63 research outputs found

    Dynamics of the first-order metamagnetic transition in magnetocaloric La(Fe,Si)(13): Reducing hysteresis

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    The influence of dynamics and sample shape on the magnetic hysteresis in first‐order magnetocaloric metamagnetic LaFe13–xSix with x = 1.4 is studied. In solid‐state magnetic cooling, reducing magnetic and thermal hysteresis is critical for refrigeration cycle efficiency. From magnetization measurements, it is found that the fast field‐rate dependence of the hysteresis can be attributed to extrinsic heating directly related to the thickness of the sample and the thermal contact with the bath. If the field is paused partway through the transition, the subsequent relaxation is strongly dependent on shape due to both demagnetizing fields and thermal equilibration; magnetic coupling between adjacent sample fragments can also be significant. Judicious shaping of the sample can both increase the onset field of the ferromagnetic–paramagnetic (FM–PM) transition but have little effect on the PM–FM onset, suggesting a route to engineer the hysteresis width by appropriate design. In the field‐paused state, the relaxation from one phase to the other slows with increasing temperature, implying that the process is neither thermally activated or athermal; comparison with the temperature dependence of the latent heat strongly suggests that the dynamics reflect the intrinsic free energy difference between the two phases

    Low-temperature specific heat in hydrogenated and Mn-doped La(Fe, Si)(13)

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    It is now well established that the paramagnetic-to-ferromagnetic transition in the magnetocaloric La(FeSi)13 is a cooperative effect involving spin, charge, and lattice degrees of freedom. However, the influence of this correlated behavior on the ferromagnetic state is as yet little studied. Here we measure the specific heat at low temperatures in a systematic set of LaFexMnySiz samples, with and without hydrogen, to extract the Sommerfeld coefficient, the Debye temperature, and the spin-wave stiffness. Substantial and systematic changes in magnitude of the Sommerfeld coefficient are observed with Mn substitution and introduction of hydrogen, showing that over and above the changes to the density of states at the Fermi energy there are significant enhanced d-band electronic interactions at play. The Sommerfeld coefficient is found to be 90–210mJmol−1K−2, unusually high compared to that expected from band-structure calculations. The Debye temperature determined from the specific heat measurement is insensitive to Mn and Si doping but increases when hydrogen is introduced into the system. The Sommerfeld coefficient is reduced in magnetic field for all compositions that have a measurable spin-wave contribution. These results move our understanding of the cooperative effects forward in this important and interesting class of materials significantly and provide a basis for future theoretical development

    Determining the first-order character of La(Fe,Mn,Si)(13)

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    Definitive determination of first-order character of the magnetocaloric magnetic transition remains elusive. Here we use a microcalorimetry technique in two modes of operation to determine the contributions to entropy change from latent heat and heat capacity separately in an engineered set of La ( Fe , Mn , Si ) 13 samples. We compare the properties extracted by this method with those determined using magnetometry and propose a model-independent parameter that would allow the degree of first-order character to be defined across different families of materials. The microcalorimetry method is sufficiently sensitive to allow observation at temperatures just above the main magnetic transition of an additional peak feature in the low field heat capacity associated with the presence of Mn in these samples. The feature is of magnetic origin but is insensitive to magnetic field, explicable in terms of inhomogeneous occupancy of Mn within the lattice resulting in antiferromagnetic ordered Mn clusters

    The association of serum calprotectin (S100A8/S100A9) levels with disease relapses in PR3-ANCA-associated vasculitis

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    OBJECTIVES: S100A8/A9 (calprotectin) has shown promise as a biomarker for predicting relapse in AAV. This study investigated serum S100A8/A9 levels as a biomarker predicting future relapse in a large cohort of patients with severe ANCA-associated vasculitis (AAV). METHODS: Serum levels of S100A8/A9 were measured at baseline, months 2, and 6 following treatment initiation in 144 patients in the RAVE trial (cyclophosphamide/azathioprine vs. rituximab for induction of remission) who attained complete remission. RESULTS: Patients were divided into 4 groups: PR3-ANCA with (n=37), and without (n=56) relapse, and MPO-ANCA with (n=6) and without (n=45) relapse. Serum S100A8/A9 levels decreased in all groups during the first 6 months of treatment. The percentage reduction from baseline to month 2 was significantly different between relapsers and non-relapsers in the PR3-AAV group (p=0.046). A significantly higher risk of relapse was associated with an increase in S100A8/A9 between baseline and month 2 (p=0.006) and baseline and month 6 (p=0.0099) for all patients. Subgroup analysis demonstrated it was patients treated with rituximab and who increased levels of S100A8/A9 who were at greatest risk of future relapse (p=0.028). CONCLUSION: An increase in serum S100A8/A9 by month 2 or 6 compared to baseline identifies a subgroup of PR3-ANCA patients treated with rituximab at higher risk of relapse by 18 months. As rituximab is increasingly used for remission induction in relapsing PR3-ANCA patients, S100A8/A9 may assist in identifying those patients requiring more intensive or prolonged treatment

    Comparative (Meta)genomic Analysis and Ecological Profiling of Human Gut-Specific Bacteriophage φB124-14

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    Bacteriophage associated with the human gut microbiome are likely to have an important impact on community structure and function, and provide a wealth of biotechnological opportunities. Despite this, knowledge of the ecology and composition of bacteriophage in the gut bacterial community remains poor, with few well characterized gut-associated phage genomes currently available. Here we describe the identification and in-depth (meta)genomic, proteomic, and ecological analysis of a human gut-specific bacteriophage (designated φB124-14). In doing so we illuminate a fraction of the biological dark matter extant in this ecosystem and its surrounding eco-genomic landscape, identifying a novel and uncharted bacteriophage gene-space in this community. φB124-14 infects only a subset of closely related gut-associated Bacteroides fragilis strains, and the circular genome encodes functions previously found to be rare in viral genomes and human gut viral metagenome sequences, including those which potentially confer advantages upon phage and/or host bacteria. Comparative genomic analyses revealed φB124-14 is most closely related to φB40-8, the only other publically available Bacteroides sp. phage genome, whilst comparative metagenomic analysis of both phage failed to identify any homologous sequences in 136 non-human gut metagenomic datasets searched, supporting the human gut-specific nature of this phage. Moreover, a potential geographic variation in the carriage of these and related phage was revealed by analysis of their distribution and prevalence within 151 human gut microbiomes and viromes from Europe, America and Japan. Finally, ecological profiling of φB124-14 and φB40-8, using both gene-centric alignment-driven phylogenetic analyses, as well as alignment-free gene-independent approaches was undertaken. This not only verified the human gut-specific nature of both phage, but also indicated that these phage populate a distinct and unexplored ecological landscape within the human gut microbiome

    Nucleation and dynamics of the metamagnetic transition in magnetocaloric La(Fe,Mn,Si)(13)

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    Refrigeration cycle rates of the order of 15 Hz are desirable for efficient solid state based magnetocaloric cooling, placing an upper bound on the combined magnetic transition and the heat transfer times of the order of tens of msecs. We use microcalorimetry and magnetometry to probe the transition dynamics as a function of magnetic field sweep-rate, sample size, thermal environment, temperature and hydrostatic pressure in LaFe11.74Mn0.06Si1.20. Although second order caloric materials follow the magnetisation or demagnetisation driving field without lag, here we show that the field driven evolution of the first-order phase transition in La(Fe,Si)13-based compounds show temporal dynamics on timescales that are significantly longer than tens of msecs, associated with the thermal linkage within the sample and the linkage to the external bath. We observe that features associated with the first nucleation of the transition are field sweep rate independent, and from measurements of the latent heat we infer that the barriers to magnetisation and demagnetisation are of different magnitude. Increasing the temperature or applying hydrostatic pressure reduces the dynamic effects, suggestive of diminishing first-order character of the transition under these conditions
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