Development of an Accelerated Methodology to Study Degradation of Materials in Supercritical Water for Application in High Temperature Power Plants
AdvisorChidambaram, Dev C.
Chemical and Materials Engineering
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The decreasing supply of fossil fuel sources, coupled with the increasing concentration of green house gases has placed enormous pressure to maximize the efficiency of power generation. Increasing the outlet temperature of these power plants will result in an increase in operating efficiency. By employing supercritical water as the coolant in thermal power plants (nuclear reactors and coal power plants), the plant efficiency can be increased to 50%, compared to traditional reactors which currently operate at ~33%. The goal of this dissertation is to establish techniques to characterize the mechanical properties and corrosion behavior of materials exposed to supercritical water. Traditionally, these tests have been long term exposure tests spanning months. The specific goal of this dissertation is to develop a methodology for accelerated estimation of corrosion rates in supercritical water that can be sued as a screening tool to select materials for long term testing. In this study, traditional methods were used to understand the degradation of materials in supercritical water and establish a point of comparison to the first electrochemical studies performed in supercritical water. Materials studied included austenitic steels (stainless steel 304, stainless steel 316 and Nitronic 50) and nickel based alloys (Inconel 625 and 718). Surface chemistry of the oxide layer was characterized using scanning electron microscopy, X-ray diffraction, FT-IR, Raman and X-ray photoelectron spectroscopies. Stainless steel 304 was subjected to constant tensile load creep tests in water at a pressure of 27 MPa and at temperatures of 200 °C, 315 °C and supercritical water at 450 °C for 24 hours. It was determined that the creep rate for stainless steel 304 exposed to supercritical water would be unacceptable for use in service. It was observed that the formation of hematite was favored in subcritical temperatures, while magnetite was formed in the supercritical region.Corrosion of stainless steel 316, Nitronic 50, Inconel 625 and Inconel 718 was exposed to supercritical water at 530 °C and ultra-supercritical water at 600 °C and was studied as a function exposure time. When exposed to supercritical water, Nitronic 50 and stainless steel 316 were observed to have similar mass gains; however, stainless steel 316 was found to gain less mass than Nitronic 50 in exposure tests performed in ultra-supercritical water. Stainless steel 316 developed surface films primarily composed of iron oxides, while the surface of Nitronic 50 contained a mixture of iron, chromium and manganese oxides. Inconels 625 and 718 samples were exposed to these temperatures for 24, 96, and 200 hours. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. For the first time, corrosion rates in supercritical water were determined using electrochemical techniques. The corrosion rates of stainless steel 316, Nitronic 50, Inconel 625 and Inconel 718 were estimated in supercritical and ultra-supercritical water using electrochemical impedance spectroscopy and electrochemical frequency modulation. For all conditions tested, the corrosion rates obtained from electrochemical testing followed similar trends to the long-term gravimetric results. As a screening tool, this protocol can potentially reduce the time required for corrosion rate studies from thousands of hours to 24 hours.