ABSTRACT. The high surface areas of nanostructured electrodes can provide for significantly enhanced surface loadings of electroactive materials. The fabrication and characterisation of nanoporous gold (np-Au) substrates as electrodes for bioelectrochemical applications is described.Robust np-Au electrodes were prepared by sputtering a gold-silver alloy onto a glass support and subsequent de-alloying of the silver component. Alloy layers were prepared with either a uniform or non-uniform distribution of silver and, post de-alloying, showed clear differences in morphology on characterisation with scanning electron microscopy. Redox reactions under kinetic control, in particular measurement of the charge required to strip a gold oxide layer, provided the most accurate measurements of the total electrochemically addressable electrode surface area, A real .Values of A real up to 28 times that of the geometric electrode surface area, A geo , were obtained. For diffusion controlled reactions overlapping diffusion zones between adjacent nanopores established limiting semi-infinite linear diffusion fields where the maximum current density was dependent on A geo . The importance of measuring the surface area available for the immobilisation was determined 2 using the redox protein, cyt c. The area accessible to modification by a biological macromolecule, A macro , such as cyt c was reduced by up to 40 % compared to A real , demonstrating that the confines of some nanopores were inaccessible to large macromolecules due to steric hindrances. Preliminary studies on the preparation of np-Au electrodes modified with osmium redox polymer hydrogels and Myrothecium verrucaria bilirubin oxidase (MvBOD) as a biocathode were performed; current densities of 500 A cm -2 were obtained in unstirred solutions.

Nanoporous gold (NPG) fabricated by sputtering is a material of versatile morphology with pores whose size can be tailored to accommodate enzymes. The process of pore formation and the size of the pores in NPG are influenced by the composition of Au and Ag in the alloy used to prepare the electrodes together with the temperature and time period of the dealloying process. On increasing the time from 1 to 60 min and the temperature from 0.5 °C to 60.5 °C in concentrated HNO3, significant increases in the average pore diameters from 4.4 to 78 nm were observed with simultaneous decreases in the roughness factor (Rf). The pores of NPG were fully addressable regardless of the diameter, with Rf increasing linearly up to an alloy thickness of 500 nm. The influence of the pore size on the bioelectrochemical response of redox proteins was evaluated using cytochrome c as a model system. The highest current densities of ca. 30 µA cm−2 were observed at cytochrome c modified NPG electrodes with an average pore size of ca. 10 nm. The pores in NPG were also tuned for the mediatorless immobilization of Myrothecium verrucaria bilirubin oxidase. High current densities of ca. 65 µA cm−2 were observed at MvBOD modified NPG electrodes prepared by dealloying at 0.5 °C for 5 min with an average pore size of 8 nm, which is too small to accommodate the enzyme into the pores, indicating that the response was from enzyme adsorbed on the electrode surface.

This paper describes the results of copper coupons exposed to a class III mixed flowing gas environment ͑MFG͒ following the guidelines given by the Battelle Laboratory and the International Electrotechnical Commission for environmental testing. Corrosion products were studied in detail using scanning electron microscope, energy dispersive X-ray spectroscopy ͑EDS͒, X-ray diffraction ͑XRD͒, focused ion beam ͑FIB͒, secondary ion mass spectroscopy ͑SIMS͒, and transmission electron microscope. The weight gain measured after each exposure was compared with the weight gain calculated from the cathodic reduction of the corrosion layers and cross sectioning using an FIB. The result shows a relatively good correlation between the measured and the calculated experimental values of weight gain. As expected, within the first week, the different corrosion layers thickened until they formed a thick layer that became the determining step for further growth. After several days of exposure the Cu coupons developed a complex multilayered structure consisting of cuprous oxide ͑Cu 2 S͒, cupric oxide ͑CuO͒, copper sulfide ͑Cu 2 S͒, covellite ͑CuS͒, and evidence of antlerite ͑3CuO SO 3 2H 2 O͒. No Cl-containing corrosion products were identified using XRD. However, EDS and SIMS analysis showed that Cl was distributed throughout the corrosion products, indicating that although Cl is inside the corrosion products, it is not part of the crystalline structure. Also, this suggests that Cl plays an important role in accelerating the corrosion of Cu during exposure to the MFG class III test. In the early 1980s, with the discovery of significant printed wiring board ͑PWB͒ and component failure modes ͑mainly due to corrosion͒, a number of firms and laboratories set out to develop accelerated corrosion test methods with a known acceleration factor. The aim of such efforts was to shrink years of service into days of testing, and prove that the field failure modes would be replicated during the tests. The PWB and its components were exposed to different levels of a mixture of gases, temperature, and relative humidity, which would simulate the environment during operating conditions. IBM, AT&T, and Battelle Laboratories participated in this effort.1 The result of this work was the development of a mixed flowing gas ͑MFG͒ test, which is primarily a laboratory test in which the temperature, relative humidity, and concentration of gaseous pollutants are carefully defined, monitored, and controlled.

Corrosion of electronic components can produce a wide range of failure signatures, from intermittent electrical faults to complete functional breakdown. This paper presents an investigation on the exposure of a simple connector-coating system. The system consists of a copper contact coated with a nickel layer underneath a gold finish layer. The system was characterized using the following techniques: optical microscopy, atomic force microscopy ͑AFM͒, scanning electron microscopy ͑SEM͒, energy dispersive X-ray spectroscopy ͑EDAX͒, secondary ion mass spectroscopy ͑SIMS͒ and focused ion beam ͑FIB͒. After initial characterization, the connector was exposed to 2, 4, 7, 15, and 30 days in an aggressive environment consisting of 90% relative humidity, 40°C, and 4 ppm H 2 S. Digital images of the corrosion products that developed on the contacts after exposure clearly demonstrated localized corrosion by-products present on the connector surface. SEM, EDAX, and SIMS analysis of the corrosion sites demonstrated the presence of copper sulfide and nickel sulfur corrosion product, which suggest a two-step mechanism: first, the Ni layer is attacked by the aggressive environment at the sites where the gold layer is not available, followed by the diffusion of copper through the nickel layer. FIB cross-sectional analysis revealed that surface defects in the gold layer resulted in sites for corrosion initiation and subsequent development of a thick copper sulfide layer of approximately 5 m. It is concluded that this copper connector coating system does not prevent the formation of insulating corrosion products on the surface of the connector in a very aggressive environment.

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