Raman spectroscopy of the copper chloride minerals nantokite, eriochalcite and claringbullite - implications for copper corrosion

The application of Raman spectroscopy to the study of the copper chloride minerals nantokite, eriochalcite and claringbullite has enabled the vibrational modes for the CuCl, CuOH and CuOH2 to be determined. Nantokite is characterised by bands at 205 and 155 cm-1 attributed to the transverse and longitudinal optic vibrations. Nantokite also has an intense band at 463 cm-1, eriochalcite at 405 and 390 cm-1 and claringbullite at 511 cm-1. These bands are attributed to CuO stretching modes. Water librational bands at around 672 cm-1 for eriochalcite have been identified and hydroxyl deformation modes of claringbullite at 970, 906 and 815 cm-1 are observed. Spectra of the three minerals are so characteristically different that the minerals are readily identified by Raman spectroscopy. The minerals are often determined in copper corrosion products by X-ray diffraction. Raman spectroscopy offers a rapid, in-situ technique for the identification of these corrosion products.

Corrosion studies on the plasma-sprayed nanostructured titanium dioxide coating

Purpose: The purpose of this paper is to report the resistance of plasma-sprayed titanium dioxide (TiO2) nanostructured coatings in a corrosive environment.----- Design/methodology/approach: Weight loss studies are performed according to ASTM G31 specifications in 3.5?wt% NaCl. Electrochemical polarization resistance measurements are made according to ASTM G59-91 specifications. Corrosion resistance in a humid and corrosive environment is determined by exposing the samples in a salt spray chamber for 100?h. Microstructural studies are carried out using an atomic force microscope and scanning electron microscope.----- Findings: The nanostructured TiO2 coatings offer good resistance to corrosion, as shown by the results of immersion, electrochemical and salt spray studies. The corrosion resistance of the coating is dictated primarily by the geometry of splat lamellae, density of unmelted nanoparticles, magnitude of porosity and surface homogeneity.----- Practical implications: The TiO2 nanostructured coatings show promising potential for use as abrasion, wear-resistant and thermal barrier coatings for service in harsh environments.----- Originality/value: The paper relates the corrosion resistance of nanostructured TiO2 coatings to their structure and surface morphology.

Novel corrosion sensor based on carbon nanotube composites for structural health monitoring

Bridges are important infrastructures of all nations and are required for transportation of goods as well as human. A catastrophic failure can result in loss of lives and enormous financial hardship to the nation. Hence, there is an urgent need to monitor our infrastructures to prolong their life span, at the same time catering for heavier and faster moving traffics. Although various kinds of sensors are now available to monitor the health of the structures due to corrosion, they do not provide permanent and long term measurements. This paper investigates the fabrication of Carbon Nanotube (CNT) based composite sensors for structural health monitoring. The CNTs, a key material in nanotechnology has aroused great interest in the research community due to their remarkable mechanical, electrochemical, piezoresistive and other physical properties. Multi-wall CNT (MWCNT)/Nafion composite sensors were fabricated to evaluate their electrical properties when subjected to chemical solutions, to simulate a chemical reaction due to corrosion and real life corrosion experimental tests. The electrical resistance of the sensor electrode was dramatically changed due to corrosion. The novel sensor is expected to effectively detect corrosion in structures based on the measurement of electrical impedances of the CNT composite.

Insights into the nature of the coupling interactions between uracil corrosion inhibitors and copper : a DFT and molecular dynamics study

In this study, the nature of the coupling interactions between copper and uracil as well as its several derivatives has been systematically investigated employing the atoms in molecules (AIM) theory and energy decomposition analyses. The whole interaction process has been investigated through the analyses of the radial distribution functions of the Cu⋯X (X = S and O) contact on the basis of the ab initio molecular dynamics. No direct relationship between the adsorption strengths and inhibition efficiencies of the inhibitors has been observed. Additionally, the possibility of the methyl-substituted dithiouracil species to act as copper corrosion inhibitors has been tested.

A facile chemical screening method for the detection of stress corrosion cracking in 9 carat gold alloys

Stress corrosion cracking (SCC) is a well known form of environmental attack in low carat gold jewellery. It is desirable to have a quick, easy and cost effective way to detect SCC in alloys and prevent them from being used and later failing in their application. A facile chemical method to investigate SCC of 9 carat gold alloys is demonstrated. It involves a simple application of tensile stress to a wire sample in a corrosive environment such as 1–10 % FeCl3 which induces failure in less than 5 minutes. In this study three quaternary (Au, Ag, Cu and Zn) 9 carat gold alloy compositions were investigated for their resistance to SCC and the relationship between time to failure and processing conditions is studied. It is envisaged that the use of such a rapid and facile screening procedure at the production stage may readily identify alloy treatments that produce jewellery that will be susceptible to SCC in its lifetime.

The electrochemical corrosion behaviour of quaternary gold alloys when exposed to 3.5% NaCl solution

Lower carat gold alloys, specifically 9 carat gold alloys, containing less than 40 % gold, and alloying additions of silver, copper and zinc, are commonly used in many jewellery applications, to offset high costs and poor mechanical properties associated with pure gold. While gold is considered to be chemically inert, the presence of active alloying additions raises concerns about certain forms of corrosion, particularly selective dissolution of these alloys. The purpose of this study was to systematically study the corrosion behaviour of a series of quaternary gold–silver–copper–zinc alloys using dc potentiodynamic scanning in saline (3.5 % NaCl) environment. Full anodic/cathodic scans were conducted to determine the overall corrosion characteristics of the alloy, followed by selective anodic scans and subsequent morphological and compositional analysis of the alloy surface and corroding media to determine the extent of selective dissolution. Varying degrees of selective dissolution and associated corrosion rates were observed after anodic polarisation in 3.5 % NaCl, depending on the alloy composition. The corrosion behaviour of the alloys was determined by the extent of anodic reactions which induce (1) formation of oxide scales on the alloy surface and or (2) dissolution of Zn and Cu species. In general, the improved corrosion characteristics of alloy #3 was attributed to the composition of Zn/Cu in the alloy and thus favourable microstructure promoting the formation of protective oxide/chloride scales and reducing the extent of Cu and Zn dissolution.

Hybrid CuTCNQ/AgTCNQ metal-organic charge transfer complexes via galvanic replacement vs. corrosion recrystallization

This study reports a hybrid of two metal-organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8-tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag+ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag0 nanoparticles and Cu(OH)2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion-recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal-organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal-organic semiconductors that will expand the scope of TCNQ-based charge transfer complexes for improved catalysis, sensing, electronics and biological applications.

Cathodic corrosion of Cu substrates as a route to nanostructured Cu/M (M = Ag, Au, Pd) surfaces

The electrochemical formation of nanostructured materials is generally achieved by reduction of a metal salt onto a substrate that does not influence the composition of the deposit. In this work we report that Ag, Au and Pd electrodeposited onto Cu under conditions where galvanic replacement is not viable and hydrogen gas is evolved results in the formation of nanostructured surfaces that unexpectedly incorporate a high concentration of Cu in the final material. Under cathodic polarization conditions the electrodissolution/corrosion of Cu occurs which provides a source of ionic copper that is reduced at the surface-electrolyte interface. The nanostructured Cu/M (M = Ag, Au and Pd) surfaces are investigated for their catalytic activity for the reduction of 4 nitrophenol by NaBH4 where Cu/Ag was found to be extremely active. This work indicates that a substrate electrode can be utilized in an interesting manner t make bimetallic nanostructures with enhanced catalytic activity.