Effect of H2S on stress corrosion cracking and hydrogen permeation behaviour of X56 grade steel in atmospheric environment

Susceptibility to stress corrosion cracking of X56 steel and its relationship with hydrogen permeation behaviour in atmospheric environment containing H2S was investigated by hydrogen permeation tests at a slow strain rate. The results show that: the fracture strain decreases with the decrease of strain rate under the same experimental conditions; the fracture strain also decreases with the increase of H2S concentration under the same strain rate, and the increased concentration of H2S has no significant effect on the hydrogen permeation in the first wet, etc. dry cycle, however has lead to increased hydrogen permeation in the later cycles. The SEM images of the fractured surfaces show clear evidences of enhanced stress corrosion cracking susceptibility by H2S.

Study on steel corrosion in different seabed sediments

A series of simulation experiments on carbon steel (A(3) steel) and low alloy steel (16 Mn steel) in marine atmosphere (MA), seawater (SW) and seabed sediment (SBS) including rough sea sand, fine sea sand and seabed mud were carried out indoors for a year or so by means of individually hanging plates (IHP) and electrically connected hanging plates (ECHP). The corrosion of steels in SBS was mainly due to the macrogalvanic cell effect. The steel plates at the bottom of SBS, as the anode of a macrogalvanic cell, showed the heaviest corrosion with a corrosion rate of up to 0.12 mm/a, approximately equal to that of steel plates in marine atmosphere. The test results showed that the corrosion rates of A(3) and 16 Mn steel in marine environment were in the order: MA > SW > SBS by the IHP method; and MA > SBS > SW by the ECHP method. The corrosion rates of steels in the water/sediment interface were directly proportional to the grain size of the SBS by the ECHP method, but those of steels in the water/sediment interface did not vary with the grain size of SBS by the IHP method. The corrosion rate of low-alloy steel was a little higher than that of carbon steel. The results of this study have important applications for design of offshore steel structures such as oil platform, pier, and port.

Hydrogen permeation behavior and corrosion monitoring atmospheric of steel in cyclic wet-dry environment

Hydrogen permeation of 16Mn steel under a cyclic wet-dry condition was investigated by Devanathan-Stachurski's electrolytic cell with a membrane covered on the exit side by a nickel layer and the weight loss was measured for each wet-dry cycle. The results show that hydrogen permeation current change with different atmospheric environment: distilled water, seawater, and seawater containing 100 ppm H2S. The results show that seawater can induce an increase in the hydrogen permeation current due to the hydrolyzation reaction. And after the increase, equilibrium is reached due to the equilibrium of hydrolyzation reaction effect and the block of the rust layer. On the other hand, H2S contamination also can induce an increase in the maximum hydrogen permeation current due to the hydrolyzation reaction. And H2S contamination delays the time that hydrogen permeation is detected because of the formation of the FeS(1-x) film. The FeS(1-x) film can block the absorption of hydrogen onto the specimen surface. The surface potential change and the pH change of the metal surface control the hydrogen permeation current. And a clear linear correlation exists between the quantities of hydrogen permeated through the 16Mn steel and the weight loss. Based on the linear correlation, we monitored the corrosion rate by monitoring the hydrogen permeation current by a sensor outside. Good coherences were shown between results in laboratory and outside.

Beyond simple imaging with energetic beams – nanopatterning, correlative microscopy and statistical analysis of inclusions

Electron microscopy (EM) has advanced in an exponential way since the first transmission electron microscope (TEM) was built in the 1930’s. The urge to ‘see’ things is an essential part of human nature (talk of ‘seeing is believing’) and apart from scanning tunnel microscopes which give information about the surface, EM is the only imaging technology capable of really visualising atomic structures in depth down to single atoms. With the development of nanotechnology the demand to image and analyse small things has become even greater and electron microscopes have found their way from highly delicate and sophisticated research grade instruments to key-turn and even bench-top instruments for everyday use in every materials research lab on the planet. The semiconductor industry is as dependent on the use of EM as life sciences and pharmaceutical industry. With this generalisation of use for imaging, the need to deploy advanced uses of EM has become more and more apparent. The combination of several coinciding beams (electron, ion and even light) to create DualBeam or TripleBeam instruments for instance enhances the usefulness from pure imaging to manipulating on the nanoscale. And when it comes to the analytic power of EM with the many ways the highly energetic electrons and ions interact with the matter in the specimen there is a plethora of niches which evolved during the last two decades, specialising in every kind of analysis that can be thought of and combined with EM. In the course of this study the emphasis was placed on the application of these advanced analytical EM techniques in the context of multiscale and multimodal microscopy – multiscale meaning across length scales from micrometres or larger to nanometres, multimodal meaning numerous techniques applied to the same sample volume in a correlative manner. In order to demonstrate the breadth and potential of the multiscale and multimodal concept an integration of it was attempted in two areas: I) Biocompatible materials using polycrystalline stainless steel and II) Semiconductors using thin multiferroic films. I) The motivation to use stainless steel (316L medical grade) comes from the potential modulation of endothelial cell growth which can have a big impact on the improvement of cardio-vascular stents – which are mainly made of 316L – through nano-texturing of the stent surface by focused ion beam (FIB) lithography. Patterning with FIB has never been reported before in connection with stents and cell growth and in order to gain a better understanding of the beam-substrate interaction during patterning a correlative microscopy approach was used to illuminate the patterning process from many possible angles. Electron backscattering diffraction (EBSD) was used to analyse the crystallographic structure, FIB was used for the patterning and simultaneously visualising the crystal structure as part of the monitoring process, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to analyse the topography and the final step being 3D visualisation through serial FIB/SEM sectioning. II) The motivation for the use of thin multiferroic films stems from the ever-growing demand for increased data storage at lesser and lesser energy consumption. The Aurivillius phase material used in this study has a high potential in this area. Yet it is necessary to show clearly that the film is really multiferroic and no second phase inclusions are present even at very low concentrations – ~0.1vol% could already be problematic. Thus, in this study a technique was developed to analyse ultra-low density inclusions in thin multiferroic films down to concentrations of 0.01%. The goal achieved was a complete structural and compositional analysis of the films which required identification of second phase inclusions (through elemental analysis EDX(Energy Dispersive X-ray)), localise them (employing 72 hour EDX mapping in the SEM), isolate them for the TEM (using FIB) and give an upper confidence limit of 99.5% to the influence of the inclusions on the magnetic behaviour of the main phase (statistical analysis).

Condition assessment of a 63-year old reinforced concrete structure exposed to the North Sea

This paper describes the condition of a reinforced concrete balustrade consisting of some 1000 individual beam elements all exposed similarly to the hostile marine environment of the North Sea at Arbroath, Scotland since 1943. A comparison is made of the condition of the original construction with the condition of repairs carried out in 1968 and in 1993. It is shown that the 1943 construction shows very little corrosion-induced cracking and little rust staining even though it does not appear to be of high construction quality. Only a very low percentage of the balustrade beams have been replaced. In contrast the beam installed in 1968 and later in 1993 show very considerable and large concrete cracks directly attributable to the corrosion of the longitudinal reinforcement, even though the concrete is of a higher quality and density. A detailed condition survey and statistics of crack sizes are presented in the paper. It is found that the higher corrosion resistance of the 1943 concrete is generally consistent with the concrete electrical resistivity measurements but the degree of corrosion of the reinforcing bars is inconsistent with chloride penetration measurements. The results are compared with the very few observations available in the literature for ageing concrete structures in marine environments. The results cast doubt on the conventional wisdom that chloride content at the reinforcement correlates well with reinforcement corrosion.

The potential of offshore windfarms to act as marine protected areas – A systematic review of current evidence

As offshore windfarm (OWF) construction in the UK is progressing rapidly, monitoring of the economic and ecological effects of these developments is urgently needed. This is to enable both spatial planning and where necessary mitigation in an increasingly crowded marine environment. One approach to mitigation is co-location of OWFs and marine protected areas (MPAs). This systematic review has the objective to inform this co-location proposal and identify areas requiring further research. A limited number of studies addressing marine renewable energy structures and related artificial structures in coastal waters were found. The results of these studies display a change in species assemblages at artificial structures in comparison to naturally occurring habitats. An increase in hard substrata associated species, especially benthic bivalves, crustaceans and reef associated fish and a decrease in algae abundance were the dominant trends. Assemblages associated with complex concrete structures revealed greater similarity to natural hard substrata compared to those around steel structures. To consider marine renewable energy sites, especially large scale OWFs as MPAs, the dissimilar nature of assemblages on the structures themselves to natural communities should be considered. However positive effects were recorded on the abundance of commercially important crustacean species. This suggests potential for incorporation of OWFs as no fishing, or restricted activity zones within a wider MPA to aid fisheries augmentation. The limited available evidence highlights a requirement for significant further research involving long term monitoring at a variety of sites to better inform management options.

Liquid and solid-state structures of 1,3-dimethylimidazolium salts

Using neutron and single crystal X-ray diffraction the structures of 1,3-dimethylimidazolim chloride and hexafluorophosphate salts have been determined in the liquid and the solid-state. The relative hydrogen bonding characteristics and sizes of the two anions force the ions to pack differently. In each case, a strong correlation between the crystal structure and liquid structure is found.

Analysis of compressive membrane action in concrete slabs

This paper summarises the results obtained from non-linear finite-element analysis (NLFEA) of a series of reinforced-concrete one-way slabs with various boundary conditions representative of a bridge deck slab strip in which compressive membrane action governs the structural behaviour. The application of NLFEA for the optimum analysis and design of in-plane restrained concrete slabs is explored. An accurate material model and various equation solution methods were assessed to find a suitable finite-element method for the analysis of concrete slabs in which arching action occurs. Finally, the results from the NLFEA are compared and validated with those from various experimental test data. Significantly, the numerical analysis was able to model the arching action that occurred as a result of external in-plane restraint at the supports and which enhanced the ultimate strength of the slab. The NLFEA gave excellent predictions for the ultimate load-carrying capacity and far more accurate predictions than those obtained using standard flexural or elastic theory.

Developments in Performance Monitoring of Concrete Exposed to Extreme Environments

The performance of the surface zone of concrete is acknowledged as a major factor governing the rate of deterioration of reinforced concrete structures as it provides the only barrier to the ingress of water containing dissolved ionic species such as chlorides which, ultimately, initiate corrosion of the reinforcement. In-situ monitoring of cover-zone concrete is therefore critical in attempting to make realistic predictions as to the in-service performance of the structure. To this end, this paper presents developments in a remote interrogation system to allow continuous, real-time monitoring of the cover-zone concrete from an office setting. Use is made of a multi-electrode array embedded within cover-zone concrete to acquire discretized electrical resistivity and temperature measurements, with both parameters monitored spatially and temporally. On-site instrumentation, which allows remote interrogation of concrete samples placed at a marine exposure site, is detailed, together with data handling and processing procedures. Site-measurements highlight the influence of temperature on electrical resistivity and an Arrhenius-based temperature correction protocol is developed using on-site measurements to standardize resistivity data to a reference temperature; this is an advancement over the use of laboratory-based procedures. The testing methodology and interrogation system represents a robust, low-cost and high-value technique which could be deployed for intelligent monitoring of reinforced concrete structures.