Simulating selected magnetic properties of TbxPr1-xAl2, a magnetocaloric compound.

TbxPr1-xAl2are ferrimagnetic materials exhibiting magnetocaloric effect that have gained considerable attention due to their potential use as an alternative in refrigeration, magnetic sensors and in information storage technology. Here using the mean field approach numerical simulations were conducted forx= 0.1, 0.2, 0.3, 0.4, 0.5, and 0.75, to analyze selected physical properties, such as x-ray and neutron powder diffraction, magnetization and heat capacity. The simulations successfully reproduced the experimental data providing a comprehensive characterization and improved understanding of this family of compound.

In situ real-time neutron imaging of gaseous H2 adsorption and D2 exchange on carbon-supported Pd catalysts.

We use in situ neutron imaging to observe the adsorption/absorption of hydrogen within a packed catalyst bed of a Pd/C catalyst at a spatial and temporal resolution of ∼430 µm and a ∼9 s respectively. Additionally, the H2/D2 exchange process across the catalyst bed is followed in real time.

A new thermography using inelastic scattering analysis of wavelength-resolved neutron transmission imaging.

Thermography using energy-dependent neutron transmission imaging can non-invasively and non-destructively visualize a real-space distribution of interior temperatures of a material in a container. Previously, resonance absorption broadening analysis and Bragg-edge shift analysis using energy-resolved neutron transmission have been developed, however some issues remain, e.g., imaging efficiency, substance limitation and temperature sensitivity. For this reason, we propose a new neutron thermography using the temperature dependence of inelastic scattering of cold neutrons. This method has some advantages, for example, the imaging efficiency is high because cold neutrons are measured with moderate wavelength resolution, and light elements can be analysed in principle. We investigated the feasibility of this new neutron thermography at pulsed neutron time-of-flight imaging instruments at ISIS in the United Kingdom and HUNS in Japan. A Rietveld-type transmission spectrum analysis program (RITS) was employed to refine temperature and atomic displacement parameters from the inelastic scattering cross-section analysis. Finally, we demonstrated interior thermography of an α-Fe sample of 10 mm thickness inside a vacuum chamber by using a neutron time-of-flight imaging detector at the compact accelerator-driven pulsed neutron source HUNS.

In-Situ Anaerobic Heating of Human Bones Probed by Neutron Diffraction.

The first neutron diffraction study of in-situ anaerobic burning of human bones is reported, aiming at an interpretation of heat-induced changes in bone, which were previously detected by vibrational spectroscopy, including inelastic neutron scattering techniques. Structural and crystallinity variations were monitored in samples of the human femur and tibia, as well as a reference hydroxyapatite, upon heating under anaerobic conditions. Information on the structural reorganization of the bone matrix as a function of temperature, from room temperature to 1000 °C, was achieved. Noticeable crystallographic and domain size variations, together with O-H bond lengths and background variations, were detected. Above 700 °C, the inorganic bone matrix became highly symmetric, devoid of carbonates and organic constituents, while for the lower temperature range (<700 °C), a considerably lower crystallinity was observed. The present pilot study is expected to contribute to a better understanding of the heat-prompted changes in bone, which can be taken as biomarkers of the burning temperature. This information is paramount for bone analysis in forensic science as well as in archeology and may also have useful applications in other biomaterial studies.

The Influence of Sintering Temperature on the Pore Structure of an Alkali-Activated Kaolin-Based Geopolymer Ceramic.

Geopolymer materials are used as construction materials due to their lower carbon dioxide (CO2) emissions compared with conventional cementitious materials. An example of a geopolymer material is alkali-activated kaolin, which is a viable alternative for producing high-strength ceramics. Producing high-performing kaolin ceramics using the conventional method requires a high processing temperature (over 1200 °C). However, properties such as pore size and distribution are affected at high sintering temperatures. Therefore, knowledge regarding the sintering process and related pore structures on alkali-activated kaolin geopolymer ceramic is crucial for optimizing the properties of the aforementioned materials. Pore size was analyzed using neutron tomography, while pore distribution was observed using synchrotron micro-XRF. This study elucidated the pore structure of alkali-activated kaolin at various sintering temperatures. The experiments showed the presence of open pores and closed pores in alkali-activated kaolin geopolymer ceramic samples. The distributions of the main elements within the geopolymer ceramic edifice were found with Si and Al maps, allowing for the identification of the kaolin geopolymer. The results also confirmed that increasing the sintering temperature to 1100 °C resulted in the alkali-activated kaolin geopolymer ceramic samples having large pores, with an average size of ~80 µm3 and a layered porosity distribution.

High-speed 4D neutron computed tomography for quantifying water dynamics in polymer electrolyte fuel cells.

In recent years, low-temperature polymer electrolyte fuel cells have become an increasingly important pillar in a zero-carbon strategy for curbing climate change, with their potential to power multiscale stationary and mobile applications. The performance improvement is a particular focus of research and engineering roadmaps, with water management being one of the major areas of interest for development. Appropriate characterisation tools for mapping the evolution, motion and removal of water are of high importance to tackle shortcomings. This article demonstrates the development of a 4D high-speed neutron imaging technique, which enables a quantitative analysis of the local water evolution. 4D visualisation allows the time-resolved studies of droplet formation in the flow fields and water quantification in various cell parts. Performance parameters for water management are identified that offer a method of cell classification, which will, in turn, support computer modelling and the engineering of next-generation flow field designs.

Preliminary paleohistological observations of the StW 573 ('Little Foot') skull.

Numerous aspects of early hominin biology remain debated or simply unknown. However, recent developments in high-resolution imaging techniques have opened new avenues in the field of paleoanthropology. More specifically, X-ray synchrotron-based analytical imaging techniques have the potential to provide crucial details on the ontogeny, physiology, biomechanics, and biological identity of fossil specimens. Here we present preliminary results of our X-ray synchrotron-based investigation of the skull of the 3.67-million-year-old Australopithecus specimen StW 573 ('Little Foot') at the I12 beamline of the Diamond Light Source (United Kingdom). Besides showing fine details of the enamel (i.e., hypoplasias) and cementum (i.e., incremental lines), as well as of the cranial bone microarchitecture (e.g., diploic channels), our synchrotron-based investigation reveals for the first time the 3D spatial organization of the Haversian systems in the mandibular symphysis of an early hominin.

Frame overlap Bragg edge imaging.

Neutron Bragg edge imaging enables spatially resolved studies of crystalline features through the exploitation and analysis of Bragg edges in the transmission spectra recorded in each pixel of an imaging detector. Studies with high spectral resolutions, as is required e.g. for high-resolution strain mapping, and with large wavelength ranges have been largely reserved to pulsed neutron sources. This is due to the fact, that the efficiency for high wavelength resolution measurements is significantly higher at short pulse sources. At continuous sources a large fraction of the available neutrons must be sacrificed in order to achieve high wavelength resolution for a relevant bandwidth e.g. through a chopper system. Here we introduce a pulse overlap transmission imaging technique, which is suited to increase the available flux of high wavelength resolution time-of-flight neutron Bragg edge imaging at continuous neutron sources about an order of magnitude. Proof-of-principle measurements utilizing a chopper with a fourfold repeated random slit distribution of eight slits were performed at a thermal neutron beamline. It is demonstrated, that disentanglement of the overlapping pulses is achieved with the correlation theorem for signal processing. Thus, the Bragg edge pattern can be reconstructed from the strongly overlapping Bragg edge spectra recorded and the results demonstrate the feasibility of the technique.

4D imaging of lithium-batteries using correlative neutron and X-ray tomography with a virtual unrolling technique.

The temporally and spatially resolved tracking of lithium intercalation and electrode degradation processes are crucial for detecting and understanding performance losses during the operation of lithium-batteries. Here, high-throughput X-ray computed tomography has enabled the identification of mechanical degradation processes in a commercial Li/MnO2 primary battery and the indirect tracking of lithium diffusion; furthermore, complementary neutron computed tomography has identified the direct lithium diffusion process and the electrode wetting by the electrolyte. Virtual electrode unrolling techniques provide a deeper view inside the electrode layers and are used to detect minor fluctuations which are difficult to observe using conventional three dimensional rendering tools. Moreover, the 'unrolling' provides a platform for correlating multi-modal image data which is expected to find wider application in battery science and engineering to study diverse effects e.g. electrode degradation or lithium diffusion blocking during battery cycling.

4D Bragg Edge Tomography of Directional Ice Templated Graphite Electrodes.

Bragg edge tomography was carried out on novel, ultra-thick, directional ice templated graphite electrodes for Li-ion battery cells to visualise the distribution of graphite and stable lithiation phases, namely LiC12 and LiC6. The four-dimensional Bragg edge, wavelength-resolved neutron tomography technique allowed the investigation of the crystallographic lithiation states and comparison with the electrode state of charge. The tomographic imaging technique provided insight into the crystallographic changes during de-/lithiation over the electrode thickness by mapping the attenuation curves and Bragg edge parameters with a spatial resolution of approximately 300 µm. This feasibility study was performed on the IMAT beamline at the ISIS pulsed neutron spallation source, UK, and was the first time the 4D Bragg edge tomography method was applied to Li-ion battery electrodes. The utility of the technique was further enhanced by correlation with corresponding X-ray tomography data obtained at the Diamond Light Source, UK.

Elusive Valence Transition in Mixed-Valence Sesquioxide Cs4O6.

Cs4O6 is a mixed-valence molecular oxide with a cubic structure, comprising valency-delocalized O24/3- units and with properties highly sensitive to cooling protocols. Here we use neutron powder diffraction to authenticate that, while upon deep quenching the cubic phase is kinetically arrested down to cryogenic temperatures, ultraslow cooling results in an incomplete structural transition to a contracted tetragonal phase. Two dioxygen anions in a 1:2 ratio are identified, providing evidence that the transition is accompanied by charge and orbital order and stabilizes a Robin-Day Class II mixed-valence state, comprising O22- and O2- anions. The phenomenology of the phase change is consistent with that of a martensitic transition. The response of the low-temperature phase assemblage to heating is complex, involving a series of successive interconversions between the coexisting phases. Notably, a broad interconversion plateau is present near 260 K, signifying reentrant kinetic arrest of the tetragonal phase upon heating because of the combined effects of increased steric hindrance for molecular rotation and melting of charge and orbital order. The geometrically frustrated pyrochlore lattice adopted by the paramagnetic S = 1/2 O2- units provides an intimate link between the crystal and magnetic properties of charge-ordered Cs4O6, naturally accounting for the absence of magnetic order.

Egyptian Grave Goods of Kha and Merit Studied by Neutron and Gamma Techniques.

Artifacts from the Egyptian grave goods of Kha and Merit preserved at the Museo Egizio in Turin were studied through a combination of non-destructive and non-invasive neutron and gamma techniques (namely neutron imaging, neutron diffraction and prompt gamma activation analysis). The results provide unprecedented morphological reconstructions of the inner parts of the two alabaster and metallic vases and their isotopic and phase composition, thereby extending our knowledge of the hitherto unknown content of the vases and their functions.

Non-Destructive Study of Bulk Crystallinity and Elemental Composition of Natural Gold Single Crystal Samples by Energy-Resolved Neutron Imaging.

Energy-resolved neutron imaging enables non-destructive analyses of bulk structure and elemental composition, which can be resolved with high spatial resolution at bright pulsed spallation neutron sources due to recent developments and improvements of neutron counting detectors. This technique, suitable for many applications, is demonstrated here with a specific study of ~5-10 mm thick natural gold samples. Through the analysis of neutron absorption resonances the spatial distribution of palladium (with average elemental concentration of ~0.4 atom% and ~5 atom%) is mapped within the gold samples. At the same time, the analysis of coherent neutron scattering in the thermal and cold energy regimes reveals which samples have a single-crystalline bulk structure through the entire sample volume. A spatially resolved analysis is possible because neutron transmission spectra are measured simultaneously on each detector pixel in the epithermal, thermal and cold energy ranges. With a pixel size of 55 µm and a detector-area of 512 by 512 pixels, a total of 262,144 neutron transmission spectra are measured concurrently. The results of our experiments indicate that high resolution energy-resolved neutron imaging is a very attractive analytical technique in cases where other conventional non-destructive methods are ineffective due to sample opacity.

The impact of charge transfer and structural disorder on the thermoelectric properties of cobalt intercalated TiS2.

A family of phases, Co x TiS2 (0 ≤ x ≤ 0.75) has been prepared and characterised by powder X-ray and neutron diffraction, electrical and thermal transport property measurements, thermal analysis and SQUID magnetometry. With increasing cobalt content, the structure evolves from a disordered arrangement of cobalt ions in octahedral sites located in the van der Waals' gap (x ≤ 0.2), through three different ordered vacancy phases, to a second disordered phase at x ≥ 0.67. Powder neutron diffraction reveals that both octahedral and tetrahedral inter-layer sites are occupied in Co0.67TiS2. Charge transfer from the cobalt guest to the TiS2 host affords a systematic tuning of the electrical and thermal transport properties. At low levels of cobalt intercalation (x < 0.1), the charge transfer increases the electrical conductivity sufficiently to offset the concomitant reduction in |S|. This, together with a reduction in the overall thermal conductivity leads to thermoelectric figures of merit that are 25% higher than that of TiS2, ZT reaching 0.30 at 573 K for Co x TiS2 with 0.04 ≤ x ≤ 0.08. Whilst the electrical conductivity is further increased at higher cobalt contents, the reduction in |S| is more marked due to the higher charge carrier concentration. Furthermore both the charge carrier and lattice contributions to the thermal conductivity are increased in the electrically conductive ordered-vacancy phases, with the result that the thermoelectric performance is significantly degraded. These results illustrate the competition between the effects of charge transfer from guest to host and the disorder generated when cobalt cations are incorporated in the inter-layer space.

Multi-scale Characterisation of the 3D Microstructure of a Thermally-Shocked Bulk Metallic Glass Matrix Composite.

Bulk metallic glass matrix composites (BMGMCs) are a new class of metal alloys which have significantly increased ductility and impact toughness, resulting from the ductile crystalline phases distributed uniformly within the amorphous matrix. However, the 3D structures and their morphologies of such composite at nano and micrometre scale have never been reported before. We have used high density electric currents to thermally shock a Zr-Ti based BMGMC to different temperatures, and used X-ray microtomography, FIB-SEM nanotomography and neutron diffraction to reveal the morphologies, compositions, volume fractions and thermal stabilities of the nano and microstructures. Understanding of these is essential for optimizing the design of BMGMCs and developing viable manufacturing methods.

Synthesis and properties of lanthanide ruthenium(III) oxide perovskites.

An extensive series of new LnRuO3 perovskites has been synthesized at high pressure. These ruthenium(III)-based oxides are ruthenium deficient, and high-pressure samples have compositions close to LnRu(0.9)O3. These phases stabilize ruthenium(III) which is very unusual in oxides. X-ray and neutron powder diffraction studies show that the materials adopt orthorhombic perovskite superstructures in which the RuO6 octahedra are tetragonally compressed. These distortions, and the Mott insulator properties of the materials, are driven by strong spin-orbit coupling.

Anionogenic mixed valency in KxBa1-xO2-δ.

We have synthesized members of an isostructural solid solution series KxBa1-xO2-δ (x < 0.41, δ < 0.11) containing mixed-valent dioxygen anions. Synthesis in liquid ammonia solution allows a continuous range of compounds to be prepared. X-ray and neutron diffraction show that KxBa1-xO2-δ adopts the tetragonal rocksalt-derived structure of the end members KO2 and BaO2, without any structural phase transition down to 5 K, the lowest temperature studied here. We identify four oxygen-oxygen stretching modes above 750 cm(-1) in the measured Raman spectra, unlike the spectra of KO2 and BaO2 which both contain just a single mode. We use density functional theory calculations to show that the stretching modes in KxBa1-xO2-δ arise from in-phase and anti-phase coupling of the stretching of nearest-neighbor oxygen dimers when the valence state of the dimers lies between -1 and -2 because of mixed cation coordination. This coupling is a direct signature of a novel type of anionogenic mixed valency.

Non-invasive chemical and phase analysis of Roman bronze artefacts from Thamusida (Morocco).

A repertory of Roman military bronze equipment (1st- 3rd century AD) found at the archaeological site of Thamusida (Rabat, Morocco) was analysed by non-destructive X-ray fluorescence and time of flight neutron diffraction (ToF-ND). Most objects are made of leaded alloys, where copper is combined with tin and/or zinc and, in six cases, to arsenic as well. A mixed technology was employed, making a limited use of "pure" semi-finished materials if compared with the large utilization of recycled materials (brass and bronze).

Metal-organic polyhedral frameworks: high h(2) adsorption capacities and neutron powder diffraction studies.

Neutron powder diffraction experiments on D(2)-loaded NOTT-112 reveal that the axial sites of exposed Cu(II) ions in the smallest cuboctahedral cages are the first, strongest binding sites for D(2) leading to an overall discrimination between the two types of exposed Cu(II) sites at the paddlewheel nodes. Thus, the Cu(II) centers within the cuboctahedral cage are the first sites of D(2) binding with a Cu-D(2) distance of 2.23(1) A.

Ordered mesoporous Fe2O3 with crystalline walls.

Alpha-Fe(2)O(3) has been synthesized with an ordered mesoporous structure and crystalline walls that exhibit a near-single crystal-like order. The unique magnetic behavior of the material, distinct from bulk nanoparticles of alpha-Fe(2)O(3) or mesoporous Fe(2)O(3) with disordered walls, has been established. Magnetic susceptibility, Mössbauer, and neutron diffraction data show that the material possesses the same long-range magnetic order as bulk alpha-Fe(2)O(3), despite the wall thickness being less than the 8 nm limit below which magnetic ordering breaks down in nanoparticulate alpha-Fe(2)O(3), yet the Morin transition of bulk alpha-Fe(2)O(3) is absent. It is also shown by TEM, PXRD, and EXAFS that alpha-Fe(2)O(3) with the same ordered mesoporous structure but disordered walls contains small crystalline domains. Mössbauer and magnetic susceptibility data demonstrate that this material exhibits no long-range magnetic order but superparamagnetic behavior.