158 research outputs found

    Exchange Anisotropy in Epitaxial and Polycrystalline NiO/NiFe Bilayers

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    (001) oriented NiO/NiFe bilayers were grown on single crystal MgO (001) substrates by ion beam sputtering in order to determine the effect that the crystalline orientation of the NiO antiferromagnetic layer has on the magnetization curve of the NiFe ferromagnetic layer. Simple models predict no exchange anisotropy for the (001)-oriented surface, which in its bulk termination is magnetically compensated. Nonetheless exchange anisotropy is present in the epitaxial films, although it is approximately half as large as in polycrystalline films that were grown simultaneously. Experiments show that differences in exchange field and coercivity between polycrystalline and epitaxial NiFe/NiO bilayers couples arise due to variations in induced surface anisotropy and not from differences in the degree of compensation of the terminating NiO plane. Implications of these observations for models of induced exchange anisotropy in NiO/NiFe bilayer couples will be discussed.Comment: 23 pages in RevTex format, submitted to Phys Rev B

    Detection of occult carcinomatous diffusion in lymph nodes from head and neck squamous cell carcinoma using real-time RT–PCR detection of cytokeratin 19 mRNA

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    The aim of the present study was to evaluate the occult lymph node carcinomatous diffusion in head and neck squamous cell carcinoma (HNSCC). A total of 1328 lymph nodes from 31 patients treated between 2004 and 2005 were prospectively evaluated by routine haematoxylin–eosin–safran (HES) staining, immunohistochemistry (IHC) and real-time Taqman reverse–transcriptase polymerase chain reaction (real-time RT–PCR) assay. Amplification of cytokeratin 19 (CK19) mRNA transcripts using real-time RT–PCR was used to quantify cervical micrometastatic burden. The cervical lymph node metastatic rates determined by routine HES staining and real-time RT–PCR assay were 16.3 and 36.0%, respectively (P<0.0001). A potential change in the nodal status was observed in 13 (42.0%) of the 31 patients and an atypical pattern of lymphatic spread was identified in four patients (12.9%). Moreover, CK19 mRNA expression values in histologically positive lymph nodes were significantly higher than those observed in histologically negative lymph nodes (P<0.0001). These results indicate that real-time RT–PCR assay for the detection of CK19 mRNA is a sensitive and reliable method for the detection of carcinomatous cells in lymph nodes. This type of method could be used to reassess lymph node status according to occult lymphatic spread in patients with HNSCC

    Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

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    [EN] Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 degrees C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H-2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.This work was supported by the Research Council of Norway (grant 256264) and the Spanish Government (SEV-2016-0683 grant).MalerΓΈd-Fjeld, H.; Clark, D.; Yuste Tirados, I.; ZanΓ³n GonzΓ‘lez, R.; CatalΓ‘n-MartΓ­nez, D.; Beeaff, D.; HernΓ‘ndez Morejudo, S.... (2017). Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss. Nature Energy. 2(12):923-931. https://doi.org/10.1038/s41560-017-0029-4S923931212Morejudo, S. H. et al. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor. Science 353, 563–566 (2016).Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).Logan, B. E. & Elimelech, M. Membrane-based processes for sustainable power generation using water. Nature 488, 313–319 (2012).Rostrup-Nielsen, J. R. Catalysis and large-scale conversion of natural gas. Catal. Today 21, 257–267 (1994).Voss, C. Applications of pressure swing adsorption technology. Adsorption 11, 527–529 (2005).Gallucci, F., Fernandez, E., Corengia, P. & van Sint Annaland, M. Recent advances on membranes and membrane reactors for hydrogen production. Chem. Eng. Sci. 92, 40–66 (2013).Boeltken, T., Wunsch, A., Gietzelt, T., Pfeifer, P. & Dittmeyer, R. Ultra-compact microstructured methane steam reformer with integrated Palladium membrane for on-site production of pure hydrogen: Experimental demonstration. Int. J. Hydrogen Energy 39, 18058–18068 (2014).Al-Mufachi, N. A., Rees, N. V. & Steinberger-Wilkens, R. Hydrogen selective membranes: A review of palladium-based dense metal membranes. Renew. Sustainable Energy Rev. 47, 540–551 (2015).Sengodan, S. et al. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells. Nat. Mater. 14, 205–209 (2015).Myung, J.-h, Neagu, D., Miller, D. N. & Irvine, J. T. S. Switching on electrocatalytic activity in solid oxide cells. Nature 537, 528–531 (2016).Iwahara, H., Uchida, H., Ono, K. & Ogaki, K. Proton conduction in sintered oxides based on BaCeO3. J. Electrochem. Soc. 135, 529–533 (1988).Hamakawa, S., Hibino, T. & Iwahara, H. Electrochemical methane coupling using proton conductors. J. Electrochem. Soc. 140, 459–462 (1993).Bonanos, N., Knight, K. S. & Ellis, B. Perovskite solid electrolytes: structure, transport properties and fuel cell applications. Solid State Ion. 79, 161–170 (1995).Norby, T. Solid-state protonic conductors: principles, properties, progress and prospects. Solid State Ion. 125, 1–11 (1999).Kreuer, K. D. On the development of proton conducting materials for technological applications. Solid State Ion. 97, 1–15 (1997).Kreuer, K. D. Aspects of the formation and mobility of protonic charge carriers and the stability of perovskite-type oxides. Solid State Ion. 125, 285–302 (1999).Kreuer, K. D. Proton-conducting oxides. Annu. Rev. Mater. Res. 33, 333–359 (2003).Tao, S. W. & Irvine, J. T. S. A stable, easily sintered proton-conducting oxide electrolyte for moderate-temperature fuel cells and electrolyzers. Adv. Mater. 18, 11581-1584 (2006).Wang, H., Peng, R., Wu, X., Hu, J. & Xia, C. Sintering behavior and conductivity study of yttrium-doped BaCeO3–BaZrO3 solid solutions using ZnO additives. J. Am. Ceram. Soc. 92, 2623–2629 (2009).Coors, W. G. in Advances in Ceramicsβ€”Synthesis and Characterization, Processing and Specific Applications (Ed. Sikalidis, C.) Ch. 22, 501–520 (InTech, UK, 2011) (2011).Manabe, R. et al. Surface protonics promotes catalysis. Sci. Rep. 6, 38007, (2016).Rohland, B., Eberle, K., StrΓΆbel, R., Scholta, J. & Garche, J. Electrochemical hydrogen compressor. Electrochimica Acta 43, 3841–3846 (1998).Kochetova, N., Animitsa, I., Medvedev, D., Demin, A. & Tsiakaras, P. Recent activity in the development of proton-conducting oxides for high-temperature applications. RSC Adv. 6, 73222–73268 (2016).Yamazaki, Y. et al. Proton trapping in yttrium-doped barium zirconate. Nat. Mater. 12, 647–651 (2013).KjΓΈlseth, C. et al. Space-charge theory applied to the grain boundary impedance of proton conducting BaZr0.9Y0.1O3-Ξ΄ . Solid State Ion. 181, 268–275 (2010).Coors, W. G A stoichiometric titration method for measuring galvanic hydrogen flux in ceramic hydrogen separation membranes. J. Membr. Sci. 458, 245–253 (2014).Zeppieri, M., Villa, P. L., Verdone, N., Scarsella, M. & De Filippis, P. Kinetic of methane steam reforming reaction over nickel- and rhodium-based catalysts. Appl. Catal. A 387, 147–154 (2010).Wang, B., Zhu, J. & Lin, Z. A theoretical framework for multiphysics modeling of methane fueled solid oxide fuel cell and analysis of low steam methane reforming kinetics. Appl. Energy 176, 1–11 (2016).Overview of Electricity Production and Use in Europe (European Environment Agency, 2016).Edwards, R., Larive, J.-F., Rickeard, D. & Weindorf, W. Well-To-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Well-to-Tank Report Version 4.a, JEC Well-to-Wheels Analysis (Joint Research Centre, 2014).Cho, V. H., Hamilton, B. A. & Kuehn, N. J. Assessment of Hydrogen Production with CO 2 Capture Volume 1: Baseline State-of-the-Art Plants (National Energy Technology Laboratory, 2010).SchjΓΈlberg, I. etΒ al. Small-Scale Reformers for On-Site Hydrogen Supply (International Energy Agency-Hydrogen Implementing Agreement, 2012).de Visser, E. et al. Dynamis CO2 quality recommendations. Int. J. Greenhouse Gas Control 2, 478–484 (2008).Bertucciolo, L. etΒ al. Development of Water Electrolysis in the European Union (Fuel Cells and Hydrogen Joint Undertaking, 2014).Edwards, R. etΒ al. Well-To-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Well-to-Wheels Report Version 4.a, JEC Well-to-Wheels Analysis (Joint Research Centre 2014).Huss, A., Maas, H. & Hass, H. Well-to-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Tank-to-Wheels Report Version 4.0, JEC Technical Reports (Joint Research Centre, 2013)

    First application of mass measurement with the Rare-RI Ring reveals the solar r-process abundance trend at A=122 and A=123

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    The Rare-RI Ring (R3) is a recently commissioned cyclotron-like storage ring mass spectrometer dedicated to mass measurements of exotic nuclei far from stability at Radioactive Isotope Beam Factory (RIBF) in RIKEN. The first application of mass measurement using the R3 mass spectrometer at RIBF is reported. Rare isotopes produced at RIBF, 127^{127}Sn, 126^{126}In, 125^{125}Cd, 124^{124}Ag, 123^{123}Pd, were injected in R3. Masses of 126^{126}In, 125^{125}Cd, and 123^{123}Pd were measured whereby the mass uncertainty of 123^{123}Pd was improved. This is the first reported measurement with a new storage ring mass spectrometery technique realized at a heavy-ion cyclotron and employing individual injection of the pre-identified rare nuclei. The latter is essential for the future mass measurements of the rarest isotopes produced at RIBF. The impact of the new 123^{123}Pd result on the solar rr-process abundances in a neutron star merger event is investigated by performing reaction network calculations of 20 trajectories with varying electron fraction YeY_e. It is found that the neutron capture cross section on 123^{123}Pd increases by a factor of 2.2 and Ξ²\beta-delayed neutron emission probability, P1nP_\mathrm{1n}, of 123^{123}Rh increases by 14\%. The neutron capture cross section on 122^{122}Pd decreases by a factor of 2.6 leading to pileup of material at A=122A=122, thus reproducing the trend of the solar rr-process abundances. The trend of the two-neutron separation energies (S2n_\mathrm{2n}) was investigated for the Pd isotopic chain. The new mass measurement with improved uncertainty excludes large changes of the S2n_\mathrm{2n} value at N=77N=77. Such large increase of the S2n_\mathrm{2n} values before N=82N=82 was proposed as an alternative to the quenching of the N=82N=82 shell gap to reproduce rr-process abundances in the mass region of A=112βˆ’124A=112-124

    Lanthanum tungstate membranes for H-2 extraction and CO2 utilization: Fabrication strategies based on sequential tape casting and plasma-spray physical vapor deposition

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    [EN] In the context of energy conversion efficiency and decreasing greenhouse gas emissions from power generation and energy-intensive industries, membrane technologies for H-2 extraction and CO2 capture and utilization become pronouncedly important. Mixed protonic-electronic conducting ceramic membranes are hence attractive for the pre-combustion integrated gasification combined cycle, specifically in the water gas shift and H-2 separation process, and also for designing catalytic membrane reactors. This work presents the fabrication, microstructure and functional properties of Lanthanum tungstates (La28-xW4+xO54+delta, LaWO) asymmetric membranes supported on porous ceramic and porous metallic substrates fabricated by means of the sequential tape casting route and plasma spray-physical vapor deposition (PS-PVD). Pure LaWO and W site substituted LaWO were employed as membrane materials due to the promising combination of properties: appreciable mixed protonic-electronic conductivity at intermediate temperatures and reducing atmospheres, good sinterability and noticeable chemical stability under harsh operating conditions. As substrate materials porous LaWO (non-substituted), MgO and Crofer22APU stainless steel were used to support various LaWO membrane layers. The effect of fabrication parameters and material combinations on the assemblies' microstructure, LaWO phase formation and gas tightness of the functional layers was explored along with the related fabrication challenges for shaping LaWO layers with sufficient quality for further practical application. The two different fabrication strategies used in the present work allow for preparing all-ceramic and ceramic-metallic assemblies with LaWO membrane layers with thicknesses between 25 and 60 mu m and H-2 flux of ca. 0.4 ml/min cm(2) measured at 825 degrees C in 50 vol% H-2 in He dry feed and humid Ar sweep configuration. Such a performance is an exceptional achievement for the LaWO based H-2 separation membranes and it is well comparable with the H-2 flux reported for other newly developed dual phase cer-cer and cer-met membranes.ProtOMem Project under the BMBF grant 03SF0537 is gratefully acknowledged. Furthermore, the authors thank Ralf Laufs for his assistance in operating the PS-PVD facility. Dr. A. Schwedt from the Central Facility for Electron Microscopy (Gemeinschaftslabor fur Elektronenmikroskopie GFE), RWTH Aachen University is acknowledged for performing the EBSD analysis on the PS-PVD samples.Ivanova, ME.; Deibert, W.; Marcano, D.; EscolΓ‘stico RozalΓ©n, S.; Mauer, G.; Meulenberg, WA.; Bram, M.... (2019). Lanthanum tungstate membranes for H-2 extraction and CO2 utilization: Fabrication strategies based on sequential tape casting and plasma-spray physical vapor deposition. Separation and Purification Technology. 219:100-112. https://doi.org/10.1016/j.seppur.2019.03.015S100112219A.A. Evers, The hydrogen society, More than just a vision? ISBN 978-3-937863-31-3, Hydrogeit Verlag, 16727 Oberkraemer, Germany, 2010.Deibert, W., Ivanova, M. E., Baumann, S., Guillon, O., & Meulenberg, W. A. (2017). Ion-conducting ceramic membrane reactors for high-temperature applications. Journal of Membrane Science, 543, 79-97. doi:10.1016/j.memsci.2017.08.016Arun C. 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Synthesis and hydrogen permeation properties of asymmetric proton-conducting ceramic membranes. Solid State Ionics, 176(35-36), 2653-2662. doi:10.1016/j.ssi.2005.07.005Kniep, J., & Lin, Y. S. (2010). Effect of Zirconium Doping on Hydrogen Permeation through Strontium Cerate Membranes. Industrial & Engineering Chemistry Research, 49(6), 2768-2774. doi:10.1021/ie9015182LIANG, J., MAO, L., LI, L., & YUAN, W. (2010). Protonic and Electronic Conductivities and Hydrogen Permeation of SrCe0.95-xZrxTm0.05O3-Ξ΄(0≀x≀0.40) Membrane. Chinese Journal of Chemical Engineering, 18(3), 506-510. doi:10.1016/s1004-9541(10)60250-9Xing, W., Inge Dahl, P., Valland Roaas, L., Fontaine, M.-L., Larring, Y., Henriksen, P. P., & Bredesen, R. (2015). Hydrogen permeability of SrCe0.7Zr0.25Ln0.05O3βˆ’ membranes (Ln=Tm and Yb). Journal of Membrane Science, 473, 327-332. doi:10.1016/j.memsci.2014.09.027Oh, T., Yoon, H., Li, J., & Wachsman, E. D. (2009). 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Serra, Hydrogen separation through tailored dual phase membranes with nominal composition BaCe0.8Eu0.2O3βˆ’Ξ΄:Ce0.8Y0.2O2βˆ’Ξ΄ at intermediate temperatures, Sci. Rep. 6 (2016) 34773–34787.S. Elangovan, B.G. Nair, T.A. Small, Ceramic mixed protonic-electronic conducting membranes for hydrogen separation (2007), US 7,258,820 B2, 1997.Rosensteel, W. A., Ricote, S., & Sullivan, N. P. (2016). Hydrogen permeation through dense BaCe 0.8 Y 0.2 O 3βˆ’Ξ΄ – Ce 0.8 Y 0.2 O 2βˆ’Ξ΄ composite-ceramic hydrogen separation membranes. International Journal of Hydrogen Energy, 41(4), 2598-2606. doi:10.1016/j.ijhydene.2015.11.053Rebollo, E., MortalΓ², C., EscolΓ‘stico, S., Boldrini, S., Barison, S., Serra, J. M., & Fabrizio, M. (2015). Exceptional hydrogen permeation of all-ceramic composite robust membranes based on BaCe0.65Zr0.20Y0.15O3βˆ’Ξ΄ and Y- or Gd-doped ceria. 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F., Schumacher, G., EscolΓ‘stico, S., … Banhart, J. (2016). Nanoscale order in the frustrated mixed conductor La5.6WO12βˆ’Ξ΄. Journal of Applied Crystallography, 49(3), 997-1008. doi:10.1107/s1600576716006415Van Holt, D., Forster, E., Ivanova, M. E., Meulenberg, W. A., MΓΌller, M., Baumann, S., & Vaßen, R. (2014). Ceramic materials for H2 transport membranes applicable for gas separation under coal-gasification-related conditions. Journal of the European Ceramic Society, 34(10), 2381-2389. doi:10.1016/j.jeurceramsoc.2014.03.001Forster, E., van Holt, D., Ivanova, M. E., Baumann, S., Meulenberg, W. A., & MΓΌller, M. (2016). Stability of ceramic materials for H2 transport membranes in gasification environment under the influence of gas contaminants. Journal of the European Ceramic Society, 36(14), 3457-3464. doi:10.1016/j.jeurceramsoc.2016.05.021Medvedev, D., Lyagaeva, J., Plaksin, S., Demin, A., & Tsiakaras, P. (2015). 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    The Discovery of LOX-1, its Ligands and Clinical Significance

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    LOX-1 is an endothelial receptor for oxidized low-density lipoprotein (oxLDL), a key molecule in the pathogenesis of atherosclerosis.The basal expression of LOX-1 is low but highly induced under the influence of proinflammatory and prooxidative stimuli in vascular endothelial cells, smooth muscle cells, macrophages, platelets and cardiomyocytes. Multiple lines of in vitro and in vivo studies have provided compelling evidence that LOX-1 promotes endothelial dysfunction and atherogenesis induced by oxLDL. The roles of LOX-1 in the development of atherosclerosis, however, are not simple as it had been considered. Evidence has been accumulating that LOX-1 recognizes not only oxLDL but other atherogenic lipoproteins, platelets, leukocytes and CRP. As results, LOX-1 not only mediates endothelial dysfunction but contributes to atherosclerotic plaque formation, thrombogenesis, leukocyte infiltration and myocardial infarction, which determine mortality and morbidity from atherosclerosis. Moreover, our recent epidemiological study has highlighted the involvement of LOX-1 in human cardiovascular diseases. Further understandings of LOX-1 and its ligands as well as its versatile functions will direct us to ways to find novel diagnostic and therapeutic approaches to cardiovascular disease
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