⁺ on polarization behavior of nickel has been investigated in 0.1 M NaClO₄ + 10⁻² M HClO₄ + x M PbO solutions (x = 0, 10⁻⁵, 10⁻⁴, 10⁻³) at room temperature. The cyclic voltammogram has suggested that Pb²⁺ degrades the stability of the passive film on Ni. The corrosion potential of Ni shifted to the more noble direction and the anodic current peak of Ni dissolution decreased with increasing Pb²⁺ concentration in solution, indicating that Pb²⁺ suppresses significantly the anodic dissolution. The underpotential deposition (UPD) of lead on Ni in the potential range more noble than −0.215 V (SHE) corresponding to the equilibrium potential of the Pb²⁺ (10⁻³ M)/Pb electrode was confirmed by XPS and GDOES analyses. The anodic Tafel slope, b⁺, of Ni dissolution changed from b⁺ = 40 mV decade⁻¹ in the absence of Pb²⁺ to b⁺ = 17 mV decade⁻¹ in the presence of 10⁻⁴ or 10⁻³ M Pb²⁺, which was ascribed to the increase in active sites of Ni surface emerged as a result of electrodesorption of Pb adatoms. The roles of Pb adatoms in active dissolution and active/passive transition of Ni were discussed from the above results.     

Corrosion behavior of alumina ceramics in aqueous HCl and H2SO4 solutions

The corrosion behavior of cold isostatically pressed (CIP) high purity alumina ceramics in aqueous HCl and H₂SO₄ solutions with various concentrations has been studied simultaneously at room temperature (25 °C). Corrosion tests were also performed with 0.65 mol/l HCl and 0.37 mol/l H₂SO₄ solutions at 40, 55 and 70 °C for 48 h. Chemical stability was monitored by determining the amount of Al³⁺, Mg²⁺, Ca²⁺, Na⁺ Si⁴⁺ and Fe³⁺ ions eluted in different concentrations of HCl and H₂SO₄ solutions by means of atomic absorption spectrometry (AAS). By increasing the concentration from 0.37 to 6.5 mol/l, it was notified that the corrosion susceptibility in HCl and H₂SO₄ solutions for the CIP alumina specimens at room temperature decreases.     

The effect of prior deformation on stress corrosion cracking growth rates of Alloy 600 materials in a simulated pressurized water reactor primary water

The effect of prior deformation on stress corrosion cracking (SCC) growth rates of Alloy 600 materials in a simulated pressurized water reactor primary water environment is studied. The prior deformation was introduced by welding procedure or by cold working. Values of Vickers hardness in the Alloy 600 weld heat-affected zone (HAZ) and in the cold worked (CW) Alloy 600 materials are higher than that in the base metal. The significantly hardened area in the HAZ is within a distance of about 2-3 mm away from the fusion line. Electron backscatter diffraction (EPSD) results show significant amounts of plastic strain in the Alloy 600 HAZ and in the cold worked Alloy 600 materials. Stress corrosion cracking growth rate tests were performed in a simulated pressurized water reactor primary water environment. Extensive intergranular stress corrosion cracking (IGSCC) was found in the Alloy 600 HAZ, 8% and 20% CW Alloy 600 specimens. The crack growth rate in the Alloy 600 HAZ is close to that in the 8% CW base metal, which is significantly lower than that in the 20% CW base metal, but much higher than that in the as-received base metal. Mixed intergranular and transgranular SCC was found in the 40% CW Alloy 600 specimen. The crack growth rate in the 40% CW Alloy 600 was lower than that in the 20% CW Alloy 600. The effect of hardening on crack growth rate can be related to the crack tip mechanics, the sub-microstructure (or subdivision of grain) after cross-rolling, and their interactions with the oxidation kinetics.     

The influence of CO2, AlCl3 · 6H2O, MgCl2 · 6H2O, Na2SO4 and NaCl on the atmospheric corrosion of aluminum

The influence of salt deposits on the atmospheric corrosion of high purity Al (99.999%) was studied in the laboratory. Four chloride and sulfate-containing salts, NaCl, Na₂SO₄, AlCl₃ · 6H₂O and MgCl₂ · 6H₂O were investigated. The samples were exposed to purified humid air with careful control of the relative humidity (95%), temperature (22.0 °C), and air flow. The concentration of CO₂ was 350 ppm or <1 ppm and the exposure time was four weeks. Under the experimental conditions all four salts formed aqueous solutions on the metal surface. Mass gain and metal loss results are reported. The corroded surfaces were studied by ESEM, OM, AES and FEG/SEM equipped with EDX. The corrosion products were analyzed by gravimetry, IC and grazing incidence XRD. In the absence of CO₂, the corrosivity of the chloride salts studied increases in the order MgCl₂ · 6H₂O < AlCl₃ · 6H₂O < NaCl. Sodium chloride is very corrosive in this environment because the sodium ion supports the development of high pH in the cathodic areas, resulting in alkaline dissolution of the alumina passive film and rapid general corrosion. The low corrosivity of MgCl₂ · 6H₂O is explained by the inability of Mg²⁺ to support high pH values in the cathodic areas. In the presence of carbon dioxide, the corrosion induced by the salts studied exhibit similar rates. Carbon dioxide strongly inhibits aluminum corrosion in the presence of AlCl₃ · 6H₂O and especially, NaCl, while it is slightly corrosive in the presence of MgCl₂ · 6H₂O. The corrosion effects of CO₂ are explained in terms of its acidic properties and by the precipitation of carbonates. In the absence of CO₂, Na₂SO₄ is less corrosive than NaCl. This is explained by the lower solubility of aluminum hydroxy sulfates in comparison to the chlorides. The average corrosion rate in the presence of CO₂ is the same for both salts. The main difference is that sulfate is less efficient than chloride in causing pitting of aluminum in neutral or acidic media.     

Effect of metal ions on corrosion inhibition of pimeloyl-1,5-di-hydroxamic acid for steel in neutral solution

The influence of metal ions on the adsorption process and corrosion inhibition of pimeloyl-1,5-di-hydroxamic acid (C7) on carbon steel surface in neutral solutions has been investigated by surface analytical and electrochemical techniques. Effective corrosion inhibition given by C7 in the presence of Zn²⁺ and Ni²⁺ is believed to be associated with the ability of the hydroxamic acid to form stable slightly soluble complexes with these cations. The influence of the metal ions on the inhibition efficiency is primarily related to the stability constants of C7-cation complexes. Magnesium has no effect on the inhibition performance as it has low stability constant with C7. It was found that the inhibition by C7/cation mixtures depends greatly on the molar ratio and immersion time.     

Hydrogen-assisted fatigue crack growth of AISI 316L stainless steel weld

The fatigue crack growth behaviors of AISI 316L stainless steel (SS) welds in air and gaseous hydrogen were evaluated, and further compared with the base plate. In air, the fatigue crack growth rate (FCGR) of the weld after heat-treatment at 1050 ^oC/1 h was similar to that of the base metal. Furthermore, all specimens became susceptible to hydrogen-accelerated crack growth. Mainly quasi-cleavage fracture related with the strain-induced martensite accounted for the accelerated crack growth in hydrogen. A smaller amount of martensite in the weld was responsible for the decreased susceptibility to hydrogen-enhanced fatigue crack growth relative to the base metal.     

Room temperature ferromagnetism in Mn-doped zinc oxide nanorods prepared by hybrid wet chemical route

Mn-doped (2.6-4.8 at%) aligned zinc oxide (Mn:ZnO) nanorod-films were synthesized by hybrid wet chemical route onto glass substrates. The chemical composition, structural, microstructural and magnetic studies were performed to investigate the origin of observed room temperature ferromagnetism (∼0.11 μ_B/Mn) in these Mn doped ZnO nanorod-films. XPS studies indicated that incorporated Mn was in Mn²⁺ and Mn⁴⁺ states. Mn²⁺ atomic concentration was found to be significantly larger than Mn⁴⁺ concentration in all the samples. Disappearance of the Raman peak at ∼577 cm⁻¹ arising due to the Zn interstitials may be related to the substitution of Mn²⁺ in the Zn²⁺ site with annealing. Thus, Mn metal inclusions as Mn²⁺ in the ZnO lattice are possibly responsible for such large magnetic moment in the films.     

An electrochemical framework to explain the intergranular stress corrosion behavior in two Al-Cu-Mg-Ag alloys as a function of aging

A modified version of the Cu-depletion electrochemical framework was used to explain the metallurgical factor causal to intergranular stress corrosion cracking (IGSCC) susceptibility in two Al-Cu-Mg-Ag alloys (i.e., Al-5.0%Cu-0.8%Mg-0.5%Ag and Al-5.4%Cu-0.5%Mg-0.5%Ag). This framework was also used to explain the specific cases of IGSCC susceptibility in the under-aged condition and increased IGSCC resistance with over-aging. Susceptibility in the under-aged and T8 (peak-aged) conditions is consistent with the grain boundary Cu-depletion mechanism and high concentrations of Cu in solid solution in grain interiors. Improvement in resistance to IGSCC of the over-aged T8+ condition (i.e., T8 temper followed by an additional thermal exposure of 5000 h at 107.2 °C) can be explained by elimination of the differential Cu concentration adjacent to the grain boundary compared to that of the grain interior. The resultant leveling of Cu concentration leads to the suppression of a preferential dissolution path at the grain boundaries associated with IGSCC.     

Electrooxidation of Cr3+ ions in sulfuric acid solutions

The effects the material nature of an anode, the cation radius and the metal-oxygen bond strength in the oxide anode on the rates of Cr³⁺ ion electrooxidation and the anode corrosion. A correlation between the rates of Cr³⁺ cation electrooxidation and corrosion of the anodes made of different metals is revealed. It is shown that the electrocatalytic activity of oxide anodes in the Cr³⁺ electrooxidation is caused by crystallographic and energy factors. The highest electrocatalytic activity is demonstrated by the oxides whose metal cation radius exceeds that of dehydrated Cr³⁺ cation and the M-O bond energy is smaller than the bond energy in Cr₂O₃. The equation suggested takes simultaneously into account the effects of the oxide electrode cation radius and the mean energy of M-O bond on the relative rate of the Cr³⁺ ion electrooxidation. Original Russian Text ? E.G. Vinokurov, V.V. Bondar’, 2007, published in Zashchita Metallov, 2007, Vol. 43, No. 2, pp. 123–127.     

Influence of local stress on initiation behavior of stress corrosion cracking for sensitized 304 stainless steel

To investigate the influence of local stress on initiation behavior of stress corrosion cracking (SCC) for sensitized Type 304 stainless steel, cracking process during constant load SCC test was monitored and recorded with an in situ crack observation system. The changes in number of cracks, sum of crack length and cracked area on the specimen surface with test time were identified from the cracking images analyzed by image processing. In the SCC tests, many cracks were initiated and coalesced on the surface, and the coalescence of cracks played an important role to primary crack growth. The influence of applied stress on crack initiation was different from that on crack growth. In addition, there was a difference between influences of stress on incubation period to crack initiation and crack initiation rate. Due to these differences, a stress of 0.8S_y was thought to cause relatively many cracks compared with 0.5S_y and 1.3S_y (S_y = 200 MPa). Through quantitative estimation of distribution in local stress around a crack by finite element analysis method, it was deduced that the crack initiation is influenced not only by bulk stress applied at the end of the body, but also by local stress formed around pre-existing cracks. According to pre-existing cracks, stress enhancement accelerates the crack growth, while the stress relaxation causes the suppression of new crack initiation. Based on the experiment and analysis results, three types of growth process were suggested, which are caused by propagation itself, by new crack initiation at vicinity of the crack tip, and by coalescence of approaching cracks. Then, it was concluded that, in order to predict/simulate the cracking behavior of this SCC system, the influence of local stress on the crack initiation should be taken into account.