Papers by Author: Vivekanand Kain

Abstract: Tempering of alloy steels in the temperature range of 400-600 °C causes temper embrittlement i.e. decrease in notch toughness of the material and the nil ductility temperature is raised to room temperature and above. The fracture in temper-embrittled steel is intergranular and propagates along prior austenitic grain boundaries. The embrittlement occurs only in the presence of specific impurities, e.g. P, Sn, Sb and As. These elements have been shown to segregate along prior austenite grain boundaries during tempering. Similar type of temper embrittlement can occur in martensitic stainless steel (SS) if tempered in the temperature range of 450-600 °C. This paper reports a case of failure of components made from martensitic SS 420 due to temper embrittlement. These components were subjected to a temperature of 120 °C in the initial stages of service and had shown brittle fractures. Scanning electron microscopic examination of the fracture surface of both the components showed intergranular fracture. The microstructures of the failed components confirmed that the materials were in hardened and tempered condition. In addition, the microstructure revealed both intergranular corrosion (IGC) and intergranular cracking. The electron backscatter diffraction study also showed retained austenite in the first components material. The material undergoing IGC might be related to a wrong heat-treatment during fabrication and subsequent pickling procedures. To confirm this, a sample each from both the components was exposed to 5% nitric acid solution at 25 °C. The results showed very high corrosion rate and the attack was intergranular in nature. The failure of both the components was concluded to be due to wrong tempering treatment in the temperature range of 450-600 °C that cause grain boundaries to become susceptible to embrittlement and corrosion.

Abstract: In the present study macro electrochemical (anodic polarization) and micro electrochemical (scanning electrochemical microscopy (SECM) area scan measurements at passive potential) techniques have been used to study the influence of sigma phase and/or the resultant chromium depletion regions on localized corrosion behavior of aged type 2205 duplex stainless steel (DSS) in neutral chloride ion solution. DSS type 2205 was subjected to aging at 750 °C for 30 min, 10 h and 48 h. The formation and growth of the sigma phase with heat treatments was assessed by optical microscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction. The influence of formation of sub-microscopic and bulky sigma phase on intergranular corrosion (IGC) and pitting corrosion was investigated by various electrochemical techniques including electrochemical potentiokinetic reactivation (EPR), potentiodynamic polarization and SECM. Apart from EPR tests, ASTM A 262 Practice B test was carried out to evaluate the presence of chromium depletion regions with heat treatments. The results showed that with increasing aging duration, the degree of sensitization and IGC rates initially increased and then decreased with heat treatment. The pitting potentials decreased continuously with increase in aging duration up to 10 h as assessed by potentiodynamic polarization tests. The SECM area scan measurements showed more metastable pitting corrosion events for 30 min and 10 h aged specimens compared to the 48 h aged specimen at passive potential in 0.1M neutral chloride ion solution.

Abstract: The in-cell stainless steel piping and erection works require extensive welding. In many instances the approach for gas tungsten arc welding (GTAW) is limited and it is not possible to provide a cover of high purity inert Argon gas (backing shield) and in some instances, oxidation of the weldment takes place. The oxide forms over the weld fusion zone (root pass) as well as a heat tint forms over the surfaces of the adjacent base material. In reprocessing and waste management plants, the welded pipes come in contact with the process fluid which is nitric acid of concentration up to 6 M and at temperatures up to boiling point. The present study was focused on preparing induced oxidized welds of type 304L using filler wire of type 308L, using gas tungsten arc welding (GTAW) process and studying their corrosion behavior in nitric acid environments. Sample welds were prepared under proper welding conditions and also with conditions in which deliberately Argon gas was not purged or partially purged. The weldments with no oxides, partial oxides and excess oxides on the weld root pass were used for corrosion and characterization studies. Micro Laser Raman spectroscopy established the oxide to be hematite. Metallographic examination of the cross-section of the weldment showed the thickness of oxide to be 200-300 mm. Corrosion tests of the weldments as per practice C, A262, ASTM were done for five periods. Metallographic examination was done after the practice C exposures and showed absence of oxides on the weld root pass. Type 304L specimens were heat treated at 500 – 900 °C for 5 minutes to generate heat tints. These specimens were tested as per practice C, A262, ASTM for 5h and four periods of 48 h each. The corrosion rate in the first five hours exposure was high for the specimen heat treated at 900 °C but it came down to normal values in subsequent exposures. To confirm the corrosion behavior of hematite and magnetite in boiling nitric acid, powders of pure Fe₂O₃ and Fe₃O₄ were tested in boiling 65% nitric acid. The results are analyzed to establish the behavior of oxides on the stainless steel welds in nitric acid.

Abstract: The susceptibility of non sensitized 304L stainless steel (SS) components towards stress corrosion cracking (SCC) has been studied here in the light of the significant role played by surface working operations. The plant experience shows that the fracture surfaces of non sensitized 304L stainless steel components have no signs of carbide precipitation. However, heavy plastic deformation has been evidenced in the form of high density of slip bands on the surface up to a depth of about 100 μm with high tensile residual stresses near the surface. The present study has established that the primary cause of the increase in SCC susceptibility is the heavy plastic deformation near the surface and high magnitude of tensile residual stresses which is a consequence of the surface finishing operations like machining and grinding. In this study, solution annealed 304L stainless steel has been subjected to a) surface working operations like machining and grinding and b) bulk deformation operations such as 10 % cold rolling operation. The materials in different conditions where then subjected to detailed a) microstructural characterisation, b) electrochemical characterisation and c) tests for determining the stress corrosion cracking susceptibility. The distinct differences in the micro structure as a result of bulk deformation vs. surface deformation of 304L austenitic stainless steel were highlighted and correlated to the susceptibility towards stress corrosion cracking. The effect of surface working on the nature and composition of high temperature (300 °C and 10 MPa) oxide formed on 304L stainless steel has been studied in-situ by contact electric resistance (CER) and electrochemical impedance spectroscopy measurements using controlled distance electrochemistry technique in high purity water (conductivity < 0.1 μScm^-1) at 300 °C and 10 MPa in an autoclave connected to a recirculation loop system. The results highlighted the distinct differences in the oxidation behaviour of surface worked material as compared to solution annealed material in terms of specific resistivity and low frequency Warburg impedance.

Abstract: The anodic polarization behavior of Sanicro 28 austenitic stainless steels has been established in the cold worked (10 to 80% reduction in thickness) samples in 1N HCl, 1M H₂SO₄+ 1.5N HCl and 3N HCl solutions at room temperature. The current oscillations during the potentiodynamic scans appeared in 3N HCl implying formation of meta stable pits and this solution more severe than 1N HCl and 1M H₂SO₄+ 1.5N HCl. Two anodic peaks were observed in as-received and the cold worked samples in 3N HCl. In as-received state, the first anodic peak appeared at-3.95 mV_SCE and the second anodic peak appeared at 116 mV_SCE. It was established that selective dissolution started from 18mV_SCE. The grains and grain boundaries were not attacked at the beginning of the first peak-168 mV_SCE and started revealing at 18 and 216 mV_SCE in the potentiodynamic polarization test. The fore-scatter detector (FSD) attached to FEI Quanta EBSD revealed the pitting morphology of the specimens. It is shown that pit dimensions, types, distribution, the shape of pits in all deformation conditions is hemispherical and number of pits did not depend on the microstructural features, irrespective of the plastic deformation and it may not be related to severity of plastic deformation.

Abstract: The austenitic stainless steels are used in nuclear spent fuel reprocessing and waste management plants and the process fluid is nitric acid at temperature up to boiling point. However incorporation of oxidizing ions e.g. fission products as well as corrosion products, in nitric acid stream make the environment highly corrosive to stainless steels. Present work aims to investigate role of process parameters and material parameters (composition and microstructure) on corrosion behaviour of stainless steels. The process parameters studied are temperature, acid concentration and oxidizing ions. It has been shown that the potential attained on stainless steel is a function of acid concentration and temperature and is further strongly affected by addition of oxidizing ions. This developed potential determines the corrosion behaviour of stainless steel. Increasing the temperature and concentration of nitric acid and concentration of oxidizing species increased the developed potential. Potentials were applied to types 304 L (nitric acid grade - NAG), 304 L (commercial purity) and 310 L stainless steels in boiling 6 M nitric acid for a period of 48 h. The corrosion rates measured in such experiments were plotted as a function of applied potential. The form of corrosion was established by microstructural examination. A clear demarcation was observed between uniform corrosion and intergranular corrosion at a potential of 960-980 mV_SCE. Above this potential range corrosion rate increased exponentially and the form of corrosion is shown to be intergranular corrosion. Below this potential range, uniform and low rate of corrosion occurred. The influence of microstructure (step, dual and ditch) of type 304 L was also studied and is described in this paper.

Abstract: Nuclear spent fuel reprocessing and waste management plants use nitric acid as process fluid and type 304 L stainless steel as construction material. Tubular products like bars, tubes and pipes are prone to End Grain Corrosion from the exposed cross-sectional surfaces. In this study, type 304 L stainless steel is subjected to different heat treatment to induce selective segregation of phosphorus. The susceptibility to End Grain Corrosion was established in tests using boiling nitric acid containing oxidizing Cr(VI) ions. A clear effect on End Grain Corrosion was found for heat treatment reported to induce phosphorus segregation. Finally, specific annealing heat treatment is developed that erases out the segregation, without affecting the grain size or sensitization.

Abstract: Thermal aging embrittlement of type 304L stainless steel weld is investigated on the basis of changes in microstructure, microhardness and electrochemical behavior after aging up to 20,000 h at 335, 365 and 400 °C. Spinodal decomposition and G-phase precipitation in the ferrite was observed after thermal aging. Aging led to increase in the hardness of ferrite phase while there was no change in the hardness of austenite. The changes in electrochemical behavior due to aging were studied using double loop electrochemical potentiokinetic reactivation (DL-EPR) test. Aging led to increase in the DL-EPR value which is attributed to Cr depletion in the ferrite phase.

Abstract: Intergranular Stress Corrosion Cracking (IGSCC) of austenitic Stainless Steels (SS) in Boiling Water Reactor (BWR) environment is generic in nature in both the sensitised and the non-sensitized conditions. IGSCC in non-sensitized austenitic SS in the strain hardened condition has been reported without any grain boundary chromium depletion or impurity segregation. The present study ascertains the reason for IGSCC in BWR environment in non-sensitized condition and investigates the effect of nitrogen content in SS on the susceptibility to IGSCC. Two heats of type 304LN stainless steel with 0.08 and 0.16 wt. % nitrogen were used. Strain hardening was done by cross rolling at 200 °C to 20 % thickness reduction (warm rolling) to simulate the weld induced strain in constrained welds. Subsequently, Transmission Electron Microscopic (TEM) examination was carried out on the rolled SS. The deformation mode observed due to warm rolling was predominantly elongated twin and shear band (SB) formation in both the SS, terminating at the grain boundary regions. This resulted in higher stresses and strains making grain boundary susceptible to IGSCC. Presence of more dislocations at grain boundaries is a key feature for such enhancement in the susceptibility of non-sensitized SS to IGSCC. Formation of twins and SB occurred to a greater extent in the SS with higher nitrogen content indicating greater susceptibility to IGSCC in BWR environment. Crack growth studies done in simulated BWR environment at different Dissolved Oxygen (DO) levels showed higher crack growth rates in the SS with higher nitrogen content in the non-sensitised and strain hardened condition, confirming the higher susceptibility of SS with a higher level of nitrogen.

Abstract: The present study had one broad objective – to systematically characterize effects of overall grain boundary nature on localized corrosion, intergranular corrosion (IGC) and stress corrosion cracking (IGSCC), of type 304 (UNS S 30400) austenitic stainless steel. Various combinations of cold rolling and solution annealing, were applied to alter relative the relative concentrations of ‘special’ or low CSL boundaries and to relate them with the local corrosion resistance, IGC and IGSCC, after respective sensitization treatments. It has been shown that both extreme high and low concentration of random (or high energy) boundaries can provide an effective means of control for localized corrosion, degree of sensitization (DOS), IGC and IGSCC, - the improvement in localized corrosion resistance at extreme grain boundary randomization being more effective.