Thermodynamics of Passive Film Formation from First Principles

Francis, Michael F; Holby, Edward F.

doi:10.1002/9781119057666.ch6

Cited by 2 publications

(2 citation statements)

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“…Shown in Figure are the lowest values of Δγ mix for a given θ S and ε forming the convex hull. ,, For all applied strains, the heat of mixing is negative, indicating the C and S to be mixed under all examined strains. The maximum heat of mixing gained varies from −0.43 eV/Å at a strain of −0.03, to −0.29 eV/Å at a strain of 0.00, and to −0.25 eV/Å at a strain of 0.03.…”

Section: Resultsmentioning

confidence: 96%

“…The described state of the art in catalyst design breaks down when adsorbate–adorbate interactions become important. Adsorbate–adsorbate interactions may be controlling in poisoning, − promotion, , the formation of chemically active surface phases, − and the distortion of descriptor theory plots. , Several catalytic processes cannot be described without interactions. ,,,,− Four types of adsorbate–adsorbate interactions have been articulated as important: (i) direct interactions due to the overlap of adsorbate wave functions, (ii) indirect interactions mediated by the electronic structure of the surface, (iii) nonlocal electrostatic interactions, and (iv) elastic interactions. Given the novel findings of mechanical work playing a large role in binding energy changes under strain and the ability to controllably engineer strain, revisiting changes in interactions under strain has become timely.…”

Section: Introductionmentioning

confidence: 99%

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Elastic Effects in Adsorbate–Adsorbate Interactions of C and S on a Stepped Ru Surface

Francis

2017

J. Phys. Chem. C

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We examine strain modification of adsorbate−adsorbate interaction in the (C*+S*)/fcc-Ru( 211) system for relevance to biomass to hydrocarbon catalysis and the broader case of interaction changes under strain. Applied biaxial strains from −3% to +3% shift the C and S binding and interaction energies by ±0.3 eV for C and ±0.1 eV for S, binding and interaction being additive and leading to stronger binding with tension, creating larger total changes in binding for the covered surfaces. Changes in the near-neighbor interactions with strain are found to be primarily electronic in originthere is little change in mechanical interaction. While mixing and thermodynamic analysis reveals that the C+S system will mix over the complete range of strains studied, the application of strain, whether tensile or compressive, may lead to reduced sulfur coverage. For biomass catalysis, the implication is that strain may be used to optimize hydrocarbon chemistry with only improvements in poisoning due to site blocking. It is argued that the serendipitous addition of binding and interaction may not be specific but a general case and, therefore, contribute to the utility of strain engineering.

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Section: Resultsmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Elastic Effects in Adsorbate–Adsorbate Interactions of C and S on a Stepped Ru Surface

Francis

2017

J. Phys. Chem. C

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Investigations of the intrinsic corrosion and hydrogen susceptibility of metals and alloys using density functional theory

Taylor¹,

2021

Corrosion Reviews

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Mechanisms for materials degradation are usually inferred from electrochemical measurements and characterization performed before, during, and after exposure testing and/or failure analysis of service materials. Predicting corrosion and other materials degradation modes, such as hydrogen-assisted cracking, from first-principles has generally been limited to thermodynamic predictions from Pourbaix or Ellingham diagrams and the Galvanic series. Using electronic structure calculations, modern first-principles methods can predict ab initio the key rate-controlling processes for corrosion and hydrogen susceptibility as a function of pH, potential, and solution chemistry, and materials composition and microstructure. Herein we review density functional theory (DFT) approaches for studying the electrochemical reactions occurring on fresh metal and alloy surfaces related to environmentally assisted cracking and localized corrosion/pitting. Predicted changes in surface chemistry as a function of the environment were correlated against experimental crack growth rate data obtained for alloys 718, 725, and pipeline steel under electrochemical control. We also review the application of the method to study the effects of alloying on the chloride susceptibility of stainless steels and Ni–Cr-based corrosion-resistant alloys. Perspectives for improving the model are given, and extending it to future fields of application in corrosion science and engineering.

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Thermodynamics of Passive Film Formation from First Principles

Cited by 2 publications

References 78 publications

Elastic Effects in Adsorbate–Adsorbate Interactions of C and S on a Stepped Ru Surface

Elastic Effects in Adsorbate–Adsorbate Interactions of C and S on a Stepped Ru Surface

Investigations of the intrinsic corrosion and hydrogen susceptibility of metals and alloys using density functional theory

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