Search Results (9)

The potentiostatic, anodic formation of gold oxide at potentials of 0.55 to 0.80 V versus SHE in aqueous KOH (0.1 M) was studied using an impedance-based Point Defect Model (PDM). The film thickness and refractive indices at each formation potential were estimated using spectroscopic ellipsometry. The thickness of the oxide increases linearly with increasing applied voltage within this range. Mott-Schottky (MS) analysis showed that gold oxide formed in KOH (0.1 M) is an n-type semiconductor, and the dominant defect (${Au}_i^{3+}$) density is calculated to be in the order of 10²¹–10²² (1/cm³). The steady-state current density of the oxide formation was independent of voltage, also in agreement with an n-type oxide. Reasonable agreement between PDM predictions and experimental observations of dominant defect density, steady-state current density, and thickness, demonstrates the value of the PDM in this system. Full article

An impedance model based on the Volmer–Heyrovsky–Tafel mechanism was developed to study the kinetics of the hydrogen evolution reaction on polycrystalline gold electrodes at moderate overpotentials in aqueous H₂SO₄ (0.5 and 1.0 M) solutions. The model was optimized on data from potentiodynamic polarization and electrochemical impedance spectroscopy, and model parameters were extracted. Consistent with expectations, the magnitude of the impedance data indicated a higher rate of hydrogen evolution at lower pH. Also, the fractional surface coverage of adsorbed hydrogen (${\theta }_{Hads}$) increases with increasing overpotential but the small value of ${\theta }_{Hads}$ indicates only weak adsorption of H on gold. Tafel slopes and exchange current densities were estimated to be in the range of 81–124 mV/dec, and 10⁻⁶ and 10⁻⁵ A/cm² in H₂SO₄ (0.5 and 1.0 M), respectively. The results show that the model accounts well for the experimental data, such as the steady-state current density. Sensitivity analysis reveals that the electrochemical parameters (${\alpha }_1, {\alpha }_2, k_1^0, k_{-1}^0, {\mathrm{a}\mathrm{n}\mathrm{d} k}_2^0)$ associated with the kinetics of the hydrogen evolution reaction have a major impact on the calculated impedance but the standard rate constant for hydrogen oxidation reaction ($k_{-2}^0)$ does not strongly affect the calculated impedance. Full article

This paper explores the roles of empiricism and determinism in science and concludes that the intellectual exercise that we call “science” is best described as the transition from empiricism (i.e., observation) to determinism, which is the philosophy that the future can be predicted from the past based on the natural laws that are condensations of all previous scientific knowledge. This transition (i.e., “science”) is accomplished by formulating theories to explain the observations and models that are based on those theories to predict new phenomena. Thus, models are the computational arms of theories, and all models must possess a theoretical basis, but not all theories need to predict. The structure of a deterministic model is reviewed, and it is emphasized that all models must contain an input, a model engine, and an output, together with a feedback loop that permits the continual updating of the model parameters and a means of assessing predictions against new observations. This latter feature facilitates the application of the “scientific method” of cyclical prediction/assessment that continues until the model can no longer account for new observations. At that point, the model (and possibly the theory, too) has been “falsified” and must be discarded and a new theory/model constructed. In this regard, it is important to stress that no amount of successful prediction can prove a theory/model to be “correct”, because theories and models are merely the figments of our imagination as developed through imperfect senses and imperfect intellect and, hence, are invariably wrong at some level of detail. Contrariwise, a single failure of a model to predict an observation invalidates (“falsifies”) the theory/model. The impediment to model building is complexity and its impact on model building is discussed. Thus, we employ instruments such as microscopes and telescopes to extend our senses to examining smaller and larger objects, respectively, just as we now employ computers to extend our intellects as reflected in our computational prowess. The process of model building is illustrated with reference to the deterministic Coupled Environment Fracture Model (CEFM) that has proven to be highly successful in predicting crack growth rate in metals and alloys in contact with high-temperature aqueous environments of the type that exist in water-cooled nuclear power reactor primary coolant circuits. Full article

The radiolysis of water is a significant cause of corrosion damage in the primary heat transport systems (PHTSs) of water-cooled, fission nuclear power reactors (BWRs, PWRs, and CANDUs) and is projected to be a significant factor in the evolution of corrosion damage in future fusion reactors (e.g., the ITER that is currently under development). In Part I of this two-part series, we reviewed the proposed mechanisms for the radiolysis of water and demonstrate that radiolysis leads to the formation of a myriad of oxidizing and reducing species. In this Part II, we review the role that the radiolysis species play in establishing the electrochemical corrosion potential (ECP) and the development of corrosion damage due to intergranular stress corrosion cracking (IGSCC) in reactor PHTSs. We demonstrate, that the radiolytic oxidizing radiolysis products, such as O₂, H₂O₂, HO₂⁻, and OH, when in molar excess over reducing species (H₂, H, and O₂²⁻), some of which (H₂) are preferentially stripped from the coolant upon boiling in a BWR PHTS, for example, renders the coolant in many BWRs oxidizing, thereby shifting the ECP in the positive direction to a value that is more positive than the critical potential (E_crit = −0.23 V_she at 288 °C) for IGSCC in sensitized austenitic stainless steel (e.g., Type 304 SS). This has led to many IGSCC incidents in operating BWRs over the past five decades that has exacted a great cost on the plant operators and electricity consumers, alike. In the case of PWRs, the primary circuits are pressurized with hydrogen to give a hydrogen concentration of 10 to 50 cm³/kgH₂O (0.89 to 4.46 ppm), such that no sustained boiling occurs, and the hydrogen suppresses the radiolysis of water, thereby inhibiting the formation of oxidizing radiolysis products from water. Thus, the ECP is dominated by the hydrogen electrode reaction (HER), although important deviations from the HER equilibrium potential may occur, particularly at low [H₂]. In any event, the ECP is displaced to approximately −0.85 V_she, which is below the critical potential for IGSCC in sensitized stainless steels but is also more negative than the critical potential for the hydrogen-induced cracking (HIC) of mill-annealed Alloy 600. This has led to extensive cracking of steam generator tubing and other components (e.g., control rod drive tubes, pressurizer components) in PWRs that has also exacted a high cost on operators and power consumers. Although the ITER has yet to operate, the proposed chemistry protocol for the coolant places it close to a BWR operating on Normal Water Chemistry (NWC) without boiling or, if hydrogen is added to the IBED-PHTS, close to a BWR on Hydrogen Water Chemistry (HWC). In the current ITER technology, the concentration of H₂ in the IBED-PHTS is specified to be 80 ppb, which is the concentration that will be experienced in both the Plasma Flux Area (PFA) and in the Out of Plasma Flux Area (OPFA). That corresponds to 0.90 cc(STP) H₂/KgH₂O, compared with 20–50 cc(STP) H₂/KgH₂O employed in a PWR primary coolant circuit and 5.5 to 22 cc(STP) H₂/KgH₂O in a BWR on hydrogen water chemistry (HWC). We predict that a hydrogen concentration of 80 ppb is sufficient to reduce the ECP in the OPFA to a level (−0.324 V_she) that is sufficient to suppress the crack growth rate (CGR) below the practical, maximum level of 10⁻⁹ cm/s (0.315 mm/a) at which SCC is considered not to be a problem in a coolant circuit but, in the PFA, the ECP is predicted to be 0.380 V_she, which gives a calculated standard CGR of 2.7 × 10⁻⁶ cm/s. This is more than three orders in magnitude greater that the desired maximum value of 10⁻⁹ cm/s. We recommend that the HWC issue in ITER be revisited to develop a protocol that is effective in suppressing both the ECP and the CGR in the PFA to levels that permit the operation of the IBED-PHTS in accordance with the experience gained in fission reactor technology. Full article

A critical review is presented on modeling of the radiolysis of the coolant water in nuclear power reactors with emphasis on ITER. The review is presented in two parts: In Part I, we assess previous work in terms of compliance with important chemical principles and conclude that no model proposed to date is completely satisfactory, in this regard. Thus, some reactions that have been proposed in various radiolysis models are not elementary in nature and can be decomposed into two or more elementary reactions, some of which are already included in the models. These reactions must be removed in formulating a viable model. Furthermore, elementary reactions between species of like charge are also commonly included, but they can be discounted upon the basis of Coulombic repulsion under the prevailing conditions (T < 350 °C) and must also be removed. Likewise, it is concluded that the current state of knowledge with respect to radiolytic yields (i.e., G-values) is also unsatisfactory. More work is required to ensure that the yields used in radiolysis models are truly “primary” yields corresponding to a time scale of nanoseconds or less. This is necessary to ensure that the impact of the reactions that occur outside of the spurs (ionizing particle tracks in the medium) are not counted twice. In Part II, the authors review the use of the radiolysis models coupled with electrochemical models to predict the water chemistry, corrosion potential, crack growth rate in Type 304 SS, and accumulated damage in the coolant circuits of boiling water reactors, pressurized water reactors, and the test fusion reactor, ITER. Based on experience with fission reactors, the emphasis should be placed on the control of the electrochemical corrosion potential because it is the parameter that best describes the state of corrosion in coolant circuits. Full article

In this paper, the passivation kinetics of AA2098–T851 was investigated by a fundamental theoretical interpretation of experimental results based on the mixed potential model (MPM). The steady state passive layer formed on the AA2098–T851 in NaHCO₃ solution in a CO₂ atmosphere upon potentiostatic stepping in the anodic direction followed by stepping in the opposite direction was explored. Potentials were selected in a way that both anodic passive dissolution of the metal and hydrogen evolution reaction (HER) occur, thereby requiring the MPM for interpretation. Optimization of the MPM on the experimental electrochemical impedance spectroscopy (EIS) data measured after each potentiostatic step revealed the important role of the migration of Al interstitials in determining the kinetics of passive layer formation and dissolution. More importantly, it is shown that the inequalities of the kinetics of formation and dissolution of the passive layer as observed in opposite potential stepping directions lead to the irreversibility of the passivation process. Finally, by considering the Butler–Volmer (B–V) equation for the cathodic reaction (HER) in the MPM, and assuming the quantum mechanical tunneling of the charge carriers across the barrier layer of the passive film, it was shown that the HER was primarily controlled by the slow electrochemical discharge of protons at the barrier layer/solution (outer layer) interface. Full article

Prediction of the accumulated pitting corrosion damage in aluminum-lithium (Al-Li) is of great importance due to the wide application of these alloys in the aerospace industry. The Point Defect Model (PDM) is arguably one of the most well-developed techniques for evaluating the electrochemical behavior of passive metals. In this paper, the passivity breakdown and pitting corrosion performance of AA 2098-T851 was investigated using the PDM with the potentiodynamic polarization (PDP) technique in NaCl solutions at different scan rates, Cl⁻ concentrations and pH. Both the PDM predictions and experiments reveal linear relationships between the critical breakdown potential (E_c) of the alloy and various independent variables, such as $a_{C{l}^{-}}$ and pH. Optimization of the PDM of the near-normally distributed E_c as measured in at least 20 replicate experiments under each set of conditions, allowing for the estimation of some of the critical parameters on barrier layer generation and dissolution, such as the critical areal concentration of condensed cation vacancies (ξ) at the metal/barrier layer interface and the mean diffusivity of the cation vacancy in the barrier layer (D). With these values obtained—using PDM optimization—in one set of conditions, the E_c distribution can be predicted for any other set of conditions (combinations of ${\mathrm{a}}_{{\mathrm{Cl}}^{-}}$ , pH and T). The PDM predictions and experimental observations in this work are in close agreement. Full article

To analyze the effect of lithium and microstructure on the pitting corrosion behavior of aluminum alloys, three types of aluminum alloys were studied via scanning electron microscopy, transmission electron microscopy, electrochemical polarization, and by immersion tests coupled with in-situ observation of pitting and statistical analysis of pit depths measured by surface profilometry. It was found that, with increasing lithium content, the resistance to pitting corrosion was enhanced and the passive range was enlarged. In-situ observation revealed that the development of pitting corrosion exhibited three stages, including an initial slow nucleation stage (Stage I), a fast development stage (Stage II), and a stabilized growth stage (Stage III). Higher lithium content contributed to shorter time periods of Stages I and II, resulting in faster pitting evolution and a higher number of pits. However, the pits were generally shallower for the specimen with the highest lithium content, which is in agreement with the results of the electrochemical analysis. Full article

The dependencies of weight gain of 9-12 Cr ferritic-martensitic steels in supercritical water on each of seven principal independent variables (temperature, oxygen concentration, flow rate, exposure time, and key chemical composition and surface condition of steels) have been predicted using a supervised artificial neural network (ANN). The relative significance of each independent variable was uncovered by fuzzy curve analysis, which ranks temperature and exposure time as the most important. The optimized ANN, not only satisfactorily represents the experimentally-known non-linear relationships between the corrosion characteristics of F-M steels and the key independent variables (demonstrating the effectiveness of this technique), but also predicts and reveals that the effects of oxygen concentration on the weight gains, to a certain degree, is influenced by the flow rate and temperature. Finally, according to the ANN predicted-results, departure of oxidation kinetics from the parabolic law, and basic cause of chromium content in steel substrate influencing the corrosion rate, and the synergetic effects of dissolved oxygen concentration, flow rate, and temperature, are discussed and analyzed. Full article