Shadow Corrosion Phenomenon – An out-of-pile Study on Electrochemical Effects

The focus of the present thesis was the study of the enhanced corrosion phenomenon named “Shadow Corrosion”. Within the context of researching based on the corrosion mechanism as well as the influencing parameters and driving forces, which cause or even intensify the corrosion, a variety of electrochemical characterization and surface analysis techniques were used. The first part of this thesis gives a short introduction with the definition of the term Shadow Corrosion and of the specific type called “Enhanced Spacer Shadow Corrosion” (ESSC). This is followed by a description of the involved materials being Zircaloy and Inconel 718. Chapter 2 introduces the background knowledge including fundamentals about environ-mental conditions under which Shadow Corrosion occurs as well as the oxidation behavior of Zircaloy and Inconel 718. Furthermore, the state of the art about the Shadow Corrosion mechanism is presented and a description of the influencing effects on the enhanced corrosion phenomenon, like galvanic corrosion, water radiolysis, and photo-effect, is given. Further information and parameters on the part of AREVA GmbH concerning water impurities and a used coating layer on Inconel 718 are listed, which are of interest for the issue concerning the phenomenon Shadow Corrosion. The last part of this chapter contains the experimental conditions and parameters for the laboratory experiments with focus on water chemistry, specimen geometry, and UV-light exposure for photoexcitation and water radiolysis. Three different working hypotheses of this thesis are described in chapter 3. One hypothesis regarding the Shadow Corrosion Phenomenon is based on a galvanic corrosion mechanism between Zircaloy and Inconel 718. In addition, it is supposed that the galvanic corrosion could be influenced by the deposition of silver on Zircaloy and Inconel 718 in the form of an increased galvanic current. A further assumption is that the galvanic current could be decreased by a CrN coating layer on Inconel 718. Objectives including a deeper knowledge about the corrosion mechanism with its influencing parameters and driving forces by studying Shadow Corrosion with out-of-pile autoclave experiments are listed in chapter 4. A further aim was to test the effectiveness of a possible spacer coating to reduce the corrosion or even to prevent the reactor plant components against Shadow Corrosion. Chapter 5 gives an overview of the experimental part with a description of the materials and chemicals, like Zircaloy and Inconel 718, as well as the specimen preparation techniques, such as etching, pre-oxidation or coating with CrN. Moreover, the three experimental test set-ups used to simulate the different conditions as a function of temperature and water chemistry parameters are depicted. The electrochemical measuring methods including electrochemical corrosion potential (ECP), galvanic corrosion (GC), electrochemical impe-dance spectroscopy (EIS) and conductometry are described. Further methods for surface analyses comprising microscopy, scanning electron microscopy (SEM), focused ion beam (FIB), transmission electron microscopy (TEM), ellipsometry, ion coupled plasma optical emission spectroscopy (ICP-OES) and spectrophotometry are presented. Results and corresponding discussions are summarized in chapter 6, which is divided into three subchapters. Chapter 6.1 deals with electrochemical parameters, like electrochemical corrosion potential, galvanic potential, and galvanic current as well as parameters obtained from electrochemical impedance spectroscopy as a function of different water chemistry parameters. The focus was on the concentration of hydrogen peroxide, the presence of impurities in the form of nitrate, and the exposure to UV-light. Furthermore, surface analyses via the focused ion beam technique and the transmission electron microscopy were gathered to visualize the oxide layer structure, composition, and thickness after exposure to oxygenated high-temperature water. Results with subsequent discussions concerning the hypothesis of the silver effect on the Shadow Corrosion Phenomenon are presented in chapter 6.2 This chapter summarizes the results of the silver deposition experiments and exposure experiments using specimens with deposited silver. The focus of chapter 6.3 is the newly constructed high-temperature autoclave and the transferability of the experimental results in the tube reactor as well as the transferability to higher test temperatures up to 250 °C. As a complement, the results obtained in the high-temperature water autoclave concerning exposure tests of specimen pairings with electrochemical measuring techniques in the form of electrochemical corrosion potential, galvanic potential, galvanic current, and electrochemical impedance spectroscopy as well as with surface analyses are summarized. Preliminary electrochemical measurements by means of exposure tests in oxygenated high-temperature water of new modified coatings on Inconel 718 are also represented. Finally, chapter 7 highlites the most significant results of this thesis and chapter 8 provides an outlook for future studies concerning the topic “Shadow Corrosion”.