Identification of Green Rust Compounds in the Aqueous Corrosion Processes of Steels; the Case of Microbially Induced Corrosion and Use of 78 K CEMS

Fe(II)-Fe(III) hydroxy-sulphate Green Rust 2, GR2(SO₄ ^–), is obtained by microbially induced corrosion of steel. Transmission Mössbauer spectroscopy (TMS) was used to characterise the corrosion products of steel sheet piles under the biofilm at low sea-water level in a harbour. To understand the process, iron coupons maintained in aqueous solutions of 4 M NaCl and 0.1 M NaHCO₃ of pH 7.4 were studied by X ray diffraction and conversion electron Mössbauer spectroscopy (CEMS) at 78 K. The Fe(II)-Fe(III) hydroxy-carbonate, GR1(CO₃ ^–), covers the surface, as predicted by the E_h-pH diagram.     

Influence of particle size on XRF wear analysis in plastics processing

Wear has to be quantified by the analytical characterization of particles in a plastic film generated by an extruder. The influence of particle size, film (matrix) thickness and particle location on the intensity of the Fe Kα peak, the Fe Kβ/Kα intensity ratios and the Compton scattering peak intensity are discussed. Experimental results are given for two synthetic matrices, vaseline and transparent tape. A comparison of the measured results with those of a simulation is made. Copyright © 2005 John Wiley & Sons, Ltd.     

Fundamental parameter approach to XRF spectroscopy measurements of arsenic in polyester resin skin phantoms

A fundamental parameter (FP) approach that explicitly incorporates the energy‐broadening response of the detector was developed. The ratio between Kα fluorescence peak area and the sum of coherently and incoherently scattered peak areas was used as an indicator of trace element concentration. The peak ratio was theoretically calculated using the FP method. The energy‐broadening response curve of the Si(Li) detector was estimated by matching the theoretical and experimental values of this ratio. The method was implemented for the analysis of the K‐shell x‐ray fluorescence (K‐XRF) spectra of six polyester resin samples corresponding to six different arsenic concentrations. A ¹⁰⁹Cd radioactive source provided the excitation radiation for spectra acquisition. The predicted detector energy resolution expressed as full width at half‐maximum (FWHM) for Fe Kα fluorescence peak (208 ± 5 eV at 6.4 keV) and As Kα fluorescence peak (222 ± 5 eV at 10.5 keV) were in agreement with the experimental measurements. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel

For fundamental studies of the atmospheric corrosion of steel, it is useful to identify the iron oxide phases present in rust layers. The nine iron oxide phases, iron hydroxide (Fe(OH)₂), iron trihydroxide (Fe(OH)₃), goethite (α-FeOOH), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH), feroxyhite (δ-FeOOH), hematite (α-Fe₂O₃), maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) are among those which have been reported to be present in the corrosion coatings on steel. Each iron oxide phase is uniquely characterized by different hyperfine parameters from M?ssbauer analysis, at temperatures of 300K, 77K and 4K. Many of these oxide phases can also be identified by use of Raman spectroscopy. The relative fraction of each iron oxide can be accurately determined from the M?ssbauer subspectral area and recoil-free fraction of each phase. The different M?ssbauer geometries also provide some depth dependent phase identification for corrosion layers present on the steel substrate. Micro-Raman spectroscopy can be used to uniquely identify each iron oxide phase to a high spatial resolution of about 1 μm. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kβ/Kα x‐ray intensity ratios for bromine and iodine compounds

Kβ/Kα x‐ray intensity ratios of some Br and I compounds were studied. The samples were excited by 59.5 keV γ‐rays emitted from an Am‐241 radioisotope source and characteristic K x‐rays emitted from the samples were counted by means of an Si(Li) detector which has a resolution 155 eV at 5.9 keV. The experimental values were compared with the calculated theoretical values for elemental Br and I. Copyright © 2003 John Wiley & Sons, Ltd.     

Numerical approach for depth profiling with GE‐XRF

The atomic percentage of implanted particles on the sample surface was estimated from the peak position of angle dependency of the experimental grazing exit X‐ray fluorescence (GE‐XRF) intensity profile. An algorithm for constructing three‐parametric Gaussian‐type depth profiles of atoms implanted in a substrate was developed. The position of the maximum and its value of the implanted particles distribution as well as a dispersion of that distribution were considered in the calculations. The model was applied to the intensity of the As Kα line emitted from As atoms implanted in a Si wafer. The least‐square method was used to minimize the overall difference between experimental and calculated GE‐XRF intensity. Optimum parameters of the particle distribution were determined in this procedure. Using that profile, the depth dependencies of effective real and imaginary parts of atomic scattering factor and complex index of refraction of the sample material were evaluated. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of surface nanocrystallization induced by fast multiple rotation rolling on hardness and corrosion behavior of 316L stainless steel

A nanostructured layer was fabricated by using fast multiple rotation rolling (FMRR) on the surface of 316L stainless steel. The microstructure in the surface was characterized by transmission electron microscopy and X-ray diffraction. The effects of FMRR on the microhardness, surface roughness and corrosion behavior of the stainless steel were investigated by microhardness measurements, surface roughness measurements, potentiodynamic polarization curves and pitting corrosion tests. The surface morphologies of pitting corrosion specimens were characterized by scanning electron microscopy. The results show that FMRR can cause surface nanocrystallization with the grain size ranges from 6 to 24 nm in the top surface layer of the sample. The microhardness of FMRR specimen in the top surface layer remarkably increases from 190 to 530 HV. However, the surface roughness slightly rises after FMRR treatment. The potentiodynamic polarization curves and pitting corrosion tests indicated that the FMRR treated 316L stainless steel with a surface nanocrystallized layer reduced the corrosion resistance in a 3.5% NaCl solution and enhanced the pitting corrosion rate in a FeCl₃ solution. Possible reasons leading to the decrease in corrosion resistance were discussed.     

Effects of weathering on in situ portable X‐ray fluorescence analyses of geological outcrops: dolerite and rhyolite outcrops from the Preseli Mountains,South Wales

Laboratory experiments were undertaken to investigate the effect of weathering on dolerite and rhyolite samples from the Preseli Mountains, South Wales, an area of archaeological significance for the provenancing of archaeological artefacts. Portable XRF (PXRF) analysis was used to construct a depth profile of elemental concentrations through the weathering layer of suitable rock samples. These measurements were made by sequentially grinding away successive layers, each time measuring the newly exposed surface by PXRF. The elements studied included K, Ca, Ti, Mn, Fe, Ba, Nb, Pb, Sr, Y and Zr. In dolerite samples, Ca, Fe and Y were generally depleted in heavily weathered surface layers, whereas K and Pb were enhanced, the latter element significantly so, probably as a result of anthropogenic activities (emissions from leaded automobile fuel). Element behaviour in rhyolites was less consistent. A correction factor was derived for each element based on the ratio of the weathered surface concentration to the corresponding steady‐state (fresh rock) concentration beneath the altered layer. This correction factor was evaluated as a possible means of compensating for elemental discrepancies when measuring weathered surfaces. Improved data were obtained for a significant number of elements, but further work is required to evaluate this procedure fully. Copyright © 2005 John Wiley & Sons, Ltd.     

Elemental mapping of frozen‐hydrated cells with cryo‐scanning X‐ray fluorescence microscopy

Visualizing the elemental distributions of cells and tissues is of growing importance in biology and medical science because such data deepen our understanding of the behavior of metal‐binding proteins and ions. Elemental mapping by X‐ray fluorescence analysis with a hard X‐ray nanobeam is very well suited for this purpose owing to its high sensitivity and high resolution. Using this technique, samples must be prepared without artifacts that are caused by treatments such as chemical fixation and staining procedures. In many studies of elemental mapping, sample preparation is not explicitly considered. To overcome this deficiency, we developed a cryo‐scanning X‐ray fluorescence microscope and installed it in the second experimental hutch of BL29XUL of SPring‐8. We used it to observe frozen‐hydrated cells that had been fixed by a quick‐freezing technique to preserve elemental data of the living state at an X‐ray energy of 11.5 keV. The distributions of K, Ca, Fe, Cu and Zn were successfully visualized. The distributions of these elements (especially those of K, Ca and Fe) differed from those in cells fixed with paraformaldehyde. Copyright © 2010 John Wiley & Sons, Ltd.     

CEMS study of corrosion products formed by NaCl aqueous solution

Conversion electron M?ssbauer spectroscopy was used to study corrosion products by NaCl aqueous solution. A drop of the solution is put on an iron foil and the foil is left at RT. During the evaporation of the solution, corrosion products are formed. Conversion electron M?ssbauer spectra were taken at temperatures between 15?K and room temperature (RT). In the M?ssbauer spectra a ferric doublet is observed at RT, but sextets are found at 15?K. These results show that the corrosion product mainly consists of γ - FeOOH and a small amount of β - FeOOH is noticed. As NaCl concentration increases, the corrosion layer becomes thick and β- FeOOH?/?γ - FeOOH ratio increases slightly. Consequently, it has been concluded that the produced amount of β- FeOOH increases more rapidly than that of γ - FeOOH with increasing NaCl concentration.     

Optical corrosion meter

In a previous study, a mathematical model relating surface and bulk behaviours of metals in aqueous solution has been developed. The model was established based on principles of holographic interferometry for measuring microsurface dissolution, i.e. mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e. corrosion current. In the present work, an optical corrosion meter was built based on the above model. The corrosion meter consists of an electrochemical cell in which the sample is immersed in aqueous solution. Furthermore, the corrosion meter has a holographic camera with a thermoplastic film for in situ processing of holograms in order to obtain real-time holographic interferoms of the sample in the electrochemical cell. Results of the present work indicate that optical holography is a very useful technique for measuring the corrosion current density of different alloys in aqueous solutions. As a result, the corrosion current density of aluminium, stainless steel, and low-carbon steel in 1 M KCl, 1 M NaCl, and 1 M NaOH solutions were obtained. A comparison between the corrosion data of samples showed that the corrosion current density of the stainless steel in 1 M NaCl is nearly three-folds higher than that of the aluminium in 1 M KCl and the low-carbon steel in 1 M NaOH.     

Evaluation of zinc phosphate coating on cold rolled steel surface by x-ray fluorescence technique

The X-ray fluorescence technique was applied to zinc phosphate coating deposited on cold rolled steel surface. The calibration plot of the intensity ratio of zinc Kα to iron Kα against the surface density gave a linear relationship where the amount of iron dissolution at the beginning of the phosphating process was obtained. A thickness of about 671±203 Å of iron dissolution was deduced from the linear plot. A linear relationship could also be established between the intensity ratio and the coating thickness. The X-ray fluorescence technique also proved to be a rapid, non-destructive and accurate technique for measuring the thickness of thin coatings.     

Micro‐EDXRF investigation of Chalcolithic gold ornaments from Portuguese Estremadura

Chalcolithic gold artefacts assigned to the Bell Beaker Culture in Portuguese Estremadura were analysed by micro‐energy dispersive X‐ray fluorescence spectrometry. These high‐status jewels comprise beads of tubular, spiral and double‐conical type, a spiral ring and a wire fragment. The collection is mainly composed of gold with 8.7–16.3 wt% Ag and <0.04 wt% Cu. Additionally, there is a typologically uncommon double‐conical bead showing a lower Ag content (6.7 wt%). The relative intensity of the Ag‐Kα and Ag‐Lα X‐rays from artefacts established the existence of a surface layer depleted in silver, while the reasonable effective penetration depth of the Ag‐Kα (about 25–30 μm) provided suitable results for such high fineness gold alloys. A uniform Au–Ag composition at the joint indicates that the double‐conical bead was made by joining two sheets without solder. Overall, the collection shows a composition that is similar to known Chalcolithic gold in Portuguese Estremadura but different from coeval gold in Southwestern Iberian Peninsula. The distinct compositional pattern of Chalcolithic gold in Portuguese Estremadura seems to be inconsistent with the natural variability of silver content in alluvial deposits of gold in Iberian Peninsula, thus suggesting a continuous use of particular sources and limited exchange of nuggets and jewels with the neighbouring region. Copyright © 2017 John Wiley & Sons, Ltd.     

Mössbauer spectroscopy and X-ray fluorescence studies on sediments from the methanic zone of the Helgoland mud area,North Sea

⁵⁷Fe Mössbauer spectroscopy (MS) and X-ray fluorescence spectroscopy (XRF) were used to determine the identity of iron(III) oxides in surface (top 30 cm ) and subsurface (> 30 cm – 500 cm)sediments from the Helgoland mud area in the German Bight of the North Sea. A 500 cm-long sediment core was cut in 25cm sections while only the top 10 cm of a 30 cm-long sediment core was sampled. Using a MIMOS spectrometer, MS spectra were recorded at 293K (RT) in backscattering geometry. At 80K and 5.5K, MS analysis was carried out in transmission geometry. At RT and 80K only illite was observed, but at 5.5K lepidocrocite was revealed in the MS spectra. The relation between Fe(III) and Fe(II) doublets of illite did not significantly vary with depth, but the relative amount of lepidocrocite increased with depth reaching about 24 % of iron phases, as revealed by MS. XRF measurements showed that the amount of Fe in the sediments varied with depth but was always less than 4 % of total elemental composition. The main component of the sediment was silica and its depth profile alternated with those of other elements, especially aluminium and iron. It was observed that elevated concentrations of dissolved iron in the subsurface sediment of the Helgoland mud area correlated with the depth-wise distribution of distinct microbial populations presumably due to microbial reduction of excess bioavailable iron minerals such as lepidocrocite. These results are thus, important in the context of microbe-mineral interactions in marine sediments as iron oxides are an electron acceptor for microbial anaerobic respiration.     

Trace elemental determination by portable total reflection X‐ray fluorescence spectrometer with low wattage X‐ray tube

A specimen containing nanograms of Sb, rare earth elements, Pb, and Bi and a specimen containing a few nanograms each of As and Pb were measured using a portable total reflection X‐ray fluorescence spectrometer. Nanograms of Sb, rare earth elements, Pb, and Bi were detected. Although the As Kα line (10.54 keV) overlapped with the Pb Lα line (10.55 keV) in a spectrum of the specimen containing nanograms of As and Pb, the Pb Lβ line was detected. Therefore, the net intensity of the As Kα line was calculated using the Pb Lα/Lβ intensity ratio in a spectrum of a Pb standard solution and the net intensity of the Pb Lβ line in the spectrum of the specimen containing As and Pb. This result indicates that these two elements can be quantified by using the portable spectrometer. Commercially available bottled drinking water was also measured. The portable spectrometer detected several tens of ppb of V in the drinking water sample. Copyright © 2013 John Wiley & Sons, Ltd.     

The investigation of K‐shell fluorescence parameters of Zn–Fe alloys with different grain size and microstrain values

It is known that zinc alloys with iron group metals have better corrosion resistance than pure zinc. Owing to the corrosion resistance of these alloys, Zn–Fe coatings are widely used in automotive industry and have excellent mechanical performance. In this work, we investigated the relationship between the changes in the measured X‐ray fluorescence parameters (K_β/K_α, σ_Kα and σ_Kβ) and the changes in the structural parameters such as microstrain or grain size values for Zn–Fe alloys that were prepared with different pH values. To explain these changes, the K_α and K_βX‐ray production cross sections, and the K_β/K_αX‐ray intensity ratio values were calculated by three different ways for the elemental forms of Zn and Fe. The structural parameters, such as microstrain and grain size, were also calculated. We expect that the outer shell electronic distribution affects the structural parameters of the produced Zn–Fe alloys, changing the measured K_α and K_βX‐ray production cross sections, and the K_β/K_αX‐ray intensity ratio values. We also show that Zn–Fe alloy mi nimum microstrain value corresponds to the maximum changes in K_βX‐ray production cross‐section values of Fe and Zn. Copyright © 2017 John Wiley & Sons, Ltd.     

Composition and corrosion resistance of coatings on the basis of nitrides of titanium and chromium

Ti-Cr-N coatings were deposited on a low-carbon steel St3 substrate by overlapping of Ti and Cr plasma flows in residual nitrogen atmosphere using ion bombardment. Auger electron spectroscopy and X-ray diffraction were used to analyze the element and phase composition of the deposited coatings. It was established that, under constant deposition conditions (the arc current, gas pressure, bias voltage), coatings possess the fcc structure of a (Ti,Cr)N solid solution with uniform distribution of elements along the depth. The growth of the substrate bias voltage leads to an increase of titanium concentration in the coating due to changes in the interaction processes (condensation and sputtering) of the deposited materials with the substrate. Corrosion tests of the coatings and steel St3 were performed in acid (1 M H₂SO₄) and salt (3% NaCl) media. It was found that the corrosion processes progress less intensely in salt solution than in acid medium.     

Study of detection limit and sensitivity of Kα and Lα spectral lines of 47Ag, 48Cd,and 50Sn elements using polychromatic wavelength dispersive X‐ray spectrometer

The purpose of this work was to evaluate the instrumental detection limit and sensitivity for determination of elemental composition of ₄₇Ag, ₄₈Cd, and ₅₀Sn elements in the standard liquid solution with highly advanced polychromatic wavelength dispersive X‐ray fluorescence (PC‐WDXRF) spectrometer equipped with ₄₅Rh X‐ray tube. To improve the sensitivity and detection limit, the bremsstrahlung coming from ₄₅Rh source were reduced by choosing suitable primary beam filters (Al and Cu). Instrumental measuring parameters as well as study of linear calibration curves of K and L shell spectral lines were evaluated to select the best conditions for ₄₇Ag, ₄₈Cd, and ₅₀Sn quantification. The detection limit of Lα spectral lines were found to be ~3 to 5 times lower than Kα spectral lines which results in high sensitivity.     

Time‐resolved x‐ray fluorescence for monitoring the intake of mineral nutrients in living plants

We have applied a time‐resolved means of measurement for studying living plants. The intake of mineral nutrients in a living plant such as stevia has been observed by this measuring instrument. A solution containing K, Ca, Mn, Fe, Cu, and Zn compounds was used as the mineral nutrient solution. The concentrations of the standard solutions were specifically chosen to obtain optimal intensities of the x‐ray peaks. The time dependence of the x‐ray fluorescence (XRF) intensity showed specific intake processes depending on the type of element. In addition, the experimental results suggest differences in the translocation of each element in the stevia stem. We conclude that time‐resolved XRF is a powerful technique for studying living plants. Copyright © 2007 John Wiley & Sons, Ltd.     

Corrosion behavior of boride layers evaluated by the EIS technique

The corrosion behavior of boride layers at the AISI 304 steel surface is evaluated in the present study. Electrochemical impedance spectroscopy (EIS) technique was used for the evaluation of the polarization resistance at the steel surface, with the aid of AUTOLAB potentiostat. Samples were treated with boron paste thickness of 4 and 5 mm, in the range of temperatures 1123 ≤ T ≤ 1273 K and exposed time of 4 and 6 h. The electrochemical technique employed 10 mV AC with a frequency scan range from 8 kHz to 3 mHz in deaerated 0.1 M NaCl solution. Nyquist diagrams show that the highest values of corrosion resistance are present in the samples borided at the temperature of 1273 K, with treatment time of 4 h and 4 mm of boron paste thickness. The values of corrosion resistance on borided steels are compared with the porosity exhibited in the layers.