In-Situ Imaging of Corrosion Processes in Nuclear Fuel Cladding Spent nuclear fuel in the UK is stored within ponds dosed with NaOH in order to inhibit corrosion and, to ensure the efficiency of storage regimes, there is a need to define and quantify the corrosion processes involved during immersion of fuel cladding. In this project, state-of-the-art characterisation techniques were employed to image the corroding surfaces of two nuclear fuel cladding materials: stainless steel and Magnox. Advanced gas-cooled reactor (AGR) fuel cladding consists of 20Cr-25Ni-Nb stabilised stainless steel and during irradiation the microstructure of the cladding undergoes significant changes, including grain boundary element depletion and segregation. Highspeed atomic force microscopy (HS-AFM) with nanoscale resolution, enabled precipitates and pit initiation in stainless steel to be imaged. Magnox is a magnesiumaluminium alloy and during irradiation in a reactor the outer metal surface oxidises, forming an adherent passive layer which subsequently hydrates when exposed to water. Corrosion processes encompass breakdown of passivity and filiform-like corrosion, both of which were imaged in-situ using the scanning vibrating electrode technique (SVET).

Atomic force microscopes (AFMs) are capable of high-resolution mapping of structures and the measurement of mechanical properties on nanometre scales within gaseous, liquid and vacuum environments. The contact mode high-speed AFM (HS-AFM) developed at Bristol Nano Dynamics Ltd. operates at speeds that are orders of magnitude faster than conventional AFMs, and is capable of capturing multiple frames per second. This allows for direct observation of dynamic events in real-time, with nanometre lateral resolution and subatomic height resolution. HS-AFM is a valuable tool for the imaging of nanoscale corrosion initiation events, such as metastable pitting, grain boundary (GB) dissolution and short crack formation during stress corrosion cracking (SCC). Within this study HS-AFM was combined with SEM and FIB milling to produce a multifaceted picture of localised corrosion events occurring on thermally sensitised AISI 304 stainless steel in an aqueous solution of 1% sodium chloride (NaCl).HS-AFM measurements were performed in situ by imaging within a custom built liquid cell with parallel electrochemical control. The high resolution of the HS-AFM allowed for measurements to be performed at individual reaction sites, i.e. at specific GB carbide surfaces. Topographic maps of the sample surface allowed for accurate measurements of the dimensions of pits formed. Using these measurements it was possible to calculate, and subsequently model, the volumes of metal reacting with respect to time, and so the current densities and ionic fluxes at work. In this manner, the local electrochemistry at nanoscale reaction sites may be reconstructed.

No abstract

Contact-mode high-speed atomic force microscopy (HS-AFM) has been utilised to measure in situ stress corrosion cracking (SCC) with nanometre resolution on AISI Type 304 stainless steel in an aggressive salt solution. SCC is an important failure mode in many metal systems but has a complicated mechanism that makes failure difficult to predict. Prior to the in situ experiments, the contributions of microstructure, environment and stress to SCC were independently studied using HS-AFM. During SCC measurements, uplift of grain boundaries before cracking was observed, indicating a subsurface contribution to the cracking mechanism. Focussed ion beam milling revealed a network of intergranular cracks below the surface lined with a thin oxide, indicating that the SCC process is dominated by local stress at oxide-weakened boundaries. Subsequent analysis by atom probe tomography of a crack tip showed a layered oxide composition at the surface of the crack walls. Oxide formation is posited to be mechanistically linked to grain boundary uplift. This study shows how in situ HS-AFM observations in combination with complementary techniques can give important insights into the mechanisms of SCC.

The appraisal is strongly focussed on challenges associated with the nuclear sector, however these are representative of what is generally encountered by a range of engineering applications. Ensuring structural integrity of key nuclear plant components is essential for both safe and economic operation. Structural integrity assessments require knowledge of the mechanical and physical properties of materials, together with an understanding of mechanisms that can limit the overall operating life. With improved mechanistic understanding comes the ability to develop predictive models of the service life of components. Such models often require parameters which can be provided only by characterisation of processes occurring in situ over a range of scales, with the sub-micrometrescale being particularly important, but also challenging. This appraisal reviews the techniques currently available to characterise microstructural features at the nanometre to micrometre length-scale that can be used to elucidate mechanisms that lead to the early stages of environmentally-assisted crack formation and subsequent growth. Following an appraisal of the techniques and their application, there is a short discussion and consideration for future opportunities.(i) crack pre-initiation and initiation (ii) small cracks (iii) long cracks

A miniature three-point bend fatigue stage for in-situ observation of fatigue microcrack initiation and growth behaviour by scanning electron microscopy (SEM) and contact mode high-speed atomic force microscopy (HS-AFM) has been developed. Details of this stage are provided along with finite element simulations of the stress profiles of said stage and specimen on loading. The proposed stage facilitates study of the micro mechanisms of fatigue damage evolution when used during SEM and HS-AFM scanning of the sample surface. High amplitude low cycle fatigue tests have been carried out on annealed AISI Type 316 stainless steel to demonstrate the applicability of the system. Characteristic features of surface topography and evolution of slip bands observed have been documented. Images obtained by SEM and HS-AFM are presented for comparison. Finally, to demonstrate the capability of the new facility combined with HS-AFM, the spacing between slip bands and their height at different grains at the centre of the metal sample are measured and compared.

In defining the corrosion control requirements for DEMO, the impact of the mixed Eurofer-97/AISI 316 steel system and plant specific effects should be considered throughout, in particular, the effect of the intense magnetic fields present. A substantial amount of data related to corrosion resistance of structural materials is available for industrial applications in fission, but applies to different materials and neutronic conditions. Experimental work is being carried out under the DEMO Breeding Blanket Project of the EUROfusion programme, which will further develop the understanding of irradiation effects. However, there is very limited information regarding magnetic field-assisted corrosion under conditions relevant for the fusion environment readily available in the literature. This work reviews current knowledge and progress in establishing the possible influence of the intense magnetic field on corrosion behaviour of the main structural material, Eurofer-97, in the breeding blanket. To support the relevance of this problem statement, preliminary corrosion experimental results of Eurofer-97 coupons, obtained by using a simple apparatus that allows exposure to a magnetic field intensity of 0.88 T and temperatures up to 80°C in water at atmospheric pressure, are presented as an initial qualitative investigation of possible magnetic field related effects.

No abstract