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211.
David Molnar Christian Niedermeier Alejandro Mora Peter Binkele Siegfried Schmauder 《Continuum Mechanics and Thermodynamics》2012,24(4-6):607-617
Kinetic Monte-Carlo (KMC) methods are used as an approach to simulate precipitation in Cu-alloyed bcc Fe. In order to characterize the process, transformed fractions, that is, the precipitated atoms, are related to Johnson-Mehl-Avrami-Kolmogorov theory. However, simulated data often deviate from corresponding fit curves and so does the resulting growth exponent when compared to theoretical expectations. Furthermore, some data may suggest the development of a metastable phase. In our study, we show that the characteristics of the transformed fraction and, as a consequence, the derived growth exponents sensitively depend on the number of atoms that are considered to form a particle and hence contribute to the transformed fraction. With a temperature dependence of the critical cluster size and additionally accounting for severe impingement of the particles, we obtain growth exponents which lie close to the expected range between n = 1.5 and n = 2.5 for pre-existing nuclei or continuous nucleation, respectively. From these, we obtain activation energies for nucleation and growth of precipitates. In this way, atomistic KMC simulations yield thermodynamical quantities, which can be valuable input parameters for larger length scale simulation methods, for example, for Phase Field Method simulations. 相似文献
212.
Sebastian B. Beil Timo Müller Sydney B. Sillart Peter Franzmann Alexander Bomm Michael Holtkamp Prof. Dr. Uwe Karst Prof. Dr. Wolfgang Schade Prof. Dr. Siegfried R. Waldvogel 《Angewandte Chemie (International ed. in English)》2018,57(9):2450-2454
A new and powerful active anode system that can be operated in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) has been discovered. In HFIP the molybdenum anode forms a compact, conductive, and electroactive layer of higher‐valent molybdenum species. This system can replace powerful but stoichiometrically required MoV reagents for the dehydrogenative coupling of aryls. This electrolytic reaction is more sustainable and allows the conversion of a broad scope of activated arenes. 相似文献
213.
Anton Wiebe Tile Gieshoff Sabine Möhle Dr. Eduardo Rodrigo Michael Zirbes Prof. Dr. Siegfried R. Waldvogel 《Angewandte Chemie (International ed. in English)》2018,57(20):5594-5619
The direct synthetic organic use of electricity is currently experiencing a renaissance. More synthetically oriented laboratories working in this area are exploiting both novel and more traditional concepts, paving the way to broader applications of this niche technology. As only electrons serve as reagents, the generation of reagent waste is efficiently avoided. Moreover, stoichiometric reagents can be regenerated and allow a transformation to be conducted in an electrocatalytic fashion. However, the application of electroorganic transformations is more than minimizing the waste footprint, it rather gives rise to inherently safe processes, reduces the number of steps of many syntheses, allows for milder reaction conditions, provides alternative means to access desired structural entities, and creates intellectual property (IP) space. When the electricity originates from renewable resources, this surplus might be directly employed as a terminal oxidizing or reducing agent, providing an ultra‐sustainable and therefore highly attractive technique. This Review surveys recent developments in electrochemical synthesis that will influence the future of this area. 相似文献
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215.
We prove the existence of multiple constant-sign and sign-changing solutions for a nonlinear elliptic eigenvalue problem under Dirichlet boundary condition involving the p-Laplacian. More precisely, we establish the existence of a positive solution, of a negative solution, and of a nontrivial sign-changing solution when the eigenvalue parameter λ is greater than the second eigenvalue λ2 of the negative p-Laplacian, extending results by Ambrosetti–Lupo, Ambrosetti–Mancini, and Struwe. Our approach relies on a combined use of variational and topological tools (such as, e.g., critical points, Mountain-Pass theorem, second deformation lemma, variational characterization of the first and second eigenvalue of the p-Laplacian) and comparison arguments for nonlinear differential inequalities. In particular, the existence of extremal nontrivial constant-sign solutions plays an important role in the proof of sign-changing solutions. 相似文献
216.
E.?V.?AltynbaevEmail author A.?S.?Sukhanov S.-A.?Siegfried V.?A.?Dyadkin E.?V.?Moskvin D.?Menzel A.?Heinemann A.?Schreyer L.?N.?Fomicheva A.?V.?Tsvyashenko S.?V.?Grigoriev 《Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques》2016,10(4):777-782
The helicoidal magnetic structure of a MnGe compound doped with 25% Fe is studied by means of small-angle neutron scattering in a wide temperature range of 10–300 K. Analysis of the scattering-function profile demonstrates that magnetic structures inherent to both pure MnGe and its doped compounds are unstable. The doping of manganese monogermanide is revealed to lead to higher destabilization of the magnetic system. In passing from MnGe to Mn0.75Fe0.25Ge, the magnetic-ordering temperature T N decreases from 130 to 95 K, respectively. It is demonstrated that, at temperatures close to 0 K, the intensity of the contribution to scattering from stable spin helices decreases and the intensity of scattering by spin helix fluctuations increases with increasing impurity-metal concentration. An increased intensity of anomalous scattering caused by spin excitations existing in the system is observed. Helicoidal fluctuations and spin excitations corresponding to low temperatures indicate the quantum nature of the instability in the doped compound. However, MnGe doping with Fe atoms has no influence on the compound’s magnetic properties at temperatures of higher than T N. The temperature range of short-range ferromagnetic correlations is independent of concentrations and is restricted by temperatures T ranging from 175 to 300 K. 相似文献
217.
Bomkamp M Siering C Landrock K Stephan H Fröhlich R Waldvogel SR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(13):3724-3732
Association constants for the interaction of almost insoluble substrates with triphenylene ketal-based receptors in toluene have been determined by means of an extraction method employing the corresponding radio-labelled substrates. Flexible and more polar receptors tend to aggregate and exhibit inferior extraction qualities. Binding constants in toluene were found to be in the range 10(5)-10(7) m(-1), which is significantly higher than in dichloromethane. X-ray analyses indicate the direct participation of a water molecule in the binding process, which may account for the surprisingly small effect of moisture in the solvent on the stability of the complexes. 相似文献
218.
Jos Gines Hernndez Cifre Siegfried Hess Martin Krger 《Macromolecular theory and simulations》2004,13(9):748-753
Summary: We present and assess the use of non‐equilibrium molecular dynamics (NEMD) simulation method for the direct study of the linear viscoelastic behavior of polymer melts. The polymer melt is modeled by a collection of repulsive, anharmonic multibead chains subjected to small amplitude oscillatory shear flow. We present results for chain lengths below the critical entanglement length and obtain good agreement with theoretical results for the viscoelastic behavior of melts of low molecular weight. The range of oscillation frequencies attainable in the simulation is of a few decades. Thus we use, as in experiments, a time‐temperature superposition rule to extend the frequency domain. As a side result, we confirm the so‐called Cox‐Merz rule.
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220.