Determination of instantaneous corrosion rates and runoff rates of copper from naturally patinated copper during continuous rain events

Instantaneous corrosion rates of naturally patinated copper of varying age (16 months, 138 and 145 years) have been determined during continuous rain events in the laboratory with electrochemical impedance spectroscopy using a two-electrode cell. The two-electrode cell was found to yield the same information in bulk rainwater as a conventional three-electrode cell.Relatively constant corrosion rates, between 0.2 and 0.6 μm/y, were determined for samples having a two-layer structure with an inner brownish layer of cuprous oxide and an outer greenish layer of basic copper salts (138, 145 years). Samples with cuprous oxide as the dominating phase of the patina (16 months) showed higher and somewhat increasing corrosion rates during a rain event (from 0.6 to 1.2 μm/y). During a continuous rain event, corrosion rates were found to be approximately 10 (brownish patina) and 25 times (greenish patina) lower than corresponding instantaneous runoff rates. The first flush phenomena of the runoff process, with an increased concentration during first flush and a relatively constant concentration during steady state, was indirectly seen as an increase in solution conductivity during the first rain volume followed by relative constant value. The contribution of the concentration in the first flush to the total annual runoff rate was significant for panels having a greenish layer (138, 145 years) whereas it was negligible for panels having a brownish layer (16 months).     

MICROSCOPIC CORROSION STUDIES OF DUPLEX STAINLESS STEELS

Electrochem,cal scanning tunneling microscopy and scanning electrochemical microscopy have been used for in situ monitoring of localized corrosion processes of different Duplex stainless steels (DSS) in acidic chloride solutions. The techniques allow imaging of local dissolution events with micrometer resolution, as opposed to conventional electrochemical techniques, which only give an overall view of the corrosion behavior. In addition, combined scanning Kelvin probe force microscopy and magnetic force microscopy were used for mapping the Volta potential variation over the surface of DSSs. A significant difference in Volta potential between the austenite and ferrite phases suggests galvanic interaction between the phases. A compositional gradient appears within 2 micrometers across the phase boundary, as seen with scanning Auger microscopy (SAM). In all, the studies suggest that higher alloyed DSS exhibit a more homogeneous dissolution behavior than lower alloyed DSS, due to higher and more similar corrosion resistance of the two phases, and enhanced resistance of the ferrite/austenite phase boundary regions.     

Tafel slopes used in monitoring of copper corrosion in a bentonite/groundwater environment

The harmonic analysis, the polarization resistance, and the noise resistance methods have been applied in an effort to monitor corrosion of pure copper in a bentonite/groundwater environment with commercially available equipment. Without the need to use a reference electrode, the first method supplies not only an estimate of the corrosion rate, but also estimates of Tafel slopes required by the other methods. The recorded corrosion rate is overestimated but to a varying degree. While the recorded corrosion rates for the first two methods give quite similar values far below 3 μm/year, the electrochemical noise resistance method gives considerably higher values.     

Superparamagnetic Twist‐Type Actuators with Shape‐Independent Magnetic Properties and Surface Functionalization for Advanced Biomedical Applications

Directed nanoparticle self‐organization and two‐photon polymerization are combined to enable three‐dimensional soft‐magnetic microactuators with complex shapes and shape‐independent magnetic properties. Based on the proposed approach, single and double twist‐type swimming microrobots with programmed magnetic anisotropy are demonstrated, and their swimming properties in DI‐water are characterized. The fabricated devices are actuated using weak rotating magnetic fields and are capable of performing wobble‐free corkscrew propulsion. Single twist‐type actuators possess an increase in surface area in excess of 150% over helical actuators with similar feature size without compromising the forward velocity of over one body length per second. A generic and facile combination of glycine grafting and subsequent protein immobilization exploits the actuator's increased surface area, providing for a swimming microrobotic platform with enhanced load capacity desirable for future biomedical applications. Successful surface modification is confirmed by FITC fluorescence.     

In situ ATR-FTIR studies of the aluminium/polymer interface upon exposure to water and electrolyte

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) with the Kretschmann configuration was applied for in situ studies of the transport of water and ionic species through a polymer film to an aluminium/polymer interface. The time dependent intensity changes of the infrared bands of water were used to follow the transport of water to the aluminium/polymer interfacial region and a NaSCN solution was employed as model electrolyte to follow the transport and accumulation of thiocyanate ions. Apart from water sorption and ion transport, the main processes identified were corrosion/oxidation of the aluminium surface and swelling of the polymer film. The method proved to be useful for detailed in situ studies of changes at a polymer coated metal surface, such as oxidation and surface film formation on the metal. It should also be possible to study the effects of defects and pores in the polymer film on the transport properties of water and ions to the metal/polymer interface, as well as adsorption and other chemical reactions and physical interactions in the metal/polymer interfacial region.     

Gildes model studies of aqueous chemistry. II. The corrosion of zinc in gaseous exposure chambers

The GILDES model has been used to perform the first theoretical mechanistic study of the atmospheric corrosion of zinc in a controlled environment. Detailed comparisons are made of model results with laboratory data for short-term (0–1000 min) and long-term (0–680 h) exposures of zinc to SO₂, NO₂ and O₃ at high relative humidities. The agreement of theory and experiment is excellent, indicating that the model has captured the principal processes (especially ligand-promoted dissolution) involved in the corrosion of zinc under these conditions.     

System for in situ studies of atmospheric corrosion of metal films using soft x-ray spectroscopy and quartz crystal microbalance

We present a versatile chamber ("atmospheric corrosion cell") for soft x-ray absorption/emission spectroscopy of metal surfaces in a corrosive atmosphere allowing novel in situ electronic structure studies. Synchrotron x rays passing through a thin window separating the corrosion cell interior from a beamline vacuum chamber probe a metal film deposited on a quartz crystal microbalance (QCM) or on the inside of the window. We present some initial results on chloride induced corrosion of iron surfaces in humidified synthetic air. By simultaneous recording of QCM signal and soft x-ray emission from the corroding sample, correlation between mass changes and variations in spectral features is facilitated.     

Elastic Properties and Structure of Interpenetrating Boron Carbide/Aluminum Multiphase Composites

We study the elastic moduli and structure of boron carbide/aluminum (B₄C/Al) multiphase composites using rigorous bounding and experimental characterization techniques. We demonstrate that rigorous bounds on the effective moduli are useful in that they can accurately predict (i) the effective elastic moduli, given the phase moduli and volume fractions, or (ii) the phase moduli (volume fractions), given the effective moduli and phase volume fractions (moduli). Using the best available rigorous bounds on the effective elastic moduli of multiphase composites involving volume-fraction information, we are able to predict the bulk and shear moduli of the Al₄BC phase, a reaction product that forms during heat treatment. These theoretical predictions are in very good agreement with recent experimental measurements of the moduli of the Al₄BC phase. Moreover, we evaluate more-refined bounds involving three-point structural correlation functions by extracting such information from an image of a sample of the B₄C/Al composite. Although experimental data for the effective moduli are unavailable for this sample, our predictions of the effective moduli based on three-point bounds should be quite accurate.     

Characterization of black rust staining of unpassivated 55% Al–Zn alloy coatings. Effect of temperature, pH and wet storage

Wet storage staining is a phenomenon that occurs on both zinc coated and 55% Al–Zn coated steel sheets during shipment or storage in damp conditions. Whereas zinc coated sheets form white corrosion products, 55% Al–Zn coated steel sheets form black corrosion products. The effect of temperature, pH and wet storage on the occurrence of black rust staining of unpassivated Aluzink samples has been investigated in the laboratory in terms of corrosion product formation and composition. A characterization of corrosion products formed has been performed mainly based on scanning electron microscopy with X-ray microanalyses (SEM/EDS) for morphological and quantitative analyses and X-ray diffraction techniques (XRD) for crystalline phase identification. Black rust formation is strongly related to alkaline pH regions and is enhanced by the temperature. All black panels show the presence of Bayerite (Al(OH)₃), mainly formed on the aluminum rich dendrite branches and a basic zinc aluminum carbonate (Zn₆Al₂(OH)₁₆CO₃·4H₂O) formed in the zinc rich interdendritic alloy regions in contact with air. Blackening of Aluzink surfaces is connected to differences in optical properties of embedded metallic zinc and/or aluminum particles of different shape and size in the corrosion layer.     

A simulation study of the combined thermoelectric extracellular stimulation of the sciatic nerve of the Xenopus laevis: the localized transient heat block

The electrical behavior of the Xenopus laevis nerve fibers was studied when combined electrical (cuff electrodes) and optical (infrared laser, low power sub-5?mW) stimulations are applied. Assuming that the main effect of the laser irradiation on the nerve tissue is the localized temperature increase, this paper analyzes and gives new insights into the function of the combined thermoelectric stimulation on both excitation and blocking of the nerve action potentials (AP). The calculations involve a finite-element model (COMSOL) to represent the electrical properties of the nerve and cuff. Electric-field distribution along the nerve was computed for the given stimulation current profile and imported into a NEURON model, which was built to simulate the electrical behavior of myelinated nerve fiber under extracellular stimulation. The main result of this study of combined thermoelectric stimulation showed that local temperature increase, for the given electric field, can create a transient block of both the generation and propagation of the APs. Some preliminary experimental data in support of this conclusion are also shown.