Sensitivity of stress corrosion cracking of stainless steel to surface machining and grinding procedure

An investigation has been undertaken to establish the effect of surface preparation method on the susceptibility of a 304 stainless steel to stress corrosion cracking under simulated atmospheric corrosion conditions. MgCl₂ was deposited onto four-point bend specimens, which were then placed in a chamber with a relative humidity of 45% and temperature of 60 °C. These test conditions were designed to reflect external exposure of stainless steel components in industrial plant, including nuclear reactor components, situated in a coastal region, but with the severity of the exposure conditions enhanced to allow discrimination of the effect of surface preparation in a short timescale (up to 1500 h). Four surface preparation methods were evaluated: transverse grinding, longitudinal grinding, transverse dressing using an abrasive flap wheel, and transverse milling. For each case, surface topography, surface defect mapping, near-surface microhardness mapping, residual stress and electron back-scattered diffraction measurements were undertaken. Stress corrosion cracks were observed for the ground and milled specimens but not for the dressed specimens, with cracks apparently originating at corrosion pits. The density of cracks increased in the order: transverse ground, milled and longitudinal ground, with the cracks notably much smaller in length for the transverse ground condition. The propensity for cracking could be linked to the high residual stress and apparent nanocrystalline microstructure at the surface. There was a greater propensity for pitting to initiate at local defect sites on the surface (laps, deeper grooves). However, the tendency was not overwhelming, suggesting that other factors such as more general roughness or the distribution of MnS inclusions had an influence, perhaps reflecting the severity of the environment.     

Fracture of sustained tensile-loaded Sn–3.0Ag–0.5Cu solder alloy in NaCl solution

The fracture of Sn–3.0Ag–0.5Cu solder alloy has been investigated by a constant sustained tensile-loading test in 0.9 wt.% NaCl aqueous solution at room temperature. Under applied stress in the solution, many cracks nucleate and propagate on the side surface of the specimen. The fracture is not an ordinary creep rupture mode and is probably caused by the decrease in cross section of the specimen due to crack propagation. The preferential dissolution of Ag and Cu ions is clearly observed under applied stress in the solution. The time to fracture and the critical stress for fracture in the solution are lower than those in the atmosphere. The present results indicate that the reliability of lead-free solder alloys must be evaluated considering the effects of the combination of environment and applied stress.     

Influence of the applied stress rate on the stress corrosion cracking of 4340 and 3.5NiCrMoV steels under conditions of cathodic hydrogen charging

Stress corrosion cracking (SCC) of as-quenched 4340 and 3.5NiCrMoV steels was studied under hydrogen charging conditions, with a cathodic current applied to the gauge length of specimens subjected to Linearly Increasing Stress Test (LIST) in 0.5 M H₂SO₄ solution containing 2 g/l arsenic trioxide (As₂O₃) at 30 °C. Applied stress rates were varied from 20.8 to 6 × 10⁻⁴ MPa s⁻¹. Both the fracture and threshold stress decreased with decreasing applied stress rate and were substantially lower than corresponding values measured in distilled water at 30 °C at the open circuit potential. The threshold stress values correspond to 0.03–0.08 σ_y for 4340 and 0.03–0.2 σ_y for the 3.5NiCrMoV steel. SCC velocities, at the same applied stress rate, were an order of magnitude greater than those in distilled water. However, the plots of the crack velocity versus applied stress rate had similar slopes, suggesting the same rate-limiting step. The fracture surface morphology was mostly intergranular, with quasi-cleavage features.     

Corrosion-induced copper runoff from naturally and pre-patinated copper in a marine environment

Corrosion-induced copper runoff has been monitored for copper sheet, naturally patinated copper and pre-patinated copper, with and without surface treatments, in a marine environment during one year. The study comprises solution measurements on total copper runoff rates, sulphates and chlorides released from the patina, and parallel surface analytical studies on patina formation, combined with electrochemical impedance measurements on changes in barrier properties during exposure. Bioassay tests and model predictions were applied to elucidate copper bioavailability at the immediate release situation. The runoff rate of copper was significantly lower compared to the corrosion rate throughout the exposure period. At comparable rain quantities, copper runoff rates were significantly lower at the marine site compared to similar data obtained in an urban environment. The bioavailable concentration of released copper was significantly lower compared to the total copper concentration.     

Evaluation of delayed fracture property of outdoor-exposed high strength AISI 4135 steels

Delayed fracture properties of AISI 4135 high strength steels with 1490 and 1310 MPa of tensile strength, represented as B15 and B13, respectively, have been studied by means of slow strain rate test (SSRT) of notched bar specimens after outdoor exposure at rural and coastal areas. The exposed specimens were kept at humid medium before SSRT to reproduce active hydrogen entry influenced by the rust layer and to homogenize hydrogen distribution. The influences of exposure site and exposure time on fracture stress have been investigated. The susceptibility of B15 to delayed fracture was obviously higher than that of B13.     

Effect of corrosion severity on fatigue evolution in Al-Zn-Mg-Cu

The effect of existing-localized corrosion on fatigue cracking of 7075-T6511 was established using crack surface marker-band analysis and a fracture mechanics model. The substantial reduction of fatigue life due to EXCO solution L-S surface pre-corrosion is nearly independent of exposure time after initial-sharp degradation, scaling with the evolution of pit-cluster size and initial stress intensity range with exposure time. Independent of exposure time, formation of a resolvable fatigue crack (∼10 μm) accounts for a similar-low (∼5%) fraction of total fatigue life at low stress range (σ_max = 150 MPa, R = 0.1). Crack formation occurs at microscopic protrusions into the corroded volume. A corrosion-modified-equivalent initial flaw size (CM-EIFS); predicted with the AFGROW tool using measured initial aspect ratio, initiation cycles, and total fatigue life inputs; accurately represents the corrosion damage effect on fatigue for a range of exposures. The similar deleterious effect of several corroding environments for various-exposed surfaces is described by a lower-bound CM-EIFS with a 300 μm depth and 1200 μm surface length suggesting fatigue is governed by a microscopic pit-based topography. Either an approximate lower-bound, or specific CM-EIFS calibrated by limited measurements of fatigue life for service-environment exposed specimens, can be used to assess the impact of corrosion in a damage tolerant framework. Complexities (e.g., local H embrittlement, 3D pit geometry, topography dependent initiation, and microstructure sensitive small-crack growth) do not compromise the CM-EIFS estimation, but must be better understood for refined modeling.     

Comparative assessment of electrochemical hydrogen absorption by pipeline steels with different strength

The assessment of ability to absorb hydrogen of three API grade pipeline steels: X52, X70 and X100 have been evaluated. The factors of cathodic hydrogen charging, time of exposure, and applied stress were taken into account. It has been shown that all steels demonstrate the sensitivity to hydrogenating in deoxygenated, near-neutral pH NS4 solution under relatively “soft” cathodic polarisation, although the efficiency of hydrogen permeation in metal is quite low and depends on time of exposure. Applied tensile stress, which equivalent to gross hoop stress in pipe wall under operating conditions, can accelerate the hydrogen absorption in several times. For studied steels the resistance to hydrogen absorption decreases with decreasing of steel strength.     

Impact of temperature excursion on stress corrosion cracking of stainless steels in chloride solution

The impact of a temperature excursion on the subsequent stress corrosion crack growth at the normal operating temperature has been investigated for 321 stainless steel (UNS32100) and 316L stainless steel (UNS31603) using precracked compact tension specimens. Although the data are preliminary the indication is that once crack growth has initiated in 321 SS at the elevated temperature, 130 °C in this study, the crack growth may be sustained at the lower temperature (40 °C), at least over the exposure time of about 700 h. However, the growth rate of 316L SS at the lower temperature was significantly lower than for 321 SS and tended to zero after 2000 h. For the 316 SS a temperature transient should not impact on structural integrity, provided it is short in duration.     

Electrochemical evaluation of under-deposit corrosion and its inhibition using the wire beam electrode method

A new experimental method has been applied to evaluate under-deposit corrosion and its inhibition by means of an electrochemically integrated multi-electrode array, namely the wire beam electrode (WBE). Maps showing galvanic current and corrosion potential distributions were measured from a WBE surface that was partially covered by sand. Under-deposit corrosion did not occur during the exposure of the WBE to carbon dioxide saturated brine under ambient temperature. The introduction of corrosion inhibitor imidazoline and oxygen into the brine was found to significantly affect the patterns and rates of corrosion, leading to the initiation of under-deposit corrosion over the WBE.     

Modelling the crack propagation rate for corrosion fatigue at high frequency of applied stress

The application of standard mathematical techniques for the solution of mass transport equations, in the case of advection that is caused by the pulsating movement of crack walls in the case of corrosion fatigue, can be very time consuming. This problem arises, due to the requirement that the time step that must be employed, when solving the non-stationary equations numerically, must be significantly smaller than the period of oscillation. For overcoming these time-consuming limitations, a simple algorithm, which is based on eliminating the convective term from the equations of mass transfer in the pulsating slab by a suitable change of variables, was developed. The estimation of the advection effect on the rate of corrosion fatigue has been performed for the cases of diffusion and mixed kinetic control at high frequencies of applied stress. It is shown that, in many cases, it is possible to use codes that were developed for describing stress corrosion cracking, i.e. for the case of mass transfer without advection at zero loading frequency, to predict corrosion fatigue crack propagation rate, by simply substituting an effective crack length. Numerical calculations that have been performed in this work also show that the method developed here yields results that are applicable not only to the elevated frequencies, but to the any arbitrary frequency from 0 to ∞ for estimating corrosion fatigue crack propagation rate.     

Creep corrosion cracking of Sn–3.0Ag and Sn–0.5Cu solder alloys in NaCl solution

The surface crack nucleation of Sn–3.0Ag and Sn–0.5Cu solder alloys has been examined by performing sustained tensile-loading tests in 0.9 mass% NaCl solution at room temperature. For Sn–3.0Ag alloy, many cracks nucleate and propagate on the side surface of the specimen, similarly to Sn–3.0Ag–0.5Cu alloy reported previously. For Sn–0.5Cu alloy, such cracks are not observed, and ordinary creep deformation occurs in the solution. The effect of sustained applied stress, i.e., creep, on the dissolution of ions is smaller for Sn–0.5Cu alloy than for Sn–3.0Ag alloy. The present results suggest that there are differences in the susceptibility to cracking under applied stress in a solution, i.e., creep corrosion cracking, among lead-free solder alloys.     

A general model for the repassivation potential as a function of multiple aqueous species. 2. Effect of oxyanions on localized corrosion of Fe–Ni–Cr–Mo–W–N alloys

A recently developed model for predicting the repassivation potential has been applied to stainless steels and nickel-base alloys in aqueous environments containing chlorides and various inhibiting anions. The model accounts for the effects of solution chemistry and temperature on the repassivation of localized corrosion by considering competitive dissolution, adsorption, and oxide formation processes at the interface between the metal and the occluded site solution. An extensive database of repassivation potentials has been established for six alloys (UNS 31603, N06600, N06690, S31254, S32205, and UNS S41425) in contact with solutions that combine chlorides with hydroxides, molybdates, vanadates, sulfates, nitrates, and nitrites at various concentrations and temperatures. Also, repassivation potentials are reported for four alloys (UNS N08367, N08800, N06625, and N10276) in chloride solutions. The database has been used to establish the parameters of the model and verify its accuracy. The model quantitatively predicts the transition between concentrations at which localized corrosion is possible and those at which inhibition is expected. It is capable of predicting the repassivation potential over wide ranges of experimental conditions using parameters that can be generated from a limited number of experimental data. The parameters of the model have been generalized as a function of alloy composition, thus making it possible to predict the repassivation potential for alloys that have not been experimentally investigated.     

Effect of stress on electrochemical characteristics of pre-cracked ultrahigh strength stainless steel in acid sodium sulphate solution

The electrochemical behaviors of ultrahigh strength stainless steel Cr12Ni5MoCo14 at crack tip under applied stress were studied by micro-electrochemical measurements as well as finite element analysis. The non-uniform distribution of the stress and strain induces a higher electrochemical activity at crack tip and promotes the anodic dissolution rate. The corrosion rate increases with increasing applied stress. In the elastic stress range, the effect of the applied stress on the electrochemical behaviors of Cr12Ni4Mo2Co14 steel is small. In the plastic stress range, the plastic deformation has a dramatic effect on the mechanical–electrochemical interaction and enhances the anodic activity.     

Gildes model studies of aqueous chemistry. III. Initial SO2-induced atmospheric corrosion of copper

The GILDES computer model, incorporating Stumm's concept of proton- and ligand-promoted dissolution, has been used to simulate the exposure of copper at room temperature to 210 ppb sulfur dioxide and 80% relative humidity. The agreement is good between the calculations and laboratory exposures performed under these exposure conditions. Surface reactions are relatively more important at lower relative humidities and the dominant corrosion products formed are solid state Cu₂SO₃, CuSO₃ and Cu₂U. Free-radical redox processes are important participants and control the relative distribution of Cu(I)- and Cu(H)-containing corrosion products.     

Environment-induced cracking of Al–Cu alloy (AA2017P-T3) under constant load in distilled water and sodium chloride solutions

The environment-induced cracking (EIC) of a commercial Al–Cu alloy has been investigated as functions of applied stress, chloride ion concentration and test temperature in distilled water and sodium chloride solutions by using a constant load method. The effect of chloride ion on EIC is complex. The EIC susceptibility increased, unchanged and then decreased with increasing the chloride ion concentration. However, whenever EIC takes place with and without chloride ion, the fracture appearance and the value of t_ss (transition time to deviation from linear elongation)/t_f (time to failure) are the same, and further the relationship between log t_f and log l_ss (steady state elongation rate) becomes the identical straight line irrespective of applied stress, chloride ion concentration and test temperature. The latter means that l_ss becomes a relevant parameter for predicting t_f. It has been concluded that EIC of Al–Cu alloy takes place by hydrogen embrittlement (HE) associated with the fracture of hydride, and a HE mechanism is qualitatively proposed to explain the results obtained.     

Stress corrosion cracking initiation under the disbonded coating of pipeline steel in near-neutral pH environment

A novel test setup has been used in this study to simulate stress corrosion cracking initiation under a disbonded coating on an X-65 pipeline steel. In this setup, the synergistic effects of cyclic loading, cathodic protection and soil solution environment under disbonded coatings have been considered. When the X-65 pipeline steel was exposed to the test environment, there existed a wide range of corrosion products on the steel surface in the gradient of cathodic protection. Increasing the test time and the maximum stress increased the possibility of stress corrosion cracking initiation in regions with a high susceptibility to pitting corrosion.     

Grain boundary structure and intergranular stress corrosion crack initiation in high temperature water of a thermally sensitised austenitic stainless steel,observed in situ

The development of an intergranular stress corrosion crack initiation site in thermally sensitised type 304 austenitic stainless steel has been observed in situ in high temperature oxygenated water using digital image correlation of time-resolved optical observations. The grain boundary normal stresses were calculated using the Schmid-Modified Grain Boundary Stress (SMGBS) model of Was et al., applying three-dimensional data for the grain boundary planes and grain orientations. The initiation site coincided with the most highly stressed sensitised boundary, demonstrating the importance of the combined contributions to crack initiation of grain boundary structure and plastic strain incompatibility.     

Analysis of the galvanostatic polarization method for determining reliable pitting potentials on stainless steels in crevice-free conditions

In this paper the potential of the galvanostatic polarization technique as accelerated method for determining the characteristic pit potentials on stainless steels in crevice-free conditions is examined. Measurement of the potential change as a function of time shows a maximum that agrees with the nucleation pit potential. Thereafter, a stationary potential is reached corresponding to the protection potential against pit. Possible limitations of this kind of measurements have been remedied by refinements in the test procedure and conditions. The state of the surface oxide film and the applied anodic current are two basic parameters that must be well defined because they govern the pitting susceptibility. It has been found that with applied anodic currents in the range 40–200 μA/cm² and with prior electrode exposures to solution between 30 and 60 min it is possible to obtain results in excellent agreement with the conventional potentiodynamic tests with the advantage of smaller data scattering and absence of crevice at electrode/holder interfaces. These effects are the result of the rapid pitting stimulated in the galvanostatic method. This implies a short duration of the experiment thus also favouring the elimination of the time-dependent crevice, which notoriously contributes to the poor reproducibility of pit potentiodynamic potentials. A detailed series of experiments have been conducted on several stainless steels and in different test conditions to validate the accuracy of the galvanostatic polarization method.     

Determination of threshold stress intensity factor for stress corrosion cracking (KISCC) of steel heat affected zone

Threshold stress intensity factor for stress corrosion cracking of heat affected zone (HAZ) of mild steel in caustic solution has been determined using circumferential notch tensile (CNT) technique. HAZ microstructure produced during manual metal arc welding of grade 250 steel was simulated over a length of 35 mm of CNT specimens, using a thermo-mechanical simulator. Inter-granular stress corrosion cracking has been confirmed with scanning electron microscope. The results presented here validate the ability of CNT technique for determination of K_ISCC of HAZ and base metal.     

New insight into the pit-to-crack transition from finite element analysis of the stress and strain distribution around a corrosion pit

A finite element (FE) analysis has been undertaken to evaluate the stress and strain distribution associated with a single corrosion pit in a cylindrical steel specimen stressed remotely in tension. A key observation was the localisation of plastic strain to the pit walls (just below the surface of the specimen). Simulation of a growing pit in a static stress field indicated corresponding plastic strain rates that were commensurate with values associated with stress corrosion cracking. This observation introduces a wholly new concept in understanding of the evolution of stress corrosion cracks from pits and correlates with recent X-ray tomography measurements.