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The effect of water chemistry, surface condition, alkalizing agent (LiOH vs . KOH), and Zn addition was investigated at 300 °C on the oxidation behaviour of reduced activation ferritic martensitic (RAF/M) EUROFER-97. EUROFER-97 is the proposed material for the water-cooled lithium lead breeder blanket (WCLL-BB) section of DEMO, but its behaviour under elevated temperature hydrogenated water has never been investigated. Advanced material characterization showed that, despite its relatively low chromium content, EUROFER-97 exhibits high corrosion resistance. This is because EUROFER-97 is protected by an inner polycrystalline FeCr 2 O 4 layer, formed regardless of the water chemistry and surface preparation investigated. The outer non-protective oxide consists of Fe 3 O 4 crystallites, which were refined when KOH was used. When injected, Zn was observed only on top of the outer crystallites without diffusing into the inner oxide layer. These findings demonstrate the excellent oxidation behaviour of EUROFER-97 in the proposed water chemistry, highlighting its suitability for the WCLL-BB section.

The self-passivating yttrium-containing WCr alloy has been developed and researched as a potential plasma-facing armour material for fusion power plants. This study explores the use of yttria (Y2O3) powders instead of yttrium elemental powders in the mechanical alloying process to assess their applicability for this material. Fabricated through field-assisted sintering, WCr-Y2O3 ingots show Y2O3 and Cr-containing oxides (Cr-O and Y-Cr-O) dispersed at grain boundaries (GBs), while WCrY ingots contain Y-O particles at grain boundaries, both resulting from unavoidable oxidation during fabrication. WCr-Y2O3 demonstrates higher flexural strength than WCrY across all temperature ranges, ranging from 850 to 1050 MPa, but lower fracture toughness, between 3 and 4 MPa·√m. Enhanced oxidation resistance is observed in WCr-Y2O3, with lower mass gain as compared to WCrY during the 20-hour oxidation test. This study confirms the effectiveness of both yttria and yttrium in the reactive element effect (REE) for the passivation of WCr alloy, suggesting the potential of Y2O3-doped WCr for first wall applications in a fusion power plant.

Plasmon-induced phenomena have recently attracted considerable attention. At the same time, relatively little research has been conducted on electrochemistry mediated by plasmon excitations. Here we report plasmon-induced formation of nanoscale quantized conductance filaments within metal-insulator-metal heterostructures. Plasmon-enhanced electromagnetic fields in an array of gold nanodots provide a straightforward means of forming conductive CrO x bridges across a thin native chromium oxide barrier between the nanodots and an underlying metallic Cr layer. The existence of these nanoscale conducting filaments is verified by transmission electron microscopy and contact resistance measurements. Their conductance was interrogated optically, revealing quantised relative transmission of light through the heterostructures across a wavelength range of 1–12 μm. Such plasmon-induced electrochemical processes open up new possibilities for the development of scalable devices governed by light.

Titanium (IV) sulphide (TiS 2 ) is a layered transition metal dichalcogenide, which we exfoliate using liquid phase exfoliation. TiS 2 is a candidate for being part of a range of future technologies. These applications are varied, and include supercapacitor and battery energy storage devices, catalytic substrates and the splitting of water. The driving force behind our interest was as a material for energy storage devices. Here we investigate a potential failure mechanism for such devices, namely oxidation and subsequent loss of sulphur. This degradation is important to understand, since these applications are highly property-dependent, and changes to the chemistry will result in changes in desired properties. Two approaches to study oxidisation were taken: ex situ oxidation by water and oxygen at room temperature and in situ oxidation by a 5% O 2 /Ar gas at elevated temperatures. Both sources of oxygen resulted in oxidation of the starting TiS 2 flakes, with differing morphologies. Water produced amorphous oxide slowly growing in from the edge of the flakes. Oxygen gas at ≥375 °C produced crystalline oxide, with a range of structures due to oxidation initiating from various regions of the observed flakes. TiS 2 oxidation: moisture is the critical element preventing environmental stability The degradation dynamics of TiS 2 reveal that the flakes oxidise in water and atmosphere, pointing towards moisture as the key driving force. A team led by Valeria Nicolosi at Trinity College Dublin used advanced electron microscopy techniques to investigate the influence of different environments on the deterioration pathways of TiS 2 , a promising candidate for future energy storage applications. By comparing the effect of ex-situ oxidation by water and oxygen at room temperature, and in-situ oxidation at high temperatures, water was proven to effectively oxidise the TiS 2 flakes from the edges thereby forming an amorphous oxide phase. Conversely, the degradation was found to proceed more slowly in atmosphere or vacuum conditions. These results suggest that TiS 2 oxidation could be avoided in a desiccated environment that would prevent water molecules from dissociating in reactive ionic species.

Ion permeation and selectivity of graphene oxide membranes with sub-nm channels dramatically alters with the change in interlayer distance due to dehydration effects whereas permeation of water molecules remains largely unaffected. Graphene oxide membranes show exceptional molecular permeation properties, with promise for many applications 1 , 2 , 3 , 4 , 5 . However, their use in ion sieving and desalination technologies is limited by a permeation cutoff of ∼9 Å (ref.  4 ), which is larger than the diameters of hydrated ions of common salts 4 , 6 . The cutoff is determined by the interlayer spacing ( d ) of ∼13.5 Å, typical for graphene oxide laminates that swell in water 2 , 4 . Achieving smaller d for the laminates immersed in water has proved to be a challenge. Here, we describe how to control d by physical confinement and achieve accurate and tunable ion sieving. Membranes with d from ∼9.8 Å to 6.4 Å are demonstrated, providing a sieve size smaller than the diameters of hydrated ions. In this regime, ion permeation is found to be thermally activated with energy barriers of ∼10–100 kJ mol –1 depending on d . Importantly, permeation rates decrease exponentially with decreasing sieve size but water transport is weakly affected (by a factor of <2). The latter is attributed to a low barrier for the entry of water molecules and large slip lengths inside graphene capillaries. Building on these findings, we demonstrate a simple scalable method to obtain graphene-based membranes with limited swelling, which exhibit 97% rejection for NaCl.

The van der Waals heterostructures, which explore the synergetic properties of 2D materials when assembled into 3D stacks, have already brought to life a number of exciting phenomena and electronic devices. Still, the interaction between the layers in such assembly, possible surface reconstruction, and intrinsic and extrinsic defects are very difficult to characterize by any method, because of the single-atomic nature of the crystals involved. Here we present a convergent beam electron holographic technique which allows imaging of the stacking order in such heterostructures. Based on the interference of electron waves scattered on different crystals in the stack, this approach allows one to reconstruct the relative rotation, stretching, and out-of-plane corrugation of the layers with atomic precision. Being holographic in nature, our approach allows extraction of quantitative information about the 3D structure of the typical defects from a single image covering thousands of square nanometers. Furthermore, qualitative information about the defects in the stack can be extracted from the convergent diffraction patterns even without reconstruction, simply by comparing the patterns in different diffraction spots. We expect that convergent beam electron holography will be widely used to study the properties of van der Waals heterostructures.