Synchrotron X-ray diffraction investigation of the surface condition of artefacts from King Henry VIII's warship the Mary Rose.

Synchrotron X-ray diffraction (XRD) measured on the XMaS beamline at the ESRF was used to characterize the alloy composition and crystalline surface corrosion of three copper alloy Tudor artefacts recovered from the undersea wreck of King Henry VIII's warship the Mary Rose. The XRD method adopted has a dynamic range ∼1:105 and allows reflections <0.002% of the height of major reflections in the pattern to be discerned above the background without smoothing. Laboratory XRD, scanning electron microscopy-energy dispersive spectroscopy, synchrotron X-ray fluorescence and X-ray excited optical luminescence-X-ray near-edge absorption structure were used as supporting techniques, and the combination revealed structural and compositional features of importance to both archaeology and conservation. The artefacts were brass links believed to be fragments of chainmail and were excavated from the seabed during 1981 and 1982. Their condition reflects very different treatment just after recovery, viz. complete cleaning and conservation, chemical corrosion inhibition and chloride removal only, and distilled water soaking only (to remove the chlorides). The brass composition has been determined for all three at least in the top 7 µm or so as Cu(73%)Zn(27%) from the lattice constant. Measurement of the peak widths showed significant differences in the crystallite size and microstrain between the three samples. All of the links are found to be almost chloride-free with the main corrosion products being spertiniite, sphalerite, zincite, covellite and chalcocite. The balance of corrosion products between the links reflects the conservation treatment applied to one and points to different corrosion environments for the other two.

Unprecedented reductive cyclisation of salophen ligands to tetrahydroquinoxalines during metal complex formation.

The synthesis of novel tetrahydroquinoxalines by a metal induced one-electron reductive cyclisation of salophen ligands was found to occur when a salophen ligand was treated with chromium(ii) chloride or decamethylcobaltocene.

Aldehyde-Mediated Protein-to-Surface Tethering via Controlled Diazonium Electrode Functionalization Using Protected Hydroxylamines.

We report a diazonium electro-grafting method for the covalent modification of conducting surfaces with aldehyde-reactive hydroxylamine functionalities that facilitate the wiring of redox-active (bio)molecules to electrode surfaces. Hydroxylamine near-monolayer formation is achieved via a phthalimide-protection and hydrazine-deprotection strategy that overcomes the multilayer formation that typically complicates diazonium surface modification. This surface modification strategy is characterized using electrochemistry (electrochemical impedance spectroscopy and cyclic voltammetry), X-ray photoelectron spectroscopy, and quartz crystal microbalance with dissipation monitoring. Thus-modified glassy carbon, boron-doped diamond, and gold surfaces are all shown to ligate to small molecule aldehydes, yielding surface coverages of 150-170, 40, and 100 pmol cm-2, respectively. Bioconjugation is demonstrated via the coupling of a dilute (50 µM) solution of periodate-oxidized horseradish peroxidase enzyme to a functionalized gold surface under biocompatible conditions (H2O solvent, pH 4.5, 25 °C).

Exploring the scope of capacitance-assisted electrochemical carbon dioxide capture.

Optimisation of a capacitance-assisted electrochemical carbon-capture process is facilitated by the physical separation of the graphite and aluminium anode electrodes. This facilitates graphite electrode recycling and enables high current and increased aluminium surface area experiments which fix carbon at a higher rate and the same cell-voltage. Quantification of the H2 cathode byproduct shows that this process could be a net energy producer if recycled aluminium is used as the sacrificial anode.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source.

SR-XRD in situ monitoring of copper-IUD corrosion in simulated uterine fluid using a portable spectroelectrochemical cell.

The objective of this work is to study the initial corrosion of copper in the presence of gold when placed in simulated uterine fluid in order to better understand the evolution of active components of copper-IUDs. In order to carry out this study, a portable cell was designed to partially simulate the uterine environment and provide a way of tracking the chemical changes occurring in the samples in situ within a controlled environment over a long period of time using synchrotron spectroelectrochemistry. The dynamically forming crystalline corrosion products are determined in situ for a range of copper-gold surface ratios over the course of a 10-day experiment in the cell. It is concluded that the insoluble deposits forming over this time are not the origin of the anticonception mechanism.

In-situ spectroelectrochemical characterization of the electrochemical growth and breakdown of a lead dodecanoate coating on a lead substrate.

This paper concerns a time lapse spectroelectrochemical study of the growth of lead dodecanoate layers on a lead substrate in an aqueous solution using cyclic voltammetry. In-situ synchrotron radiation X-ray diffraction measurements were carried out on station BM26A (DUBBLE) at the European Synchrotron Radiation Facility (ESRF) in France. The diffraction pattern images were taken using a two-dimensional Mar CCD camera. After deposition of the coating, a spectroelectrochemical study of a linear sweep voltammetry experiment using an acetic acid electrolyte, simulating 'active' lead corrosion, was carried out on both a bare and lead dodecanoate coated sample. The results show that the coating inhibits the formation of new lead corrosion products.

Evaluation of an X-ray-excited optical microscope for chemical imaging of metal and other surfaces.

The application of a modular system for the nondestructive chemical imaging of metal and other surfaces is described using heritage metals as an example. The custom-built X-ray-excited optical luminescence (XEOL) microscope, XEOM 1, images the chemical state and short-range atomic order of the top 200 nm of both amorphous and crystalline surfaces. A broad X-ray beam is used to illuminate large areas (up to 4 mm(2)) of the sample, and the resulting XEOL emission is collected simultaneously for each pixel by a charge-coupled device sensor to form an image. The input X-ray energy is incremented across a range typical for the X-ray absorption near-edge structure (XANES) and an image collected for each increment. The use of large-footprint beams combined with parallel detection allows the power density to be kept low and facilitates complete nondestructive XANES mapping on a reasonable time scale. In this study the microscope was evaluated by imaging copper surfaces with well-defined patterns of different corrosion products (cuprite Cu2O and nantokite CuCl). The images obtained show chemical contrast, and filtering the XEOL light allowed different corrosion products to be imaged separately. Absorption spectra extracted from software-selected regions of interest exhibit characteristic XANES fingerprints for the compounds present. Moreover, when the X-ray absorption edge positions were extracted from each spectrum, an oxidation state map of the sample could be compiled. The results show that this method allows one to obtain nondestructive and noninvasive information at the micrometer scale while using full-field imaging.

Assessment of copper corrosion from frameless copper IUDs after long-term in utero residence.

OBJECTIVE: To assess the site-specific corrosive behavior of the frameless intrauterine device (IUD) following long-term exposure to the uterine environment. STUDY DESIGN: A qualitative and morphological study using X-ray diffraction (XRD) and scanning electron microscopy (SEM). RESULTS: Three GyneFix® IUDs that were in site up to 150 months were examined. In utero corroded copper sleeves were divided into 10 different groups based on their shape (U or O), orientation (inside or outside) and in utero residence time. XRD indicated the presence of solely cuprite (Cu2O) as corrosion product on both the inside and the outside of the copper sleeves, regardless of their shape. These results were confirmed by backscattered electron micrographs recorded on the inside, the outside and the cross-section of the IUD sleeve. SEM results suggest that shape and orientation slightly affect the corrosion rate. CONCLUSION: The apparent copper loss from both sides of GyneFix copper tubes proves that both sides are a potential copper source and therefore justifies the design of GyneFix IUD. This could be beneficial for women as the IUD could be reduced in size and therefore better tolerated. The impact on bleeding could also be minimized. IMPLICATION STATEMENT: Release of copper ions from both sides of the copper tubes of the frameless GyneFix® IUD allows the IUD to be reduced in size, contributing to better toleration. The impact on menstrual bleeding is also minimized by a smaller size of the foreign body.

Real time observation of X-ray-induced surface modification using simultaneous XANES and XEOL-XANES.

In experiments preliminary to the design of an X-ray-excited optical luminescence (XEOL)-based chemical mapping tool we have used X-ray micro (4.5 × 5.2 µm) and macro (1 × 6 mm) beams with similar total fluxes to assess the effects of a high flux density beam of X-rays at energies close to an absorption edge on inorganic surfaces in air. The near surface composition of corroded cupreous alloys was analyzed using parallel X-ray and optical photoemission channels to collect X-ray absorption near-edge structure (XANES) data at the Cu K edge. The X-ray fluorescence channel is characteristic of the composition averages over several micrometers into the surface, whereas the optical channel is surface specific to about 200 nm. While the X-ray fluorescence data were mostly insensitive to the X-ray dose, the XEOL-XANES data from the microbeam showed significant dose-dependent changes to the superficial region, including surface cleaning, changes in the oxidation state of the copper, and destruction of surface compounds responsible for pre-edge fluorescence or phosphorescence in the visible. In one case, there was evidence that the lead phase in a bronze had melted. Conversely, data from the macrobeam were stable over several hours. Apart from localized heating effects, the microbeam damage is probably associated with the O3 loading of the surface and increased reaction rate with atmospheric water vapor.

The use of synchrotron X-rays to observe copper corrosion in real time.

We have developed and tested two complementary methods for making time-lapse synchrotron X-ray diffraction (XRD) measurements of the growth of synthetic corrosion layers using a protocol for producing copper(I) chloride (nantokite), on copper as a test. In the first method, a copper coupon was spin-coated with saturated copper(II) chloride solution in air while the surface was characterized in real time using XRD with a fast one-dimensional (1-D) detector. In the second, a droplet of the same reagent was suspended from an X-ray-transparent window in a hermetically sealed cell and the coupon was brought into contact with this while XRD diffractograms were acquired with a charge-coupled device (CCD) camera. The protocol is completed by a deionized water rinse, which was also studied. The XRD shows nantokite precipitation in solution as well as growth on the surface, but the end products were variable proportions of nantokite, cuprite (Cu(2)O), and paratacamite (Cu(2)(OH)(3)Cl). The latter two were observed forming in a reaction between the nantokite and the rinsing water. Comparisons between samples analyzed in the synchrotron and at lower power densities show that the effects of any radiolysis or slight heating of the sample are insignificant in this case. It would be simple to extend these methods to other corrosion or surface reaction systems.

Overcoming low Ge ionization and erosion rate variation for quantitative ultralow energy secondary ion mass spectrometry depth profiles of Si(1-x)Ge(x)/Ge quantum well structures.

We specify the O(2)(+) probe conditions and subsequent data analysis required to obtain high depth resolution secondary ion mass spectrometry profiles from multiple Ge/Si(1-x)Ge(x) quantum well structures (0.6 ≤ x ≤ 1). Using an O(2)(+) beam at normal incidence and with energies >500 eV, we show that the measured Ge signal is not monotonic with concentration, the net result being an unrepresentative and unquantifiable depth profile. This behavior is attributed to a reduced Ge ionization rate as x approaches 1. At lower beam energies the signal behaves monotonically with Ge fraction, indicating that the Ge atoms are now ionizing more readily for the whole range of x, enabling quantitative profiles to be obtained. To establish the depth scale a point-by-point approach based on previously determined erosion rates as a function of x is shown to produce quantum well thicknesses in excellent agreement with those obtained using transmission electron microscopy. The findings presented here demonstrate that to obtain reliable quantitative depth profiles from Ge containing samples requires O(2)(+) ions below 500 eV and correct account to be taken of the erosion rate variation that exists between layers of different matrix composition.

The coordinated use of synchrotron spectroelectrochemistry for corrosion studies on heritage metals.

Corrosion is a major source of degradation in heritage metal objects, and any remedial measures are subject to a strong (Western) ethic that favors conservation as opposed to restoration. Accordingly, major scientific challenges exist for developing appropriate treatment methods to stabilize and protect artifacts after they are recovered from an archaeological site, both before and during their display or storage in a museum. Because inappropriate treatments can cause irreversible damage to irreplaceable objects, it is crucial that the chemical processes involved are fully understood and characterized before any preservation work is undertaken. In this regard, large infrastructural facilities such as synchrotrons, neutron sources, and particle accelerators provide a wealth of analytical possibilities, unavailable in smaller scale laboratories. In general, the intensity of the radiation available allows measurements on a short time scale or with high spatial resolution (or both), so heterogeneous changes induced by a chemical process can be recorded while they occur. The penetrative nature of the radiation (e.g., X-rays, protons, or neutrons) also allows a sample to be studied in air. If necessary, complete artifacts (such as paintings or statuettes) can be examined. In situ analysis in a controlled environment, such as a liquid or corrosive atmosphere, also becomes an exciting possibility. Finally, there are many complementary techniques (local atomic structure or crystal structure determination, macroscopic 3-D imaging (tomographies), imaging chemical analysis, and so on) so the many distinct details of a problem can be thoroughly explored. In this Account, we discuss the application of this general philosophy to studies of corrosion and its prevention in cultural heritage metals, focusing on our recent work on copper alloys. More specifically, we use synchrotron-based techniques to evaluate the use of corrosion potential measurements as a possible monitoring method for copper-based objects recovered from marine environments. The extraction of chlorides from such artifacts is a process that must take place before the artifacts are put on display or stored, because air exposure of untreated metal will result in severe damage or loss in as little as a few weeks. Chloride is removed by soaking the artifact for up to two years in tap water or dilute sodium sesquicarbonate, with regular solution changes. Our research supports the effectiveness of this treatment for thin nantokite (copper(I) chloride) layers, but it raises questions for copper hydroxychlorides (atacamite and paratacamite), especially when these minerals are trapped in fissures. Electrochemical parameters such as the corrosion potential are shown to be insensitive to the physical presence of large hydroxychloride coverages if they overlie a cuprite (Cu(2)O) layer. X-ray absorption spectroscopy proves to be a good monitor for the chloride in solution over the working electrode, whereas X-ray diffraction offers the potential for real-time measurement of the surface chloride composition. In principle, the two techniques together offer the possibility of monitoring surface and fluid levels simultaneously.

Optically detected X-ray absorption spectroscopy measurements as a means of monitoring corrosion layers on copper.

XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity. Where the near-visible photons have a shorter range in a material, the data will be more surface specific. Moreover, optical radiation may escape more readily than X-rays through liquid in an environmental cell. Here, we describe a first test of optically detected X-ray absorption spectroscopy (ODXAS) for monitoring electrochemical treatments on copper-based alloys, for example, heritage metals. Artificially made corrosion products deposited on a copper substrate were analyzed in air and in a 1% (w/v) sodium sesquicarbonate solution to simulate typical conservation methods for copper-based objects recovered from marine environments. The measurements were made on stations 7.1 and 9.2 MF (SRS Daresbury, UK) using the mobile luminescence end station (MoLES), supplemented by XAS measurements taken on DUBBLE (BM26 A) at the ESRF. The ODXAS spectra usually contain fine structure similar to that of XAS spectra measured in X-ray fluorescence. Importantly, for the compounds examined, the ODXAS is significantly more surface specific, and >98% characteristic of thin surface layers of 0.5-1.5-microm thickness in cases where X-ray measurements are dominated by the substrate. However, EXAFS and XANES from broadband optical measurements are superimposed on a high background due to other optical emission modes. This produces statistical fluctuations up to double what would be expected from normal counting statistics because the data retain the absolute statistical fluctuation in the original raw count, while losing up to 70% of their magnitude when background is removed. The problem may be solved in future through optical filtering to isolate the information-containing band, combined with the use of higher input X-ray fluxes available on third-generation light sources.

Insights into electrolytic stabilization with weak polarization as treatment for archaeological copper objects.

Immersion of corroded copper artefacts in dilute sodium sesquicarbonate solution is a well-recognized stabilization technique--especially in the conservation of objects recovered from marine environments and therefore saturated with chlorides. Here we describe three linked experiments performed to investigate a variation on this treatment, involving the application of a low potential to the artefact in order to drive the chloride extraction process. This includes a new spectroelectrochemical approach which allows 2-D pseudorandom X-ray reflection diffraction patterns to be obtained without interrupting the reaction in solution. Experiments were carried out on synthetically produced chloride layers on copper (nantokite and atacamite). We show that a thick chloride layer is, in general, replaced by a thin cuprite layer through a mechanism which involves detachment of the chloride crystallites from the surface prior to dissolution.

Cell for simultaneous synchrotron radiation X-ray and electrochemical corrosion measurements on cultural heritage metals and other materials.

We describe the construction of an electrochemical cell of the Bragg type suitable for in situ synchrotron X-ray measurements on rough, heterogeneous metals such as cultural heritage alloys and simulants with corroding or passivated surfaces. The cell features a working electrode, which may be moved under remote control from a position close to an X-ray window to full immersion in the electrolyte. A pocket of electrolyte in contact with the bulk can be maintained on the working electrode surface at all times. Its thickness (typically 100-200 microm) can be controlled by adjusting the working electrode position and, independently, altering the conformation of the X-ray window with hydrostatic pressure. Alternatively, the electrode may be lowered into the bulk of the electrolyte. Early results from the cell showing a time-resolved study of the reduction of nantokite to cuprite in sodium sesquicarbonate, accompanied by corrosion potential measurements obtained in parallel, are presented here.