Quantitative In Situ Analysis of Deformation in Sliding Metals: Effect of Initial Strain State

Using in situ, high-speed imaging of a hard wedge sliding against pure aluminum, and image analysis by particle image velocimetry, the deformation field in sliding is mapped at high resolution. This model system is representative of asperity contacts on engineered surfaces and die-workpiece contacts in deformation and machining processes. It is shown that large, uniform plastic strains of 1-5 can be imposed at the Al surface, up to depths of 500 mu m, under suitable sliding conditions. The spatial strain and strain rate distributions are significantly influenced by the initial deformation state of the Al, e.g., extent of work hardening, and sliding incidence angle. Uniform straining occurs only under conditions of steady laminar flow in the metal. Large pre-strains and higher sliding angles promote breakdown in laminar flow due to surface fold formation or flow localization in the form of shear bands, thus imposing limits on uniform straining by sliding. Avoidance of unsteady sliding conditions, and selection of parameters like sliding angle, thus provides a way to control the deformation field. Key characteristics of the sliding deformation such as strain and strain rate, laminar flow, folding and prow formation are well predicted by finite element simulation. The deformation field provides a quantitative basis for interpreting wear particle formation. Implications for engineering functionally graded surfaces, sliding wear and ductile failure in metals are discussed.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Development of a Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) Cell for the In Situ Analysis of Co-Electrolysis in a Solid Oxide Cell

Co-electrolysis of carbon dioxide and steam has been shown to be an efficient way to produce syngas, however further optimisation requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the solid oxide cell (SOC) during operation. Whilst electrochemical measurements are currently conducted in situ, many analytical techniques can only be used ex situ and may even be destructive to the cell (e.g. SEM imaging of microstructure). In order to fully understand and characterise co-electrolysis, in situ monitoring of the reactants, products and SOC is necessary. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) is ideal for in situ monitoring of co-electrolysis as both gaseous and adsorbed CO and CO2 species can be detected, however it has previously not been used for this purpose. The challenges of designing an experimental rig which allows optical access alongside electrochemical measurements at high temperature and operates in a dual atmosphere are discussed. The rig developed has thus far been used for symmetric cell testing at temperatures from 450[degree]C to 600[degree]C. Under a CO atmosphere, significant changes in spectra were observed even over a simple Au|10Sc1CeSZ|Au SOC. The changes relate to a combination of CO oxidation, the water gas shift reaction and carbonate formation and decomposition processes, with the dominant process being both potential and temperature dependent.

In situ analysis and structural elucidation of sainfoin (Onobrychis viciifolia) tannins for high-throughput germplasm screening

A rapid thiolytic degradation and cleanup procedure was developed for analyzing tannins directly in chlorophyll-containing sainfoin (Onobrychis viciifolia) plants. The technique proved suitable for complex tannin mixtures containing catechin, epicatechin, gallocatechin, and epigallocatechin flavan-3-ol units. The reaction time was standardized at 60 min to minimize the loss of structural information as a result of epimerization and degradation of terminal flavan-3-ol units. The results were evaluated by separate analysis of extractable and unextractable tannins, which accounted for 63.6−113.7% of the in situ plant tannins. It is of note that 70% aqueous acetone extracted tannins with a lower mean degree of polymerization (mDP) than was found for tannins analyzed in situ. Extractable tannins had between 4 and 29 lower mDP values. The method was validated by comparing results from individual and mixed sample sets. The tannin composition of different sainfoin accessions covered a range of mDP values from 16 to 83, procyanidin/prodelphinidin (PC/PD) ratios from 19.2/80.8 to 45.6/54.4, and cis/trans ratios from 74.1/25.9 to 88.0/12.0. This is the first high-throughput screening method that is suitable for analyzing condensed tannin contents and structural composition directly in green plant tissue.

In situ analysis of the tensile deformation mechanisms in extruded Mg–1Mn–1Nd (wt%)

An extruded Mg–1Mn–1Nd (wt%) (MN11) alloy was tested in tension in an SEM at temperatures of 323K (50°C), 423 K (150°C), and 523 K (250°C) to analyse the local deformation mechanisms through in situ observations. Electron backscatter diffraction was performed before and after the deformation. It was found that the tensile strength decreased with increasing temperature, and the relative activity of different twinning and slip systems was quantified. At 323K (50C), extension twinning, basal, prismatic (a) and pyramidal (c+a) slip were active. Much less extension twinning was observed at 423K (150ºC) while basal slip and prismatic (a) slip were dominant and presented similar activities. At 523K (250ºC), twinning was not observed, and basal slip controlled the deformation.

Recycling old screen-printed electrodes with newly designed plastic antibodies on the wall of carbon nanotubes as sensory element for in situ detection of bacterial toxins in water

Using low cost portable devices that enable a single analytical step for screening environmental contaminants is today a demanding issue. This concept is here tried out by recycling screen-printed electrodes that were to be disposed of and by choosing as sensory element a low cost material offering specific response for an environmental contaminant. Microcystins (MCs) were used as target analyte, for being dangerous toxins produced by cyanobacteria released into water bodies. The sensory element was a plastic antibody designed by surface imprinting with carefully selected monomers to ensure a specific response. These were designed on the wall of carbon nanotubes, taking advantage of their exceptional electrical properties. The stereochemical ability of the sensory material to detect MCs was checked by preparing blank materials where the imprinting stage was made without the template molecule. The novel sensory material for MCs was introduced in a polymeric matrix and evaluated against potentiometric measurements. Nernstian response was observed from 7.24 × 10−10 to 1.28 × 10−9 M in buffer solution (10 mM HEPES, 150 mM NaCl, pH 6.6), with average slopes of −62 mVdecade−1 and detection capabilities below 1 nM. The blank materials were unable to provide a linear response against log(concentration), showing only a slight potential change towards more positive potentials with increasing concentrations (while that ofthe plastic antibodies moved to more negative values), with a maximum rate of +33 mVdecade−1. The sensors presented good selectivity towards sulphate, iron and ammonium ions, and also chloroform and tetrachloroethylene (TCE) and fast response (<20 s). This concept was successfully tested on the analysis of spiked environmental water samples. The sensors were further applied onto recycled chips, comprehending one site for the reference electrode and two sites for different selective membranes, in a biparametric approach for “in situ” analysis.

Characterisation of soils containing naturally occurring radioactive material (NORM) using in situ and rapid laboratory techniques. Case study: South Terras, Cornwall

In situ analysis has become increasingly important for contaminated land investigation and remediation. At present, portable techniques are used mainly as scanning tools to assess the spread and magnitude of the contamination, and are an adjunct to conventional laboratory analyses. A site in Cornwall, containing naturally occurring radioactive material (NORM), provided an opportunity for Reading University PhD student Anna Kutner to compare analytical data collected in situ with data generated by laboratory-based methods. The preliminary results in this paper extend the author‟s poster presentation at last September‟s GeoSpec2010 conference held in Lancaster.

Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs

The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130◦C, 138◦C, 140◦C and 150◦C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two C H bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid–gas–solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol−1 to 368 kJ mol−1 for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance

Potential misidentification of in situ archaeological tool-residues: starch and conidia

Microscopic identification of organic residues in situ on the surface of archaeological artefacts is an established procedure. Where soil components morphologically similar to use-residue types exist within the soil, however, there remains the possibility that these components may be misidentified as authentic residues. The present study investigates common soil components known as conidia, fungal spores which may be mistaken for starch grains. Conidia may exhibit the rotating extinction cross under cross-polarised light commonly diagnostic of starch, and may be morphologically indistinguishable from small starch grains, particularly at the limits of microscope resolution. Conidia were observed on stone and ceramic archaeological artefacts from Honduras, Palau and New Caledonia, as well as experimental artefacts from Papua New Guinea. The findings act as a caution that in situ analysis of residues, and especially of those less than 5 mu m in size, may be subject to misidentification. (c) 2005 Elsevier Ltd. All rights reserved.

In-situ based reanalysis of the global ocean temperature and salinity with ISAS: variability of the heat content and steric height

The In Situ Analysis System (ISAS) was developed to produce gridded fields of temperature and salinity that preserve as much as possible the time and space sampling capabilities of the Argo network of profiling floats. Since the first global re-analysis performed in 2009, the system has evolved and a careful delayed mode processing of the 2002-2012 dataset has been carried out using version 6 of ISAS and updating the statistics to produce the ISAS13 analysis. This last version is now implemented as the operational analysis tool at the Coriolis data centre. The robustness of the results with respect to the system evolution is explored through global quantities of climatological interest: the Ocean Heat Content and the Steric Height. Estimates of errors consistent with the methodology are computed. This study shows that building reliable statistics on the fields is fundamental to improve the monthly estimates and to determine the absolute error bars. The new mean fields and variances deduced from the ISAS13 re-analysis and dataset show significant changes relative to the previous ISAS estimates, in particular in the southern ocean, justifying the iterative procedure. During the decade covered by Argo, the intermediate waters appear warmer and saltier in the North Atlantic and fresher in the Southern Ocean than in WOA05 long term mean. At inter-annual scale, the impact of ENSO on the Ocean Heat Content and Steric Height is observed during the 2006-2007 and 2009-2010 events captured by the network.

Long-Term In Situ Survey of Reactive Iron Concentrations at the EMSO-Azores Observatory

A study of the temporal dynamics of iron concentrations and temperature on a faunal assemblage at the Lucky Strike vent was performed using the Tempo ecological module at the EMSO-Azores deep-sea observatory. The CHEMINI in situ analyzer was implemented on this structure to determine reactive iron concentrations in unfiltered seawater samples along with a temperature probe. Stability tests were performed on the CHEMINI analyzer before deployment (optical module, hyperbaric tests, and deep-sea calibration) for long-term in situ analysis of reactive iron (six months, 2013–2014) at the Tour Eiffel active edifice. Recorded daily, the in situ standard (25 \mu mol.L {}^{-1} ) showed excellent reproducibility (1.07%, n=522 ), confirming satisfactory analytical performance of the CHEMINI analyzer and thus validating the iron concentrations measured by the instrument. Furthermore, the analyzer proved to be reliable and robust over time. The averaged reactive iron concentration for the six-month period remained low ([Fe] =text{7.12}\pm text{2.11} \mu mol.L {}^{-1} , n=519 ), but showed some noticeable variations with temperature. Reactive iron concentrations and temperature were significantly correlated emphasizing reactive iron stabilization over the time of deployment. Period spectra indicated strong tidal influence and relevant frequencies of four to five days for both variables.

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance