Using high throughput experimental data and in silico models to discover alternatives to toxic chromate corrosion inhibitors

Winkler, David A.; Breedon, Michael; White, P. A.; Hughes, Alison; Sapper, Erik D.; Cole, Ivan

doi:10.1016/j.corsci.2016.02.008

Cited by 112 publications

(64 citation statements)

References 34 publications

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“…For a more thorough approach, which involves a deconstruction of various relevant elements and their integration into a multiscale model, see the recent paper of Taylor et al [10]. Another promising approach, aimed towards the rational design of new corrosion inhibitors, utilizes machine-learning methods (e.g., see the recent review of Winkler [11]), with which it is possible to generate reasonably robust and predictive quantitative models, but the success comes at the expense of much lower mechanistic insight compared to computationally intensive physics-based methods [12,13].…”

Section: Introductionmentioning

confidence: 99%

DFT Study of Azole Corrosion Inhibitors on Cu2O Model of Oxidized Copper Surfaces: I. Molecule–Surface and Cl–Surface Bonding

Gustinčič

Kokalj

2018

Metals

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Abstract:The adsorption of three simple azole molecules-imidazole, triazole, and tetrazole-and Cl on various sites of several Cu 2 O(111)-and Cu 2 O(110)-type surfaces, including Cu and O vacancies, was characterized using density functional theory (DFT) calculations; the three molecules can be seen as models of azole corrosion inhibitors and Cl as a corrosion activator. Both non-dissociative and dissociative adsorption modes were considered for azole molecules; the latter involves the N-H bond cleavage, hence we also addressed the adsorption of H, which is a co-product of the dissociative adsorption. We find that molecules and Cl bind much stronger to unsaturated Cu sites compared to saturated ones. Dissociated molecules bind considerably stronger to the surface compared to the intact molecules, although even the latter can bind rather strongly to specific unsaturated Cu sites. Bader analysis reveals that binding energies of dissociated molecules at various Cu sites correlate with Bader charges of Cu ions before molecular adsorption, i.e., the smaller the Cu charge, the stronger the molecular bonding. All three azole molecules display similar non-dissociative adsorption energies, but significant difference between them appears for dissociative adsorption mode, i.e., dissociated triazole and tetrazole bind much stronger than dissociated imidazole because the former two can form two strong N-Cu bonds, but imidazole cannot due to its incompatible molecular geometry. Dissociative adsorption is consequently favorable only for triazole and tetrazole, but only at oxygen vacancy sites, where it proceeds barrierlessly (or almost so). This observation may suggest that, for imidazole, only the neutral form, but, for triazole and tetrazole, also their deprotonated forms are the active species for inhibiting corrosion under near neutral pH conditions, where copper surfaces are expected to be oxidized. As for the comparison with the Cl-surface bonding, the calculations indicate that only dissociated triazole and tetrazole bind strong enough to rival the Cl-surface bonds.

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Section: Introductionmentioning

confidence: 99%

DFT Study of Azole Corrosion Inhibitors on Cu2O Model of Oxidized Copper Surfaces: I. Molecule–Surface and Cl–Surface Bonding

Gustinčič

Kokalj

2018

Metals

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“…They developed a 12-element, spatially addressable electrochemical platform interfaced to a commercial EIS instrument [20]. Recently, White et al described a novel method for assessing corrosion inhibition via a high-throughput testing rig ( Figure 1) [1,21]. Up to 88 simultaneous corrosion inhibition tests can be carried out on a single plate, with positive and negative controls, in approximately one day.…”

Section: High-throughput Synthesis and Testing Of Organic Corrosion Imentioning

confidence: 99%

“…For example, the use of chromate inhibitors is being phased out in most countries. It has been estimated that workers exposed to chromate residues when aircraft is sanded and recoated have up to a 250,000-fold higher risk of cancer than the general public [1].…”

Section: Introductionmentioning

confidence: 99%

Predicting the Performance of Organic Corrosion Inhibitors

Winkler

2017

Metals

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Abstract:The withdrawal of effective but toxic corrosion inhibitors has provided an impetus for the discovery of new, benign organic compounds to fill that role. Concurrently, developments in the high-throughput synthesis of organic compounds, the establishment of large libraries of available chemicals, accelerated corrosion inhibition testing technologies, and the increased capability of machine learning methods have made discovery of new corrosion inhibitors much faster and cheaper than it used to be. We summarize these technical developments in the corrosion inhibition field and describe how data-driven machine learning methods can generate models linking molecular properties to corrosion inhibition that can be used to predict the performance of materials not yet synthesized or tested. We briefly summarize the literature on quantitative structure-property relationships models of small organic molecule corrosion inhibitors. The success of these models provides a paradigm for rapid discovery of novel, effective corrosion inhibitors for a range of metals and alloys in diverse environments.

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“…[38,141] The resulting grafted macrocyclic complex was investigated using scanning tunnelling microscopy (STM) and X-ray H24MBA was found to be an effective corrosion inhibitor for both alloys, while H23MBA was a poor inhibitor for AA2024-T3 and accelerated corrosion in the case of AA7075-T6. [142,143,144] Experimental work has been supplemented by computational studies, which investigated ionisation and deprotonation energies as indicators of the effectiveness of various small molecules (including H24MBA) as functional coatings.…”

Section: Metal Surfacesmentioning

confidence: 99%

Coordination chemistry of 3- and 4-mercaptobenzoate ligands: Versatile hydrogen-bonding isomers of the thiosalicylate (2-mercaptobenzoate) ligand

Tiekink

Henderson

2017

Coordination Chemistry Reviews

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This review summarises the coordination chemistry of the isomeric 3-and 4-mercaptobenzoate ligands, derived from HSC6H4COOH, being analogues to the widely-studied 2-mercaptobenzoate (thiosalicylate) ligand. The 3-and 4-mercaptobenzoate ligands show a wide range of coordination modes, including monodentate (through either S or less commonly O), chelation through the carboxylate group alone, as well as a wide range of bridging modes.However, S,O-chelation, which is prevalent for thiosalicylate complexes, is not found in the 3MBA and 4MBA analogues. In the solid-state, complexes of 3MBA and 4MBA ligands containing protonated carboxylic acid groups typically undergo aggregation through formation of classical hydrogen-bonded carboxylic acid dimer motifs, which can be supplemented by additional interactions such as aurophilic (Au···Au) interactions in the case of gold (I) complexes. The hybrid hard-soft nature of 3MBA and 4MBA ligands facilitates the use of these ligands in the construction of early-late heterobimetallic complexes. These ligands also find numerous applications (such as the protection of metallic gold and silver nanoparticles), which are especially prevalent for 4MBA where the para carboxylate/carboxylic acid group is remote from the sulphur coordination site.

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Using high throughput experimental data and in silico models to discover alternatives to toxic chromate corrosion inhibitors

Cited by 112 publications

References 34 publications

DFT Study of Azole Corrosion Inhibitors on Cu2O Model of Oxidized Copper Surfaces: I. Molecule–Surface and Cl–Surface Bonding

DFT Study of Azole Corrosion Inhibitors on Cu2O Model of Oxidized Copper Surfaces: I. Molecule–Surface and Cl–Surface Bonding

Predicting the Performance of Organic Corrosion Inhibitors

Coordination chemistry of 3- and 4-mercaptobenzoate ligands: Versatile hydrogen-bonding isomers of the thiosalicylate (2-mercaptobenzoate) ligand

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