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graphene_01 | In addition, the redox Cu2+ species ensures direct O2 adsorption at the active site and leads to the desired four-electron ORR pathway. | [
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graphene_01 | Particularly, the present work highlights that, thanks to a fast and green microwave- assisted process, is possible to synthesize unconventional high-performance catalysts, aiming at application in a wide range it of challenging electrochemical splitting and CO2 reduction. | [
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graphene_01 | METHODS | [
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graphene_01 | Computational details | [
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graphene_01 | To partially heal the underestimation of the energy gap typical of PBE when applied to transition metals, such as Cu, we applied to the relaxed structures a Hubbard U correction to the Cu-3d orbital (UCu = 11.50 eV) obtained following the procedure reported in ref. | [
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graphene_01 | Electrochemical characterizations | [
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graphene_01 | All electrochemical characterizations were performed at room temperature with a CHI760D electrochemical workstation and an ALS RRDE−3A rotating ring disk electrode apparatus. | [
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graphene_01 | Rotating disk electrode tests were carried out in the potential range 1.18 V–0.18 V with a scan rate of 5 mV/s. | [
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graphene_01 | DATA AVAILABILITY | [
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graphene_01 | All data generated or analyzed during this study are included in this published article (and its Supplementary information file). | [
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oastm_01 | Grain boundary excess volume and defect annealing of copper after high-pressure torsion | [
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oastm_01 | The release of excess volume upon recrystallization of ultrafine-grained Cu deformed by high-pressure torsion (HPT) was studied by means of the direct technique of high-precision difference dilatometry in combination with differential scanning calorimetry (DSC) and scanning electron microscopy. | [
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oastm_01 | From the length change associated with the removal of grain boundaries in the wake of crystallite growth, a structural key quantity of grain boundaries, the grain boundary excess volume or expansion eGB=(0.46±0.11)×10-10 m was directly determined. | [
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oastm_01 | Activation energies for crystallite growth of 0.99±0.11 and 0.96±0.06eV are derived by Kissinger analysis from dilatometry and DSC data, respectively. | [
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oastm_01 | A comprehensive understanding of these enhanced properties and of the process of grain refinement during severe plastic deformation is currently a major research topic in materials science. | [
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oastm_01 | In particular, the roles of the various types of defects produced during deformation are widely studied. | [
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oastm_01 | It has already been shown that athermally produced excess vacancies are present in high concentrations that are otherwise found only close to the melting temperature [5,6]. | [
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oastm_01 | A complex defect annealing kinetics is suggested from volume and grain boundary diffusion studies in SPD-processed Cu and Ni [7,8]. | [
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oastm_01 | During annealing, abundant and highly mobile vacancies may, for example, agglomerate or form a percolating porosity network in combination with triple junctions of grain boundaries. | [
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oastm_01 | In addition, ultrafine-grained SPD materials give access to basic physical key parameters and processes such as thermally activated grain boundary relaxation prior to grain growth, as well as to the grain boundary excess volume, often also denoted as grain boundary expansion, of relaxed high-angle grain boundaries [9]. | [
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oastm_01 | For this purpose, the direct experimental method of difference dilatometry is applied in the present work in combination with differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). | [
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oastm_01 | The subjects of the present study are high-purity samples of the face-centered cubic (fcc) metals Cu and Ni. | [
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oastm_01 | A Cu disk with a purity of 99.995wt.% was deformed by high-pressure torsion (HPT) at room temperature, with six revolutions being applied at 2.2GPa (for details see Refs. | [
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oastm_01 | This corresponds to a von Mises equivalent strain of ε>23, ensuring a regime, where the deformation is in saturation, i.e. where further deformation will not lead to further grain refinement. | [
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oastm_01 | For the dilatometric measurements, a total of nine prism-shaped specimens with the dimension of 3×3×7mm3 were prepared. | [
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oastm_01 | The direction of the length change measurement is defined with regard to the HPT deformation axis (see Fig. 1, axial, tangential and radial directions). | [
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oastm_01 | Here, seven samples were prepared in the axial direction and one each in the tangential and radial directions. | [
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oastm_01 | Experiments were performed with a high-precision, vertical double-dilatometer (Linseis, L75VD500 LT), which allows the simultaneous measurement of two samples under an argon (5N) gas flow. | [
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oastm_01 | One of the two samples served as a reference and was made from the same Cu material, which was well annealed and coarse grained (grain size >100μm). | [
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oastm_01 | The experimental data, plotted as a dilatometric length change curve Δl/l0, represents the difference signal between the specimen and the reference (so-called difference dilatometry). | [
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oastm_01 | The length change is directly related to the defect volume via the relation 3×Δl/l0=ΔV/V0, assuming an isotropic distribution and annealing of defects [12]. | [
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oastm_01 | The temperature of the maximum defect release rates can be determined from the minima of the derivative d(Δl/l0)/dT of the length change curve with respect to temperature. | [
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oastm_01 | For the case of a constant linear heating rate, dT/dt, the temperature, T, is directly proportional to the time, t. | [
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oastm_01 | For the DSC measurements, 14 samples, taken from three different positions of the HPT disk, were prepared. | [
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oastm_01 | Six samples were cut from the disk at a radius of r=9mm at different heights. | [
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oastm_01 | The measurements were performed with a Perkin Elmer DSC7 differential calorimeter, which determines the heat release for the annealing processes at different linear heating rates. | [
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oastm_01 | A subsequent re-run served as the reference measurement and baseline for the analysis (for details see Ref. [13]). | [
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oastm_01 | Crystallite sizes were determined by a scanning electron microscope (LEO 1525 field emission scanning electron microscope, with a nominal resolution of 1.5nm at 20kV) equipped with a backscattering detector. | [
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oastm_01 | For correlating the dilatometric length changes with modifications of microstructure, microscopy samples were prepared from the same part of the HPT disk as the dilatometric samples and subsequently annealed under identical conditions in the dilatometer up to predefined temperatures at a heating rate of 5K/min, followed by rapid cooling to ambient temperature at a rate of about 30K/min. | [
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oastm_01 | The crystallite size was determined from the SEM images by analyzing the area of the grains using the software program ImageJ [14]. | [
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oastm_01 | A spherical grain shape was assumed for the analysis, and the arithmetic mean value of the diameters was calculated. | [
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} | oastm_01 | train5 | steel |
Subsets and Splits