Materials under pressure

Pressure in manufacturing and life sciences is a key parameter in defining the state of matter. In this special issue of MRS Bulletin, we focus on several of the many and diverse domains of advanced materials research where the pressure (or stress) applied is used to alter or otherwise garner information on the material properties. We give an overview of research in which the application of high pressure – often combined with high temperatures and advanced analysis – has led to technological progress in the preparation of superhard materials, in discovering new chemistry for the dense forms of low-Z elements, and in the interplay and mimicking of chemical-induced versus pressure-induced structural and electronic changes to prepare new magnetic and energy materials. In addition, the response of materials such as glasses and perovskites to high stress conditions is discussed, where pressures in the gigapascal regime can easily be achieved in everyday usage. Finally, the structural, dynamical and phase behavior of biological systems is considered

Calibration of key temperature-dependent ocean microbial processes in the cGENIE.muffin Earth system model

Temperature is a master parameter in the marine carbon cycle, exerting a critical control on the rate of biological transformation of a variety of solid and dissolved reactants and substrates. Although in the construction of numerical models of marine carbon cycling, temperature has been long-recognised as a key parameter in the production and export of organic matter at the ocean surface, it is much less commonly taken into account in the ocean interior. There, bacteria (primarily) transform sinking particulate organic matter into its dissolved constituents and thereby consume dissolved oxygen (and/or other electron acceptors such as sulphate) and release nutrients, which are then available for transport back to the surface. Here we present and calibrate a more complete temperature-dependent representation of marine carbon cycling in the cGENIE.muffin Earth system model, intended for both past and future climate applications. In this, we combine a temperature-dependent remineralisation scheme for sinking organic matter with a biological export production scheme that also includes a temperature-dependent limitation on nutrient uptake in surface waters (and hence phytoplankton growth). Via a parameter ensemble, we jointly calibrate the two parameterisations by statistically contrasting model projected fields of nutrients, oxygen, and the stable carbon isotopic signature (δ13C) of dissolved inorganic carbon in the ocean, with modern observations. We find that for the present-day, the temperature-dependent version shows as-good-as or better fit to data than the existing tuned non-temperature dependent version of the cGENIE.muffin. The main impact of adding temperature-dependent remineralisation is in driving higher rates of remineralisation in warmer waters and hence a more rapid return of nutrients to the surface there – stimulating organic matter production. As a result, more organic matter is exported below 80 m in mid and low latitude warmer waters as compared to the standard model. Conversely, at higher latitudes, colder water temperature reduces the rate of nutrient supply to the surface as a result of slower in-situ rates of remineralisation. We also assess the implications of including a more complete set of temperature-dependent parameterisations by analysing a series of historical transient experiments. We find that between the pre-industrial and the present day, in response to a simulated air temperature increase of 0.9 °C and ocean warming of 0.12 °C (0.6 °C in surface waters and 0.02 °C in deep waters), a reduction in POC export at 80 m of just 0.3 % occurs. In contrast, with no assumed temperature-dependent biological processes, global POC export at 80 m falls by 2.9 % between the pre-industrial and present day as a consequence of ocean stratification and reduced nutrient supply to the surface. This suggests that increased nutrient recycling in warmer conditions offsets some of the stratification-induced surface nutrient limitation in a warmer world, and that less carbon (and nutrients) then reaches the inner and deep ocean. This extension to the cGENIE.muffin Earth system model provides it with additional capabilities in addressing marine carbon cycling in warmer past and future worlds

What the geological past can tell us about the future of the ocean’s twilight zone

Paleontological reconstructions of plankton community structure during warm periods of the Cenozoic (last 66 million years) reveal that deep-dwelling ‘twilight zone’ (200–1000 m) plankton were less abundant and diverse, and lived much closer to the surface, than in colder, more recent climates. We suggest that this is a consequence of temperature’s role in controlling the rate that sinking organic matter is broken down and metabolized by bacteria, a process that occurs faster at warmer temperatures. In a warmer ocean, a smaller fraction of organic matter reaches the ocean interior, affecting food supply and dissolved oxygen availability at depth. Using an Earth system model that has been evaluated against paleo observations, we illustrate how anthropogenic warming may impact future carbon cycling and twilight zone ecology. Our findings suggest that significant changes are already underway, and without strong emissions mitigation, widespread ecological disruption in the twilight zone is likely by 2100, with effects spanning millennia thereafter

Na–Ni–H phase formation at high pressures and high temperatures: hydrido complexes [NiH5]3– versus the perovskite NaNiH3

The Na-Ni-H system was investigated by in situ synchrotron diffraction studies of reaction mixtures NaH-Ni-H-2 at around 5, 10, and 12 GPa. The existence of ternary hydrogen-rich hydrides with compositions Na3NiH5 and NaNiH3, where Ni attains the oxidation state II, is demonstrated. Upon heating at similar to 5 GPa, face-centered cubic (fcc) Na3NiH5 forms above 430 degrees C. Upon cooling, it undergoes a rapid and reversible phase transition at 330 degrees C to an orthorhombic (Cmcm) form. Upon pressure release, Na3NiH5 further transforms into its recoverable Pnma form whose structure was elucidated from synchrotron powder diffraction data, aided by first-principles density functional theory (DFT) calculations. Na3NiH5 features previously unknown square pyramidal 18- electron complexes NiH53-. In the high temperature fcc form, metal atoms are arranged as in the Heusler structure, and ab initio molecular dynamics simulations suggest that the complexes are dynamically disordered. The Heusler-type metal partial structure is essentially maintained in the low temperature Cmcm form, in which NiH53- complexes are ordered. It is considerably rearranged in the low pressure Pnma form. Experiments at 10 GPa showed an initial formation of fcc Na3NiH5 followed by the addition of the perovskite hydride NaNiH3, in which Ni(II) attains an octahedral environment by H atoms. NaNiH3 is recoverable at ambient pressures and represents the sole product of 12 GPa experiments. DFT calculations show that the decomposition of Na3NiH5 = NaNiH3 + 2 NaH is enthalpically favored at all pressures, suggesting that Na3NiH5 is metastable and its formation is kinetically favored. Ni-H bonding in metallic NaNiH3 is considered covalent, as in electron precise Na3NiH5, but delocalized in the polyanion [NiH3](-).Funding Agencies|Swedish Research Council (VR)Swedish Research Council [2019-05551]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; Carl Tryggers Stiftelse (CTS) [16:198, 17:206]</p

Unconventional Route to High-Pressure and -Temperature Synthesis of GeSn Solid Solutions

Ge and Sn are unreactive at ambient conditions. Their significant promise for optoelectronic applications is thus largely confined to thin film investigations. We sought to remove barriers to reactivity here by accessing a unique pressure, 10 GPa, where the two elements can adopt the same crystal structure (tetragonal, $I4_1$/$amd$) and exhibit compatible atomic radii. The route to GeSn solid solution, however, even under these directed conditions, is different. Reaction upon heating at 10 GPa occurs between unlike crystal structures (Ge, $Fd3m$ and Sn, $I$4/$mmm$), which also have highly incompatible atomic radii. They should not react, but they do. A reconstructive transformation of $I$4/$mmm$ into the $I$4$_1$/$amd$ solid solution then follows. The new tetragonal GeSn solid solution ($I$4$_1$/$amda$ = 5.280(1) Å, c = 2.915(1) Å, Z = 4 at 9.9 GPa and 298 K) also constitutes the structural and electronic bridge between 4-fold and newly prepared 8-fold coordinated alloy cubic symmetries. Furthermore, using this high-pressure route, bulk cubic diamond-structured GeSn alloys can now be obtained at ambient pressure. The findings here remove confining conventional criteria on routes to synthesis. This opens innovative avenues to advanced materials development

What the geological past can tell us about the future of the ocean's twilight zone.

Paleontological reconstructions of plankton community structure during warm periods of the Cenozoic (last 66 million years) reveal that deep-dwelling 'twilight zone' (200-1000 m) plankton were less abundant and diverse, and lived much closer to the surface, than in colder, more recent climates. We suggest that this is a consequence of temperature's role in controlling the rate that sinking organic matter is broken down and metabolized by bacteria, a process that occurs faster at warmer temperatures. In a warmer ocean, a smaller fraction of organic matter reaches the ocean interior, affecting food supply and dissolved oxygen availability at depth. Using an Earth system model that has been evaluated against paleo observations, we illustrate how anthropogenic warming may impact future carbon cycling and twilight zone ecology. Our findings suggest that significant changes are already underway, and without strong emissions mitigation, widespread ecological disruption in the twilight zone is likely by 2100, with effects spanning millennia thereafter

IGRT/ART phantom with programmable independent rib cage and tumor motion

Abstract PURPOSE: This paper describes the design and experimental evaluation of the Methods and Advanced Equipment for Simulation and Treatment in Radiation Oncology (MAESTRO) thorax phantom, a new anthropomorphic moving ribcage combined with a 3D tumor positioning system to move target inserts within static lungs. METHODS: The new rib cage design is described and its motion is evaluated using Vicon Nexus, a commercial 3D motion tracking system. CT studies at inhale and exhale position are used to study the effect of rib motion and tissue equivalence. RESULTS: The 3D target positioning system and the rib cage have millimetre accuracy. Each axis of motion can reproduce given trajectories from files or individually programmed sinusoidal motion in terms of amplitude, period, and phase shift. The maximum rib motion ranges from 7 to 20 mm SI and from 0.3 to 3.7 mm AP with LR motion less than 1 mm. The repeatability between cycles is within 0.16 mm root mean square error. The agreement between CT electron and mass density for skin, ribcage, spine hard and inner bone as well as cartilage is within 3%. CONCLUSIONS: The MAESTRO phantom is a useful research tool that produces programmable 3D rib motions which can be synchronized with 3D internal target motion. The easily accessible static lungs enable the use of a wide range of inserts or can be filled with lung tissue equivalent and deformed using the target motion system.status: publishe

BronchUK: protocol for an observational cohort study and biobank in bronchiectasis

Bronchiectasis has been a largely overlooked disease area in respiratory medicine. This is reflected by a shortage of large-scale studies and lack of approved therapies, in turn leading to a variation of treatment across centres. BronchUK (Bronchiectasis Observational Cohort and Biobank UK) is a multicentre, prospective, observational cohort study working collaboratively with the European Multicentre Bronchiectasis Audit and Research Collaboration project. The inclusion criteria for patients entering the study are a clinical history consistent with bronchiectasis and computed tomography demonstrating bronchiectasis. Main exclusion criteria are 1) patients unable to provide informed consent, 2) bronchiectasis due to known cystic fibrosis or where bronchiectasis is not the main or co-dominant respiratory disease, 3) age <18 years, and 4) prior lung transplantation for bronchiectasis. The study is aligned to standard UK National Health Service (NHS) practice with an aim to recruit a minimum of 1500 patients from across at least nine secondary care centres. Patient data collected at baseline includes demographics, aetiology testing, comorbidities, lung function, radiology, treatments, microbiology and quality of life. Patients are followed up annually for a maximum of 5 years and, where able, blood and/or sputa samples are collected and stored in a central biobank. BronchUK aims to collect robust longitudinal data that can be used for analysis into current NHS practice and patient outcomes, and to become an integral resource to better inform future interventional studies in bronchiectasis

The impact on staff of working with personality disordered offenders: A systematic review

© 2015 Freestone et al. Background: Personality disordered offenders (PDOs) are generally considered difficult to manage and to have a negative impact on staff working with them. Aims: This study aimed to provide an overview of studies examining the impact on staff of working with PDOs, identify impact areas associated with working with PDOs, identify gaps in existing research,and direct future research efforts. Methods: The authors conducted a systematic review of the English-language literature from 1964-2014 across 20 databases in the medical and social sciences. Results: 27 papers were included in the review. Studies identified negative impacts upon staff including: negative attitudes, burnout, stress, negative counter-transferential experiences; two studies found positive impacts of job excitement and satisfaction, and the evidence related to perceived risk of violence from PDOs was equivocal. Studies demonstrated considerable heterogeneity and meta-analysis was not possible. The overall level of identified evidence was low: 23 studies (85%) were descriptive only, and only one adequately powered cohort study was found. Conclusions: The review identified a significant amount of descriptive literature, but only one cohort study and no trials or previous systematic reviews of literatures. Clinicians and managers working with PDOs should be aware of the potential impacts identified, but there is an urgent need for further research focusing on the robust evaluation of interventions to minimise harm to staff working with offenders who suffer from personality disorder Copyright