Constant-distance mode AC-SECM for the visualisation of corrosion pits

The local visualisation of corrosion pits has so far failed to convincingly prove the advantage of scanning microscopy in overcoming Abbey’s Limit. Thus, for imaging pit initiation and instant pit growth the resolution of the methods used for detecting the related changes in local electrochemical activity has to be significantly improved. Progress into this direction has been achieved by combining shear force based constant-distance mode scanning electrochemical microscopy (SECM) with the alternating current mode of this technique (AC-SECM). A very small corrosion pit was generated by inducing active corrosion underneath an accurately positioned 5 μm diameter Pt disk SECM tip that served as counter electrode in the direct mode of SECM. Before and after pit initiation, constant-distance mode AC-SECM images were recorded and subsequently used to identify the area of broken passivity. The results demonstrate the feasibility of the suggested approach to image actively corroding sites with overall dimensions of only a few micrometers. Combination of constant-distance scanning with AC-SECM is an important prerequisite for further improving spatial resolution by employing smaller-diameter micro- or even nano-electrodes as SECM tips.     

Evaporation of material and influence of auxiliary spark gap on the spectral excitation by means of laser emission spectroscopy for local analysis of graphite

For the determination of impurities in graphite, laser-micro-emission spectroscopy allows the analysis of much smaller sample areas than possible by spectroscopic analysis of arc or spark discharges.Because the maximum quantity of material which can be evaporated by a laser beam is only approximately 8μg, it was found necessary to introduce a spark gap above the evaporation pit to provide additional excitation of the plasma, thereby increasing the sensitivity of the analysis. In this way, the radiation intensity of the plasma was increased by two orders of magnitude.The effects of the spark gap parameters, voltage, capacitance and inductance, on the spectral excitation were investigated. Voltage and capacitance determine the energy supplied to the spark gap, whereas capacitance, together with inductance, controls the duration and characteristic of the discharge. To obtain the optimum additional excitation, the duration of the spark discharge had to be matched with the time taken for the material to evaporate.The catalytic effect of some impurity elements on the corrosion of graphite was identified by using the technique to analyse material in the corrosion pits of irradiated graphite fuel elements.     

Electrochemical instabilities due to pitting corrosion of iron

Electrochemical instabilities induced by chlorides and bromides due to pitting corrosion of iron in sulfuric acid solutions are investigated. Analysis of the electrochemical instabilities as a function of the applied potential and the nature and concentration of the aggressive chemical species shows that the system exhibits a transition from aperiodic bursting of large-amplitude to small-amplitude chaotic oscillations at a critical potential (bifurcation potential, E _bif). The E _bif is determined by the halide concentration inside the pits and coincides with the repassivation potential defined in corrosion studies to explain pit repassivation due to changes in pit chemistry. Surface observations show that, at E < E _bif, an active-passive state dissolution (etching) occurs, while at E > E _bif, a polishing state dissolution is reached. Spatial interactions between early initiated pits and the adjacent electrode surface, oxide film alteration, aggressive species accumulation around active pits, and formation of ferrous salt layers in front of the Fe electrode are all considered to be associated with electrochemical instabilities emerging during pitting corrosion of iron under different dissolution states. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 535–550. The text was submitted by the authors in English.     

Development of pitting corrosion on 20Kh13 steel

The nucleation and propagation of corrosion pits on 20Kh13 steel in the NaCl solutions with various concentrations, temperatures, and pH values are studied under the potentiostatic conditions and at the free-corrosion potential. In the potentiostatic experiments, the variations of the depth and diameter of pits and their number with the time are determined. It is shown that the state of metal surface in a certain area adjacent to the active pits changes. The dimensions of the area are estimated. The results, which were obtained at the free-corrosion potential, were much less reproducible. At the free-corrosion potential, in contrast to the potentiostatic conditions, the pit depth increased only slightly and the pit width increased to a larger extent. It is shown that the pH value of NaCl solutions has a pronounced effect on the development of pitting corrosion on 20Kh13 steel.     

Stochastic approach to the spatial analysis of pitting corrosion and pit interaction

This paper presents a stochastic analysis of spatial point patterns as effect of localized pitting corrosion. A test of randomness is performed by means of the inter-event distance method. The robustness of the method is tested with two artificially generated samples. The method is applied to published empirical data. The results complied when spatial regularity of pits was found and showed discrepancy when pit interaction was observed.     

The effect of acetic acid on the pit propagation in CO2 corrosion of carbon steel

The role of acetic acid (HAc) on the pit growth in CO₂ corrosion of carbon steel pipelines is studied by means of an artificial pit electrode. The current flowing between the artificial pit and the outer surface was measured with a zero resistance ammeter. It is shown that the corrosion potential increases with increasing HAc concentration. Depletion of HAc inside the pit imposed a potential difference that triggered the pit growth. The pit did not grow in absence of HAc. The pit growth was self-sustained only to a certain pit depth, beyond which the dissolution current at the bottom of the pit vanished. This is in good agreement with field observations mainly in the case of top-of-line corrosion phenomena.     

Local damage of HT-materials by laser irradiation in the SEM

By using a pulsed Nd:YAG laser the high temperature materials zirconium oxide, fine grain graphite and silicon nitride were rapidly irradiated (heating thermal shock) and their damage behavior was investigated. The laser beam parameters at sample surface were detected by a laser beam analyzing system and correlated with the local damage mechanisms of the materials as erosion, crack formation and solid-solid phase transformation. For the investigations image analysis, localized x-ray analysis, and the ion beam slope cutting technique were applied. The temperature field in the material was simulated by using temperature dependent material parameters for different laser beam parameters. The results illustrate both the strong influence of the temporal and spatial laser energy profile and the materials properties to the material damage.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Development of a new total reflection X‐ray fluorescence instrument using polycapillary X‐ray lens

A new TXRF instrument combined with micro‐XRF analytical technique was proposed. An X‐ray micro‐beam was obtained by using a polycapillary X‐ray lens. The evaluated diameter of the X‐ray beam at the focal distance was 35 μm. In order to satisfy the total reflection condition of the present instrument, we attempted to cut the X‐ray micro‐beam above the critical angle of the total reflection with a slit. After the slit was applied, a clear critical angle could be observed. Using this proposed instrumental setup, we applied this to the analysis of a single particle on a flat Si substrate.     

Development of pitting corrosion of stainless steel 403 in sodium chloride solutions

Pitting corrosion of stainless steel 403 in the NaCl solutions is studied. It is shown that the experimental results obtained under the potentiostatic conditions do not provide sufficient information on the behavior of steel under the conditions of free corrosion. The corrosion experiments take long time, their results exhibit poor reproducibility; however, they are necessary for obtaining reliable data on the corrosion behavior of steel. The development of corrosion process is reflected in the variation of corrosion potential with time. The effect of concentration and temperature of NaCl solutions on the development of pitting corrosion is studied. The peculiarities of the distribution of pits over the test specimen surface are revealed. In 1 M NaCl solution at 20°C, few pits arise. Some of them repassivate; some pits grow, initially, in diameter and depth and, then, almost only in depth. The examples of through pit formation on the specimens 4 mm thick are presented.     

Pitting Corrosion Mechanisms and Characteristics of Aluminum in Solar Heating Systems

The complex characteristics and mechanisms of aluminum pitting corrosion in a solar heating system were studied by the chemical immersion method and electrochemical techniques as well as fractal theory. The results showed that pitting corrosion of Al occurred in a tap water environment due to the local enrichment of Cl^? ions. The higher the Cl^? ions concentration, the more negative the critical pitting potential (E_b) of Al. A linear relationship between E_b and the logarithm of Cl^? ions concentration was observed. The pitting corrosion mechanism of Al in neutral water was explained in terms of complexation corrosion theory. The corrosion surface images of aluminum immersed in tap water were captured and analyzed by image processing technique and box‐dimension method. The fractal characteristics of pit distribution, described by fractal dimension, have been identified. The fractal dimension of the pit distribution increased with the increase of immersion time and had the same trend as that of the weight loss. Fractal dimension can, thus, be used as an important parameter for quantitative evaluation of pitting corrosion of aluminum.     

Quantitative multi-element mapping of ancient glass using a simple and robust LA-ICP-MS rastering procedure in combination with image analysis

The surface of two glass artefacts in mosaic style, probably fragments of conglomerate glass bowls dating back two millennia, was investigated by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). By rastering with the laser beam over a selected area of the surface of the glass artefacts, elemental oxide maps were generated. Quantification of the elemental oxides in the maps was achieved using a so-called sum normalization procedure, summating the elements—54 in total—as their oxides to 100% (w/w), without using an internal standard and applying only one external standard (NIST SRM glass 610). This results in a robust mapping procedure which automatically corrects for drift and defocusing issues. Sum normalization was applied to each pixel in the map separately and required a custom source code to process all the data in the tens of thousands of pixels to generate the elemental oxide concentration maps. The digital element maps generated upon rastering of the two glass artefacts are very compelling and are an excellent entry point to gain detailed insight into their fabrication and provenance using image analysis software for retrieval of localized elemental oxide concentrations and correlations.     

Fractal analysis of pit morphology of Inconel alloy 600 in sulphate,nitrate and bicarbonate ion-containing sodium chloride solution at temperatures of 25–100 °C

Pit morphology of Inconel alloy 600 in sulphate (SO₄ ^2-), nitrate (NO₃ ^-) and bicarbonate (HCO₃ ^-) ion-containing 0.5 M sodium chloride (NaCl) solution was analysed in terms of fractal geometry as functions of solution temperature and anion concentration using the potentiostatic current transient technique, scanning electron microscopy, image analysis and ac-impedance spectroscopy. Potentiostatic current transients revealed that the pitting corrosion is facilitated by the increase in solution temperature, irrespective of anion additives, and that it is hindered by the increase in NO₃ ^- and HCO₃ ^- ion concentration, regardless of solution temperature. Above 60 °C, it was also found that the addition of SO₄ ^2- ions impedes pit initiation, but enhances pit growth. The value of fractal dimension D _f of the pits increased with increasing solution temperature and with decreasing NO₃ ^- and HCO₃ ^- ion concentration. Moreover, the value of D _f increased above 60 °C with increasing SO₄ ^2- ion concentration. This is caused by the increase in the ratio of pit perimeter to pit area, implying the formation of pits with micro-branched shape due to the acceleration of the local attack in the pits. From the decrease of the depression parameter with increasing solution temperature, it is inferred that the roughness of the pits increased with increasing solution temperature. In addition, the depression parameter was found to increase with increasing NO₃ ^- and HCO₃ ^- ion concentration. But, above 60 °C, in the case of SO₄ ^2- ion addition, the depression parameter decreased with increasing SO₄ ^2- ion concentration. From the experimental findings, the three-dimensional pit morphology is discussed in terms of the values of D _f of the pits and the depression parameter, with respect to anion concentration and solution temperature.     

Block Copolymer Micelles with Near Infrared Metal Phthalocyanine Dyes for Laser Induced Writing

A route has been developed to disperse metal‐containing phthalocyanine dyes in a non‐polar medium based on amphiphilic block copolymer micelles of poly[styrene‐block‐(4‐vinylpyridine)] (PS‐b‐P4VP) and poly[styrene‐block‐(acrylic acid)] (PS‐b‐PAA) copolymers. Polar P4VP and PAA efficiently encapsulate cobalt(II ), manganese(II ), and nickel(II ) phthalocyanine dyes by axial coordination of nitrogen and µ‐oxo bridged dimerization with the transition metals, respectively. Good dispersion of the dyes is confirmed by the linear enhancement of Q‐bands in UV–vis absorption spectra with dye concentration. A thin monolayered PS‐b‐P4VP micelle film that contained a nickel(II ) phthalocyanine dye which efficiently adsorbs a laser beam on a localized area to generate a local heat higher than the glass transition temperatures of both blocks. One‐dimensional laser writing on the dye‐containing film allows the fabrication of a few submicrometer wide line patterns in which the self‐assembled nanostructure of the block copolymer is modified by the directional heat arising from laser scanning.

     

Laser embedding of TiC particles into the surface of phosphor bronze‐bearing material

A carbon film containing 5% TiC particles is formed on a pre‐prepared bronze surface prior to laser treatment. The carbon film provides increased absorption of the incident laser beam and hosts TiC particles with a uniform distribution at the workpiece surface. Optical and scanning electron microscopy are used to examine the metallurgical and morphological changes in the laser treated layer. Micro‐hardness of the laser‐treated surface is measured, and the residual stress formed in the surface vicinity is measured using the X‐ray diffraction technique. It was found that a dense layer with fine grains was formed in the laser‐treated layer. The micro‐hardness of the laser‐treated surface increases almost three times compared with the base material hardness. The presence of a dense layer and the formation of Cu₃N in the surface region contribute to the hardness enhancement at the surface. Copyright © 2012 John Wiley & Sons, Ltd.     

Al 2024-T3合金局部腐蚀的扫描微电极研究

应用扫描微电极技术和扫描电子显微镜技术研究Al 2024 T3合金在NaCl溶液中开路状态下的局部腐蚀发生的早期过程.实验表明,当Al合金浸入NaCl溶液,其表面即刻发生局部微点腐蚀,这些微点腐蚀与合金表面第二相颗粒密切相关,Al合金表面第二相Al2CuMg颗粒可表现为三种不同的腐蚀行为.     

A Neural Network Model in the Calibration of Glucose Sensor Based on the Immobilization of Glucose Oxidase into Polypyrrole Matrix

The immobilization of enzymes on an electrode surface is of great importance in bioelectrochemistry. The entrapment of enzymes into a polymer matrix is simple and a speedy technique for the production of biosensors. This procedure of enzyme immobilization by electropolymerization has a great significance in fabrication of micro sensors in the preparation of multiplayer devices. In current study, glucose oxidase enzyme that is specific for the glucose determination was entrapped into polypyrrole matrix containing p‐benzoquinone in PIPES buffer and glucose sensitivity of the biosensor was investigated. Then, artificial neural network analysis was done for the nonlinear calibration plot. This implementation can be used for the sensor failure detection, as well. The estimation power of the neural network used in the direct and inverse calibration modelling was examined by statistical methods. It presented the good performance for the estimation power.     

Morphological evolution of Ge islands on the Si(100) surface: from huts to pits

The morphological evolution on the size and shape of Ge island on the Si(100) surface by depositing and subsequent annealing processes is studied in situ by using scanning tunneling microscopy at ultrahigh vacuum environment. A slower growth rate is maintained when the islands grow to larger sizes beyond the wetting layers. While at room temperature, the epitaxial strain is relieved by the formation of three‐dimensional islands (so‐called ‘hut’ clusters). When the sample is annealed at 200 °C, the strain is relieved by forming pits, having the circular cone shape but with their apex pointing down, with Ge clusters formed at the rim of pits. Copyright © 2016 John Wiley & Sons, Ltd.     

Droplet-size distribution gradient induced by laser curing in polymer dispersed liquid crystals

We have studied the morphology and electro-optical properties of polymer dispersed liquid crystals prepared by polymerization-induced phase separation (PIPS) under high intensity UV laser curing. The results have shown that localized high intensity curing generates a gradient of the droplet size distribution outside the directly irradiated area as a consequence of the non-uniform spatial distribution of the scattered intensity. Such a distribution of the droplet size reflects in a peculiar electro-optical behaviour that could find potential application in optical devices. Both shape and spatial extent of the droplet size gradient are affected by the spatial velocity of polymerization which in turn strongly depends on the intensity of the curing laser beam. This dependence has also been experimentally investigated.     

Droplet-size distribution gradient induced by laser curing in polymer dispersed liquid crystals

We have studied the morphology and electro-optical properties of polymer dispersed liquid crystals prepared by polymerization-induced phase separation (PIPS) under high intensity UV laser curing. The results have shown that localized high intensity curing generates a gradient of the droplet size distribution outside the directly irradiated area as a consequence of the non-uniform spatial distribution of the scattered intensity. Such a distribution of the droplet size reflects in a peculiar electro-optical behaviour that could find potential application in optical devices. Both shape and spatial extent of the droplet size gradient are affected by the spatial velocity of polymerization which in turn strongly depends on the intensity of the curing laser beam. This dependence has also been experimentally investigated.     

SECM and SKPFM Studies of the Local Corrosion Mechanism of Al Alloys – A Pathway to an Integrated SKP‐SECM System

Scanning Kelvin Probe Force Microscopy and Scanning Electrochemical Microscopy were applied for the investigation of localized corrosion on heterogeneous aiming on the investigation of the possible correlation between the local surface potential differences, measured by the Kelvin probe technique in ambient conditions, and corrosion during immersion in a corrosive electrolyte. A model sample mimicking the interaction of Al and Cu in Al alloys was chosen to demonstrate the complementary nature of the information received from SKPFM and SECM. The necessary prerequisites for a future integration of SKP and SECM into a single set‐up are discussed.