The Properties of Electrochemically-Grown Copper Sulfide Films

Martino, Taylor; Smith, J.; Chen, Jian; Qin, Z.; Noël, James J.; Shoesmith, David W.

doi:10.1149/2.0321902jes

Cited by 20 publications

(22 citation statements)

References 25 publications

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“…Although the location of the previously discussed base layer and its apparent thickness are indicated in Figure 8d, they are difficult to observe, owing to the presence of much larger features. The formation of such a thick crystalline outer deposit was consistent with our previous observations [ 6–15 ] and with our demonstration that growth of this deposit occurred at the film/solution interface, supported by the transport through the pores of the base layer of Cu(I), as both sulfide complexes (Cu(SH) 2 − ) and Cu 3 S 3 clusters, formed at the Cu surface. [ 15,24–29 ]…”

Section: Resultssupporting

confidence: 91%

The nature of the copper sulfide film grown on copper in aqueous sulfide and chloride solutions

Guo

Chen

Martino

et al. 2020

Materials & Corrosion

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In this paper, the properties of copper sulfide films formed both anodically and naturally in deaerated/anoxic aqueous sulfide and chloride solutions were investigated using a series of electrochemical and surface analytical techniques. A combination of cyclic voltammetric, corrosion potential (Ecorr), and cathodic stripping voltammetric experiments showed that the sulfide film growth kinetics and film morphologies were controlled by the supply of SH− from the bulk solution to the copper surface. There was no passive barrier layer observed on the copper surface under either electrochemical or corrosion conditions. The film morphology was dependent on the type and concentration of anions (SH−, Cl−) present in the solution. Scanning electron microscopy on both surfaces and focused ion beam‐cut cross‐sections showed the growth of a thin, but porous, base layer of chalcocite (Cu2S) after short immersion periods (up to 2 hr) and the continuous growth of a much thicker crystalline outer deposit over longer immersion periods (≥36 hr), suggesting a solution species transport‐based film formation process and the formation of an ineffective thin “barrier‐type” layer on copper.

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Section: Resultssupporting

confidence: 91%

The nature of the copper sulfide film grown on copper in aqueous sulfide and chloride solutions

Guo

Chen

Martino

et al. 2020

Materials & Corrosion

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“…Therefore, the probability of pitting corrosion is most likely low. Separation of the sulfide layer from the Cu substrate confirms that the corroded copper surface is roughened, but not pitted [37]. However, the potentiodynamic polarization curves for copper in deaerated sulfide and chloride containing solutions indicate that copper is passive in a wide potential range and shows passivity breakdown and hysteresis in the current upon reversing the potential sweep after breakdown has occurred.…”

Section: Corrosion Of Coppermentioning

confidence: 85%

“…Once oxygen in the repository is consumed by general corrosion and anaerobic conditions are established, the major concern to the long-term durability of the copper canisters is, thus, corrosion by sulfide induced reactions. Corrosion studies in aqueous solutions containing sulfide ions (SH -) have shown that sulfide corrosion is a two-step process where adsorption on copper surface occurs first to form the chemisorbed species Cu(SH)ads, which leads to deposition of Cu2S on the Cu surface by reaction of the chemisorbed species with Cu and SH - [34]- [37]: Cu + SH -Cu(SH)ads + e -Cu + Cu(SH)ads + SH -Cu2S +H2S + e -Hydrogen evolution under anoxic conditions is the viable cathodic reaction:…”

Section: Corrosion Of Coppermentioning

confidence: 99%

“…The Cu2S film growth occurs as two distinct layers, with the initially grown porous base layer achieving only limited thickness of about 200 nm, while most of the film growth occurs as a much thicker, more compact but still porous, outer chalcocite (Cu2S) deposit layer [37]. Passivation of the surface does not occur due to the porosity of the film.…”

Section: Corrosion Of Coppermentioning

confidence: 99%

“…A dual-layer film forms when the SHcontent increases above 5×10 -4 M and the SHflux is high. Thus, a number of electrochemical measurements indicate that formation of a passive barrier layer does not occur on the copper surface [34]- [37].…”

Section: Corrosion Of Coppermentioning

confidence: 99%

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Hydrogen effects on mechanical performance of nodular cast iron

2019

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The KBS-3 method for long-term disposal of spent nuclear fuel is designed with an external self-standing copper shell, which provides the most important barrier against corrosion and escape of radionuclides, and an internal nodular cast iron insert, which provides the load-bearing structure against external loads. The material intended for the load-bearing insert is ferritic nodular cast iron EN 1563 grade EN-GJS-400-15U. In this paper, hydrogen uptake and sensitivity to hydrogen-induced cracking of the cast iron were studied using tensile testing under continuous electrochemical charging in 1 N H2SO4 solution. Hydrogen uptake was measured by using the thermal desorption method. It was found that the hydrogen desorption profile manifests three distinct peaks at initial locations of 400, 500, and 700 K with a heating rate of 6 K/min. Plastic deformation results in a remarkable increase of the 400 K peak, which indicates hydrogen uptake during deformation. In the constant extension rate tests (CERT) and the constant load tests (CLT), electrochemical hydrogen charging reduced markedly the elongation to fracture and time to fracture, respectively. In CLT, hydrogen charging increased dramatically the creep rate at the applied load of about 0.7 yield stress. Ligaments between the graphite nodules exhibit brittle cleavage facets in the presence of hydrogen, while the ligaments show a characteristic ductile appearance of shear and small dimples when testing in air or distilled water. The obtained results are discussed in terms of the known mechanisms of hydrogen-induced cracking and the role of the graphite nodules in the embrittlement of ductile cast iron.

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Sulphide‐induced stress corrosion cracking and hydrogen absorption of copper in deoxygenated water at 90°C

Forsström

Becker

Hänninen

et al. 2020

Materials & Corrosion

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Stress corrosion cracking (SCC) of oxygen‐free phosphorous‐alloyed copper was investigated in sulphide‐ and chloride‐containing deoxygenated water at 90°C with sulphide concentrations of 0.001 and 0.00001 M. Several intergranular defects were found in the specimen exposed to the high sulphide environment. Similar defects were not found in the low sulphide environment, where only slight corrosion on grain boundaries and slip lines occurred. Hydrogen content measurements show an increase in hydrogen uptake of the plastically deformed specimens, which is dependent on the sulphide concentration and on plastic deformation of copper. However, the highest hydrogen content was measured in friction stir welds, welded in air without shielding gas, and tested in the high sulphide environment. The embedded oxide particles in the weld metal act as local hydrogen trapping sites and selectively react with the sulphide solution. A relatively thick air‐formed oxide film covers the copper canisters when deposited, which transforms into a sulphide film in the repository conditions. Thus, some of the coupon specimens were pre‐oxidised. The conversion of the pre‐existing Cu2O film into Cu2S film occurs quickly and the transformation is almost 100% efficient. The structure and properties of the Cu2S films, susceptibility of copper to sulphide‐induced SCC and hydrogen uptake of copper in reducing, anoxic repository conditions are discussed.

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The Properties of Electrochemically-Grown Copper Sulfide Films

Cited by 20 publications

References 25 publications

The nature of the copper sulfide film grown on copper in aqueous sulfide and chloride solutions

The nature of the copper sulfide film grown on copper in aqueous sulfide and chloride solutions

Hydrogen effects on mechanical performance of nodular cast iron

Sulphide‐induced stress corrosion cracking and hydrogen absorption of copper in deoxygenated water at 90°C

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