Mechanism and Predictive/Deterministic Aspects of Corrosion

A special issue of Corrosion and Materials Degradation (ISSN 2624-5558).

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 15171

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Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA
Interests: corrosion science; electrochemistry; battery science; nuclear power reactors

Special Issue Information

Dear Colleagues,

Complex industrial systems are unique, even when they are of the same design, often because of unique operating conditions and histories. As failures of complex industrial systems are rare events, it is generally impossible to develop an effective calibrating database to cover all failure scenarios via empiricism. Thus, empirical models are generally expensive, because of the need for large, labor-intensive calibrating databases that cover the impact of all conceivable independent variables. Empirical models also fail to capture the mechanism of failure and they, generally, fail to yield the accuracy of prediction to make them useful for maintenance and life extension analyses of complex industrial systems (e.g., nuclear power reactors or oil and gas pipelines). Of great importance is that empirical models have limited prediction factors, PF (time of prediction/calibrating data record). Commonly, for an empirical model, 1 < PF < 10, whereas for deterministic models, 1 < PF < 1000 or more. Indeed, this feature of determinism is being exploited in modeling the fate of metallic canisters for the disposal of high-level nuclear waste (HLNW) where a PF of > 100,000 is required to ensure that the waste can be isolated from the biosphere for sufficient time for the fission product nuclides to decay to harmless levels.

In a more mundane scenario, we might ask: “Why is accurate prediction important?” Corrosion damage is responsible for huge economic losses in industrialized societies (3–4.5% of GDP per year or about USD 0.630 to USD 0.945 trillion in the US in 2020 based on a GDP of USD 21 trillion). The worldwide cost is three to four times greater, making corrosion one of the costliest of all-natural phenomena. For comparison, the cost of hurricanes and earthquakes is estimated to be < USD 100 billion annually. Approximately 30% of that cost could be avoided by better application of existing corrosion control technology, if only we knew in advance where and when corrosion damage might occur. Thus, if we knew when and where failures might occur, systems might be serviced during scheduled outages (SOs), thereby avoiding costly, unscheduled down time, because the cost of an SO is already built into the price of the product. The most insidious forms of corrosion are localized corrosion, such as pitting, stress corrosion cracking, corrosion fatigue, hydrogen embrittlement, and crevice corrosion, because they often produce failures with little outward sign of accumulated damage. To date, prediction has been made largely upon the basis of empirical models, e.g., extreme value statistics, which generally have failed to produce the required accuracy of prediction to be truly useful in an engineering sense.

Much has been written about the philosophical basis of science, extending all the way back 2870 years when Aristotle (384–322 BC) published his treatise, Physics [1] in 350 BC. Although Aristotle is often credited with defining the concept of causality, upon which modern scientific philosophy is based, in the opinion of the author, this attribution is perhaps a little overstated. Although he did discuss at some length the nature of “cause” and the resulting “effect”, but not always in those specific terms, he did not do so in terms of quantifiable concepts, such as “force” or “displacement”, respectively. Nevertheless, Aristotle, for his time, displayed great insight into the philosophical basis of the natural world as is displayed by his statement: “It is plain then that nature is a cause, a cause that operates for a purpose.” Indeed, in his writings, it is possible to detect the foundation of Newton’s Laws of Motion, which are generally regarded as being the foundation of modern physics but which were formulated about 2200 years later. Undoubtedly, Newton was conversant with the writings of Aristotle, as were many prominent natural philosophers of Newton’s time. A comprehensive discussion of the philosophical basis of science is well beyond the scope of this Special Issue and the reader will find many, outstanding treatise on the subject identified on the Web. Names such as Plato, Al Ghazali, Al-Khwarizmi, Bacon, Kant, Newton, Galilei, Descartes, Leibniz, Mach, Poincaré, Einstein, Russell, Whitehead, Popper, Kuhn, and Torretti, to name but a few of the more prominent philosophers spanning the period from Aristotle to the present day. Below, the views on “science” are strictly those of the author and no pretense is made that the views represent those of mainstream scientists or previous or current scientific philosophers.

Extensive enquiry by the author on the nature of science and the role of determinism in the scientific process has led him to conclude that “science” is a process wherein there occurs a transition from empiricism (what we observe) to determinism (the condensation of scientific knowledge in the form of the natural laws). A particularly important feature of the natural laws is that they are time and space invariant. Accordingly, the laws are as valid on Planet Mars as they are on Planet Earth and they will remain valid for all time. It is true that, occasionally, natural laws are revised to reflect a more complete understanding of the bases of the laws. A good example is the reformulation of the laws of energy conservation and mass conservation into the law of mass–energy conservation on the basis of Einstein’s famous formula, E = mc2, where m is the rest mass, and c is the velocity of light in a vacuum.

The transition from empiricism to determinism involves the development of theories and models, with the “scientific method” being used to nudge the models toward reality. In this regard, we can never achieve “reality”, because we view our surroundings through imperfect senses and we interpret the results through imperfect intellects. Indeed, the purpose in developing more precise instruments (e.g., electron microscopes) is to extend our senses to higher resolution. Likewise, the development of high-speed computers has extended our intellect into the analysis of more complex systems. In any event, theories represent an understanding of how a system operates and interacts with its surroundings. Importantly, not all theories predict or calculate. For example, Darwin’s Theory of Evolution explains the evolution of biological systems through the process of natural selection but it cannot tell us how the human race will evolve over the next million years. On the other hand, the predictive arm of a theory, if it exists, must have a theoretical basis (the theory itself) and, if it is deterministic, its predictions are constrained by the relevant natural laws. Thus, for an electrochemical/corrosion model, the prediction is constrained by the laws of mass–energy and charge conservation and by mass–charge equivalency (Faraday’s law). It is this characteristic that imbues the model with the quality of “determinism”.

Finally, it is vital in deterministic prediction to recognize the concept of the system evolutionary path (SEP), which is defined as the path taken by the system in terms of those independent variables that have a significant impact on the damage accumulation rate. For example, in the case of the intergranular stress corrosion cracking (IGSCC) of sensitized stainless steel in the coolant (water at 288 oC) circuit of a Boiling Water (Nuclear) Reactor (BWR), the relevant independent variables are identified as temperature, corrosion potential (ECP), stress intensity factor, coolant flow velocity, coolant conductivity, degree of sensitization of the steel, including sensitization induced by neutron irradiation of in-core components, hardness and yield strength (if annealing occurs during operation), and possibly many others. Variables, such as steel composition, that remain invariant during the operation of the system are not included unless they affect some other independent variable that does change over the operating history of the system. For example, stainless steel contains a certain amount of carbon (typically 0.02–0.1%) that is instrumental in the phenomenon of sensitization, whereby the carbon reacts with chromium to precipitate chromium carbide (Cr23C6) on the grain boundaries and depleting the neighboring regions adjacent to the boundaries of passivity-inducing Cr. These grain boundaries become the preferred paths for the propagation of cracks in the phenomenon of IGSCC. As sensitization may occur at the operating temperature of a BWR (288 oC), albeit slowly, and noting that the formation of grain boundary chromium carbides may be accelerated by neutron irradiation, the chromium content becomes an important independent variable that should be included in defining the SEP. As we cannot predict the idiosyncrasies of future plant operation, specification of the SEP is usually carried out upon the bases of the past operating histories of similar plants or on idealized paths that are specified by the designers and/or the operators. Regardless, the accurate prediction of the accumulation of damage requires accurate specification of the SEP, and that is frequently one of the more difficult tasks in the overall problem.

  1. 350 BC PHYSICS by Aristotle, translated by R. P. Hardie and R. K. Gaye

Prof. Dr. Digby Macdonald
Guest Editor

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Published Papers (7 papers)

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Research

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16 pages, 4527 KiB  
Article
Scanning Kelvin Probe for Detection in Steel of Locations Enriched by Hydrogen and Prone to Cracking
by Andrei Nazarov, Varvara Helbert and Flavien Vucko
Corros. Mater. Degrad. 2023, 4(1), 158-173; https://doi.org/10.3390/cmd4010010 - 02 Mar 2023
Cited by 2 | Viewed by 1830
Abstract
Hydrogen, due to corrosion processes, can degrade high strength steels (HSS) through embrittlement and stress corrosion cracking mechanisms. Scanning Kelvin probe (SKP) mapping of surface potential was applied, to visualize the locations with an increased subsurface concentration of hydrogen in mild steel and [...] Read more.
Hydrogen, due to corrosion processes, can degrade high strength steels (HSS) through embrittlement and stress corrosion cracking mechanisms. Scanning Kelvin probe (SKP) mapping of surface potential was applied, to visualize the locations with an increased subsurface concentration of hydrogen in mild steel and martensitic HSS. This work can help to determine the reasons behind hydrogen localization in a steel microstructure, leading to embrittlement and hydrogen-assisted cracking. Cathodic charging was used to insert hydrogen, which decreased the steel potential. Hydrogen effusion in air passivates steel, increasing the potential of HSS and mild steel. The passivation of steels was monitored depending on different conditions of cathodic pre-charging and the amount of absorbed hydrogen. The SKP could determine the area of diffusible hydrogen and the area of cracks. In addition, low potential locations linked to the hydrogen trapped in the deformed HSS microstructure were also determined, which delayed the steel passivation. Mild steel showed a uniform potential distribution related to interstitial hydrogen, without potential extremes attributed to locally accumulated hydrogen. Thus, SKP sensing can detect locations containing increased concentrations of hydrogen and sensitive to steel cracking. Full article
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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Review

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76 pages, 5357 KiB  
Review
Review of the Modelling of Corrosion Processes and Lifetime Prediction for HLW/SF Containers—Part 1: Process Models
by Fraser King, Miroslav Kolàř, Scott Briggs, Mehran Behazin, Peter Keech and Nikitas Diomidis
Corros. Mater. Degrad. 2024, 5(2), 124-199; https://doi.org/10.3390/cmd5020007 - 28 Mar 2024
Viewed by 627
Abstract
The disposal of high-level radioactive waste (HLW) and spent nuclear fuel (SF) presents a unique challenge for the prediction of the long-term performance of corrodible structures since HLW/SF containers are expected, in some cases, to have lifetimes of one million years or longer. [...] Read more.
The disposal of high-level radioactive waste (HLW) and spent nuclear fuel (SF) presents a unique challenge for the prediction of the long-term performance of corrodible structures since HLW/SF containers are expected, in some cases, to have lifetimes of one million years or longer. Various empirical and deterministic models have been developed over the past 45 years for making predictions of long-term corrosion behaviour, including models for uniform and localised corrosion, environmentally assisted cracking, microbiologically influenced corrosion, and radiation-induced corrosion. More recently, fracture-mechanics-based approaches have been developed to account for joint mechanical–corrosion degradation modes. Regardless of whether empirical or deterministic models are used, it is essential to be able to demonstrate a thorough mechanistic understanding of the corrosion processes involved. In addition to process models focused on specific corrosion mechanisms, there is also a need for performance-assessment models as part of the overall demonstration of the safety of a deep geological repository. Performance-assessment models are discussed in Part 2 of this review. Full article
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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29 pages, 4640 KiB  
Review
A Review on Tribocorrosion Behavior of Aluminum Alloys: From Fundamental Mechanisms to Alloy Design Strategies
by Zhengyu Zhang, Raja Shekar Bhupal Dandu, Edwin Eyram Klu and Wenjun Cai
Corros. Mater. Degrad. 2023, 4(4), 594-622; https://doi.org/10.3390/cmd4040031 - 18 Oct 2023
Cited by 1 | Viewed by 2027
Abstract
Tribocorrosion, a research field that has been evolving for decades, has gained renewed attention in recent years, driven by increased demand for wear- and corrosion-resistant materials from biomedical implants, nuclear power generation, advanced manufacturing, batteries, marine and offshore industries, etc. In the United [...] Read more.
Tribocorrosion, a research field that has been evolving for decades, has gained renewed attention in recent years, driven by increased demand for wear- and corrosion-resistant materials from biomedical implants, nuclear power generation, advanced manufacturing, batteries, marine and offshore industries, etc. In the United States, wear and corrosion are estimated to cost nearly USD 300 billion per year. Among various important structural materials, passive metals such as aluminum alloys are most vulnerable to tribocorrosion due to the wear-accelerated corrosion as a result of passive film removal. Thus, designing aluminum alloys with better tribocorrosion performance is of both scientific and practical importance. This article reviews five decades of research on the tribocorrosion of aluminum alloys, from experimental to computational studies. Special focus is placed on two aspects: (1) The effects of alloying and grain size on the fundamental wear, corrosion, and tribocorrosion mechanisms; and (2) Alloy design strategies to improve the tribocorrosion resistance of aluminum alloys. Finally, the paper sheds light on the current challenges faced and outlines a few future research directions in the field of tribocorrosion of aluminum alloys. Full article
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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22 pages, 3187 KiB  
Review
Improved and Innovative Accident-Tolerant Nuclear Fuel Materials Considered for Retrofitting Light Water Reactors—A Review
by Raul B. Rebak
Corros. Mater. Degrad. 2023, 4(3), 466-487; https://doi.org/10.3390/cmd4030024 - 24 Aug 2023
Cited by 1 | Viewed by 1716
Abstract
Since 2011, there has been an international effort to evaluate the behavior of newer fuel rod materials for the retrofitting of existing light water reactors (LWR). These materials include concepts for the cladding of the fuel and for the fuel itself. The materials [...] Read more.
Since 2011, there has been an international effort to evaluate the behavior of newer fuel rod materials for the retrofitting of existing light water reactors (LWR). These materials include concepts for the cladding of the fuel and for the fuel itself. The materials can be broadly categorized into evolutionary or improved existing materials and revolutionary or innovative materials. The purpose of the newer materials or accident-tolerant fuels (ATF) is to make the LWRs more resistant to loss-of-coolant accidents and thus increase their operation safety. The benefits and detriments of the three main concepts for the cladding are discussed. These include (i) coatings for existing zirconium alloys; (ii) monolithic iron–chromium–aluminum alloys; and (iii) composites based on silicon carbide. The use of ATF materials may help extend the life of currently operating LWRs, while also being a link to material development for future commercial reactors. Full article
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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62 pages, 12998 KiB  
Review
The Role of Determinism in the Prediction of Corrosion Damage
by Digby D. Macdonald
Corros. Mater. Degrad. 2023, 4(2), 212-273; https://doi.org/10.3390/cmd4020013 - 27 Mar 2023
Cited by 1 | Viewed by 1588
Abstract
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 [...] Read more.
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
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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14 pages, 38339 KiB  
Review
Reflections on Early Stages of Environmentally Assisted Cracking from Corrosion Pits
by Alan Turnbull
Corros. Mater. Degrad. 2021, 2(4), 568-581; https://doi.org/10.3390/cmd2040030 - 28 Sep 2021
Cited by 7 | Viewed by 3086
Abstract
A perspective is presented on the evolution of damage due to environmentally assisted cracking (EAC), from crack precursor development through to long crack growth. The variable nature of crack precursors is highlighted with an observation that uncontrolled chemistry excursions or fabrication defects could [...] Read more.
A perspective is presented on the evolution of damage due to environmentally assisted cracking (EAC), from crack precursor development through to long crack growth. The variable nature of crack precursors is highlighted with an observation that uncontrolled chemistry excursions or fabrication defects could eliminate any significant delay associated with that step in the damage evolution process. Specimen preparation by machining and grinding can be critical in determining the apparent susceptibility of the metal to EAC and corrosion, and an example for 316L stainless steel is given to show how physical defects generated by the grinding wheel can become the dominant site for pitting attack relative to MnS inclusions. Corrosion pits are the most commonly observed precursor to cracks in aqueous chloride environments. The loci of sites of crack initiation around a pit are discussed and the inherent challenges in quantifying the growth of cracks smaller than the pit depth described with implications for modelling of the pit-to-crack transition. The remarkably enhanced stress corrosion crack growth rate data for short and small cracks in a 12Cr steam turbine blade in a simulated condensate environment are discussed in the context of crack electrochemistry modelling and the implications for engineering integrity. Full article
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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Other

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8 pages, 2289 KiB  
Technical Note
The Virtual Corrosion Engineer
by Aarthi Thyagarajan, Wouter Hamer, Joy Phophichitra, Valliappan Valliappan, Abitha Ramesh, Prathamesh Shenai and Nicholas Laycock
Corros. Mater. Degrad. 2021, 2(4), 762-769; https://doi.org/10.3390/cmd2040041 - 13 Dec 2021
Cited by 1 | Viewed by 3044
Abstract
The conventional corrosion management process consists of defining the expected process conditions, identifying potential corrosion threats, and estimating their likely rate, then using that information to develop mitigation plans and inspection schedules. The Virtual Corrosion Engineer (VCE) project aims to improve this process [...] Read more.
The conventional corrosion management process consists of defining the expected process conditions, identifying potential corrosion threats, and estimating their likely rate, then using that information to develop mitigation plans and inspection schedules. The Virtual Corrosion Engineer (VCE) project aims to improve this process by utilizing online monitoring data to automate the running of the best available corrosion models and provide a continuously updated dashboard in real time. This paper provides an overview of the VCE, together with a brief discussion of the underlying models for two exemplar damage mechanisms, High-Temperature Hydrogen Attack (HTHA) and Under Deposit Corrosion (UDC) in steam generators. Full article
(This article belongs to the Special Issue Mechanism and Predictive/Deterministic Aspects of Corrosion)
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