Potential influence of microorganisms on the corrosion of carbon steel in the French high- and intermediate-level long-lived radioactive waste disposal context

In the context of the high-level radioactive waste disposal CIGEO, the corrosion rate due to microbially influenced corrosion (MIC) has to be evaluated. In France, it is envisaged to dispose of high- and intermediate-level long-lived radioactive waste at a depth of 500 m in a deep geological disposal, drilled in the Callovo-Oxfordian claystone (Cox) formation. To do so, a carbon steel casing will be inserted inside disposal cells, which are horizontal tunnels drilled in the Cox. A specific cement grout will be injected between the carbon steel casing and the claystone. A study was conducted to evaluate the possibility of MIC on carbon steel in the foreseeable high radioactive waste disposal. The corrosiveness of various environments was investigated at 50°C and 80°C with or without microorganisms enriched from samples of Andra's underground research laboratory. The monitoring of corrosion during the experiments was ensured using gravimetric method and real-time corrosion monitoring using sensors based on the measurements of the electrical resistance. The corrosion data were completed with microbiological analyses including cultural and molecular characterizations.     

The anoxic corrosion behaviour of carbon steel in anoxic alkaline environments simulating a Swiss L/ILW repository environment

The Swiss waste management programme foresees that low- and intermediate-level radioactive waste will be disposed of in a deep geological repository constructed in Opalinus Clay. Gas generation is expected in the repository due to the decomposition of organic materials and the corrosion of metals, with carbon steel being the primary source. The corrosion behaviour of mild steel under anoxic conditions has been studied over the course of several years to better understand the long-term hydrogen evolution profile under anticipated repository conditions. Steel, either bare or encased within mortar, was tested in water vapour or immersed in electrolytes representative of aged cement waters at 50°C. The corrosion rate was measured indirectly through the hydrogen analysis using a solid-state probe. The hydrogen evolution behaviour of grout was also monitored to more accurately determine the hydrogen generating from the corrosion of the embedded steel. For steel in water vapour or in alkaline environments, embedded in cementitious material or immersed in simulated aged cement pore water, corrosion rates were invariably <1 nm/year after several years of analysis.     

Design and evaluation of chimney liners for a new system power plant using fiberglass reinforced plastics

A new system power plant using liquid natural gas (LNG) as fuel is being constructed in Osaka harbor area. It has a capacity of 1,800,000 KW; the height of chimney is to be 200 m, and FRP liners 5.3 m in diameter are installed in a ferro-concrete construction. The temperature of the flue gas is 118°C under normal natural gas burning conditions. In the case of emergency, the allowed temperature must be limited to 200°C because of the heat resistance of the construction material. For such severe environmental conditions, the selection of materials becomes important. Starting in 1984, FRP or fiberglass reinforced plastics have been examined for use in components of large power plant chimneys. FRP has been estimated as a material of good resistance for such environments, and three types of vinylester resin and two types of isophthalic acid unsaturated polyester were evaluated for environmental resistance under static conditions, such as high temperature heating tests (140°C and 200°C), cyclic tests involving heating and cooling (140°C–30°C), one-side immersion tests in sulfuric acid at 90 °C constant or cyclic tests (90°C–40°C), and also by field tests in actual running power station. After such evaluations, corrosion tests under dynamic conditions were carried out by the stress relaxation method (newly standardized method in Japan: JIS K7107-1987) and by the chemical fatigue tests. Especially, the fatigue strength of adhesive bonded joint of FRP is very important, so the tensile fatigue tests under environmental conditions were carried out. In addition to these laboratory tests using small size specimens, actual size specimens were tested for static and fatigue strength at normal temperature. As to the material for the top part of the chimney, glass flake/vinylester resin lining was assumed to be the most preferable material. In addition, a moisture permeation test at 80°C and constant cycling (80°C–20°C) temperature was carried out, too. This series of tests has allowed to assess the reliability and life of FRP parts and to proceed with construction design.     

Stress corrosion cracking of cold-worked austenitic stainless steels

Stress corrosion cracking (SCC) of AISI 304L and AISI 316L stainless steels, cold-worked under various conditions (i.e. at different degrees of deformation obtained by drawing and rolling at room temperature and at liquid nitrogen temperature) has been carried out in H₂O containing 1000 ppm Cl^? at 250°C and in a boiling MgCl₂ solution. The effect of heat treatments at 400 and 900°C on the SCC of previously cold-worked steels has also been studied. Particular attention was directed towards heat treatment at 400°C. In steels deformed at room temperature, it increases the SCC resistance. By contrast, for steels deformed at liquid nitrogen temperature, heat treatment at 400°C reduces the SCC resistance if carried out for short periods of time (1–6 h). Hardness measurements, structural analyses via X-rays, scanning and transmission electron microscopy (SEM and TEM), as well as modified Strauss tests, seem to prove that reduced stress corrosion resistance is not to be related to the chromium-rich carbides precipitation which could have been accelerated by the presence of α′-martensite. Instead, they tend to suggest that perhaps this phenomenon is connected to an increase in the level of internal micro-stresses which are generated by a reciprocal re-ordering of the α′ and γ structural phases.     

Straining metal electrode as a SCC test. Type 304 stainless steel in MgCl2, CaCl2 and LiCl solutions

Straining metal electrode experiments are a valuable technique for predicting crack propagation rates and crack morphologies when anodic dissolution is the rate-determining step in stress corrosion cracking (SCC). The straining test provides the same information found through more conventional SCC tests, with the advantage of being considerably less time-consuming. In the present work this technique was applied to Type 304 stainless steel in MgCl₂, CaCl₂ and LiCl solutions, tested at room temperature and at 90° and 100°C. The predicted effects of temperature and electrode potential were in good agreement with those reported in the literature. A limit crack propagation rate from about 10^?8 to 10^?7 m s^?1 was found, in agreement with values reported by other authors from fracture mechanic tests. Above the pitting potential the crack propagation rate was found to remain constant, but there was a sharp decrease in the bare metal/filmed metal current ratio, and SCC was replaced by generalized corrosion and pitting.     

Evaluation of SCC susceptibility of supermartensitic stainless steel using slow strain rate tests

Abstract

The susceptibility to chloride stress corrosion cracking (Cl-SCC) of supermartensitic stainless steel (SMSS) was evaluated at different temperatures through slow strain rate tests. In order to evaluate the Cl-SCC susceptibility the reduction in area and the time to failure ratio were considered. It is clear that all specimens tested in the chloride solution exhibited a generally high resistance to chloride SCC. However, according to the slow strain rate tests results, at lower temperature (5°C) the susceptibility to Cl-SCC increases compared to the other temperatures studied; also an increase in the corrosion rate was observed as the temperature decreased according to electrochemical impedance spectroscopy measurement. The corrosion mechanism observed on the material under dynamic stress was a combination of high activation resistivity with a diffusive process on the metallic interface given by a thin film from a protector layer of chromium oxides. This mechanism generates a high corrosion resistance and therefore good performance to chloride induced SCC.     

Corrosion resistance of a cast steel overpack for high-level radioactive waste disposal in Japan

The corrosion rate and stress corrosion cracking (SCC) susceptibility of a cast steel are studied for its application to metal containers (namely overpacks) for geological disposal of high-level radioactive waste. Specimens for corrosion tests are cut from a prototype overpack manufactured by full-scale casting. Casting defects are widely distributed in the prototype overpack; however, the flat-bottom hole equivalent diameters for all defects detected by an ultrasonic test are 3.6 mm or less, which is relatively small. Forged steels and rolled steels are also tested for comparison of their corrosion properties with the cast steel. The corrosion rates are obtained by immersion tests in bentonite saturated with synthetic seawater under anaerobic conditions at 80°C for up to 1 year. The corrosion rate for the cast steel calculated by the weight loss during the experiments is close to that for the forged steels and rolled steels. The SCC susceptibility is examined using slow strain rate tests in a 1.5-mol L⁻¹ carbonate–bicarbonate solution, in which the occurrence of high-pH SCC is often reported for carbon steels. The SCC susceptibility increased with the increase in the carbon content of the products; however, there are no clear differences between casting and forging.     

Thermal effects on the enhanced ductility in non-monotonic uniaxial tension of DP780 steel sheet

To understand the material behavior during non-monotonic loading, uniaxial tension tests were conducted in three modes, namely, the monotonic loading, loading with periodic relaxation and periodic loading-unloadingreloading, at different strain rates (0.001/s to 0.01/s). In this study, the temperature gradient developing during each test and its contribution to increasing the apparent ductility of DP780 steel sheets were considered. In order to assess the influence of temperature, isothermal uniaxial tension tests were also performed at three temperatures (298 K, 313 K and 328 K (25 °C, 40 °C and 55 °C)). A digital image correlation system coupled with an infrared thermography was used in the experiments. The results show that the non-monotonic loading modes increased the apparent ductility of the specimens. It was observed that compared with the monotonic loading, the temperature gradient became more uniform when a non-monotonic loading was applied.     

Einfluß des Kriechens auf die Spannungsrißkorrosion austenitischer Chrom-Nickel-Stähle in heißer 35%iger Magnesiumchloridlösung

Creep effect on stress corrosion cracking of austenitic CrNi steels in boiling 35% magnesium chloride solution Potentiostatic and potentiodynamic polarization curves of steel X 5 CrNi 18 9 in 35% MgCl₂-solution at 120° C do not show significant differences. Important for SCC tests is a narrow potential region before the onset of the potential of pit nucleation. SCC-experiments were carried out using two different techniques:

• (a) loading in the electrolyte
• (b) prestraining in air at 120° C; after transient creep the SCC test was initated.

Applying the technique described under (b) a decrease of SCC-susceptibility according to the crack nucleation expected in the slip dissolution model does not take place. Accordingly the dependence of time to failure on potential as well as on stress is found to be almost similar. Only in the absence of pitting a SCC threshold stress exists with its value in the range of yield strength. On the other hand SCC failure in the elastic region (< 0.1 σ_y) is observed when crack nucleation starts in corrosions pits.     

Spannungsrißkorrosion von Rohren aus INCONEL 600: Einfluß von Wärmebehandlung,NaOH-Konzentration und Temperatur

Stress corrosion cracking of Inconel 600 tubing: Influence of thermal treatment, NaOH concentration and temperature A study has been performed concerning the role of thermal treatments on the SCC behaviour of Inconel 600 tubing in NaOH solutions in the temperature range 315–360°C. An additional investigation was undertaken to establish the effect of the NaOH concentration built-up under magnetite deposits. The changes in the microstructural variables in the four metallurgical conditions studied were indentified by transmission electron microscopy (TEM). C-ring and slow strain rate tests (10^?6s^?1) yielded identical results. SEM fractographs were additionally taken to reveal the cracking mode. It has been found that thermal treatment improves the SCC resistance in hot caustic solutions; particularly annealing at 650°C for 50 h appeared to impart the maximum improvement of SCC resistance.     

Analysis of Tempering Treatment on Material Properties of DIN 41Cr4 and DIN 42CrMo4 Steels

DIN 41Cr4 and DIN 42CrMo4 materials have been widely used in automotive driving elements. Although 42CrMo4 is more expensive than 41Cr4, it is more preferable in terms of material properties. In this study, these two materials were heat treated by austenitizing in a continuous furnace at 850 °C and quenched in oil at 90 °C. After they were tempered at various temperatures, mechanical properties were determined for each tempering temperature. The material properties for both materials were compared with each other. Results indicated that same mechanical properties for 41Cr4 and 42CrMo4 can be achieved by tempering 41Cr4 about 50 °C lower temperature than for 42CrMo4. In addition to the mechanical tests, fatigue tests were performed for both materials. Weibull distributions were plotted. Results indicated that 42CrMo4 had a longer life than 41Cr4 material.     

Coarsening of AA6013-T6 Precipitates During Sheet Warm Forming Applications

The use of warm forming for AA6xxx-T6 sheet is of interest to improve its formability; however, the effect warm forming may have on the coarsening of precipitates and the mechanical strength of these sheets has not been well studied. In this research, the coarsening behavior of AA6013-T6 precipitates has been explored, in the temperature range of 200-300 °C, and time of 30 s up to 50 h. Additionally, the effect of warm deformation on coarsening behavior was explored using: (1) simulated warm forming tests in a Gleeble thermo-mechanical simulator and (2) bi-axial warm deformation tests. Using a strong obstacle model to describe the yield strength (YS) evolution of the AA6013-T6 material, and a Lifshitz, Slyozov, and Wagner (LSW) particle coarsening law to describe the change in precipitate size with time, the coarsening kinetics were modeled for this alloy. The coarsening kinetics in the range of 220-300 °C followed a trend similar to that previously found for AA6111 for the 180-220 °C range. There was strong evidence that coarsening kinetics were not altered due to warm deformation above 220 °C. For warm forming between 200 and 220 °C, the YS of the AA6013-T6 material increased slightly, which could be attributed to strain hardening during warm deformation. Finally, a non-isothermal coarsening model was used to assess the potential reduction in the YS of AA6013-T6 for practical processing conditions related to auto-body manufacturing. The model calculations showed that 90% of the original AA6013-T6 YS could be maintained, for warm forming temperatures up to 280 °C, if the heating schedule used to get the part to the warm forming temperature was limited to 1 min.     

Thermally Sprayed Aluminum (TSA) Coatings for Extended Design Life of 22%Cr Duplex Stainless Steel in Marine Environments

In this article, evaluation of sealed and unsealed thermally sprayed aluminum (TSA) for the protection of 22%Cr duplex stainless steel (DSS) from corrosion in aerated, elevated temperature synthetic seawater is presented. The assessments involved general and pitting corrosion tests, external chloride stress corrosion cracking (SCC), and hydrogen-induced stress cracking (HISC). These tests indicated that DSS samples, which would otherwise fail on their own in a few days, did not show pitting or fail under chloride SCC and HISC conditions when coated with TSA (with or without a sealant). TSA-coated specimens failed only at very high stresses (>120% proof stress). In general, TSA offered protection to the underlying or exposed steel by cathodically polarizing it and forming a calcareous deposit in synthetic seawater. The morphology of the calcareous deposit was found to be temperature dependent and in general was of duplex nature. The free corrosion rate of TSA in synthetic seawater was measured to be ~5-8 μm/year at ~18 °C and ~6-7 μm/year at 80 °C.     

Inhibition von Niedertemperaturkreisläufen in Kraftwerken mit Lithiumhydroxid

Inhibition of low temperature circulating systems with lithium hydroxide in power stations Corrosion current density measurements of mild steel St 37 in deionized, air-saturated water between 20 and 60°C showed that addition of small quantities of lithium hydroxide (ca. 25 ppm) protects against corrosion attacks similar to pitting corrosion and is found adequate even up to 5 ppm chloride ion concentration. Constant strain rate tests of mild steel St 37 showed no indication of stress corrosion cracking (SCC) at 70°C, up to 500 ppm lithium hydroxide, and 100 ppm chloride ion concentration. Metallographic examination of specimens indicated intergranular stress cracking with cracks of 1–30 m?m depth in environments containing 2%, 4%, and saturated lithium hydroxide (with solid excess salt) at 70°C. Accumulation of lithium hydroxide should therefore be avoided. No SCC was observed in austenitic stainless steel X 5 CrNi 18 9 specimens in the above environments.     

An internal variable approach of orientation dependent deformation mechanism of rolled AZ31 magnesium alloy

Load relaxation behavior of an AZ31 Mg alloy has been studied in relation to temperature and orientation dependence. The rolled plate with 50 mm thickness was first homogenized at 400 °C for 4 h before preparing test specimens in the directions of 0° (RD), 45°, and 90° (ND) from the rolling direction. A series of tensile tests was consequently carried out under a strain rate of 10⁻²/s at room temperature (RT), 100 °C, and 200 °C. The RD specimens were found to deform mainly by dislocation slips without twinning. The 45° and 90° specimens were, on the other hand, found to deform in a combined mode of twinning and dislocation slips. Load relaxation tests were also performed to obtain flow curves in terms of stress and strain rate at the three different temperatures. The flow curves in terms of stress vs. strain rate were also found to consist of a plasticity curve due to dislocation glides in the lower strain rate region and a twin curve in the high strain rate range for the 45° and 90° specimens as prescribed by an internal variable theory. These results were consistent with the tensile test results and were further confirmed by microstructure observations.     

Effect of annealing temperature on pitting behavior and microstructure evolution of hyper‐duplex stainless steel 2707

Hyper‐duplex stainless steel (HDSS) 2707 is a competitive material for application in extremely caustic environments. In this study, different annealing temperatures ranging from 1020°C to 1200°C were examined by electrochemical tests and microstructure analysis. The microstructure characterization indicated that precipitations were detected when the annealing temperature was below 1050°C and a relatively balanced austenite–ferrite phase structure was obtained at 1100°C. Through electrochemical measurements in NaBr solution, it was revealed that with the increase of temperature the pitting resistance of HDSS 2707 first rose then declined, peaking at 1100°C. The highest critical pitting temperature was about 67°C. In addition, the pitting position shifted from austenite phase to austenite–ferrite boundary and finally to ferrite interior with the annealing temperature increasing, which was in agreement with the pitting resistance equivalent values (PREN) of the two phases.     

Functional Characterization of a Novel Shape Memory Alloy

A novel shape memory alloy (SMA) has been developed as an alternative to currently available alloys. This alloy, commercially known by its proprietary brand SMARQ, shows a higher working range of temperatures with respect to the SMA materials used until now in actuators, limited to environment temperatures below 90 °C. SMARQ is a high temperature SMA (HTSMA) based on a fully European material technology and production processes, which allows the manufacture of high quality products, with tuneable transformation temperatures up to 200 °C. Both, material and production processes have been evaluated for its use in space applications. A full characterization test campaign has been completed in order to obtain the material properties and check its suitability to be used as active material in space actuators. In order to perform the functional characterization of the material, it has been considered as the key element of a basic SMA actuator, consisting in the SMA wire and the mechanical and electrical interfaces. The functional tests presented in this work have been focused on the actuator behavior when heated by means of an electrical current. Alloy composition has been adjusted in order to match a transition temperature (As) of +145 °C, which satisfies the application requirements of operating temperatures in the range of ?70 and +125 °C. Details of the tests and results of the characterization test campaign, focused in the material unique properties for their use in actuators, will be presented in this work. Some application examples in the field of space mechanisms and actuators, currently under development, will be summarized as part of this work, demonstrating the technology suitability as active material for space actuators.     

Correlation of microstructural and mechanical properties of K-doped tungsten fibers used as reinforcement of tungsten matrix for high temperature applications

Reinforcement of tungsten by tungsten fibers (W_f) is considered an attractive option to mitigate the intrinsic brittleness of this material and to possibly extend the operational temperature window to ensure safe operation of the plasma facing component. By now, it has been demonstrated that tungsten fiber-reinforced tungsten composites (W_f/W) acquire pseudo ductility even at room temperature, and crack propagation is determined by the interaction of the fibers with the propagating crack. In view of strong temperature oscillations, expected during operation in the fusion plasma, the mechanical properties of tungsten fibers annealed at different temperatures (up to 2300 °C) were assessed, and the role of potassium (K) doping on the modification of the mechanical properties of as-annealed wires was studied. While K-doping was found to delay the brittleness induced by heat exposure at least up to 1600 °C, still a strong reduction of the fiber strength was observed in tests performed at elevated temperatures. In this work, we investigate the reasons for this effect by performing scanning electron microscopy coupled with electron backscatter diffraction measurements. The longitudinal and transversal cross-sections of W fibers were analyzed to deduce the morphology and size distribution of the grains. Consistent with the mechanical data, we found that annealing at 2100 °C resulted in the full recrystallization of the elongated grains, otherwise formed due to the extrusion fabrication process. Even at 1900 °C, the longitudinal cross-section still exhibits elongated grains. The transversal shape of the grains undergoes a change from needle-like fine structure to equiaxed grain shape upon annealing above 1600 °C. Few scans done for 2300 °C annealed wire revealed that the microstructure contains one or several grains with a dimension of 70–150 μm. The obtained results are discussed and analyzed in the frame of mechanistic model connecting microstructure with the mechanical response.     

Precipitation behavior in Al-Zn-Mg-Cu alloy after direct quenching

The precipitation behavior in an Al-6.8Zn-1.9Mg-1.0Cu-0.12Zr alloy after direct quenching from solution heat treatment temperature of 470 °C to 205–355 °C was investigated by means of hardness tests, electrical conductivity tests, and transmission electron microscopy. At temperatures below 265 °C, the hardness increased gradually to a peak value and then decreased rapidly with time. At 265 °C, the hardness was almost unchanged within the initial 2000 s and then decreased gradually. At higher temperatures, the hardness decreased slowly with time. The electrical conductivity started to increase after a certain period of time and then tended to maintain a constant value at all temperatures. Microstructure examination indicated heterogeneous precipitation of the η phase at grain boundaries and inside grains during holding at 205 °C and 325 °C. Based on the electrical conductivity data, the precipitation kinetics could be described quite well by the Johnson-Mehl-Avrami-Komolgorov relationship with a n value varying between 0.78 and 1.33. The activation energy was estimated to be about 44.9 kJ/mol, which is close to that expected for a dislocation diffusion mechanism. Time-temperature-transformation diagrams were constructed and the nose temperature ranged from 295 °C to 325 °C.     

Non-isothermal creep at very high temperature of the nickel-based single crystal superalloy MC2

The non-isothermal creep of a second-generation single crystal nickel-based superalloy was investigated at very high temperature. During the creep tests at 1050 °C, short temperature jumps to 1200 °C were performed. Various testing routes – 1050, 1200 and 1050 °C – were investigated. The best non-isothermal creep properties are obtained for the highest heating and cooling rates during the temperature jump. These were performed with a special testing device. In these conditions (i) if the overheating is applied to an as-received material, the residual life of the material remains unchanged compared with the isothermal creep life; and (ii) when applied to a pre-crept material, surprisingly, the longer the overheating at 1200 °C, the longer the residual life and the larger the deformation at failure at 1050 °C. This behavior is discussed on the basis of the γ’ phase and dislocation arrangement evolutions.