Diffusion and Thermal Transport in Bulk and Nano-Materials

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Authors: Volker Döge, Árpád W. Imre
Abstract: Charge transport is one of the most important phenomena, which directly influences the performance of the energy storage and conversation devices. In this work, the authors provide an overview of various rechargeable energy storage battery chemistries and designs, and discuss the charge transport processes related to power capability of the lithium-ion technology. The load distribution by parallel connection of high power batteries or supercapacitor and high-energy cells is discussed and general conclusions are provided. Thus, the reduced peak power load on the high-energy cells are approved by simulation and experiment in passive parallel circuitry of high power and a high energy lithium-ion cells. The definition and advantages of the earlier deduced electrical loss time are explained. It is shown, that at a constant C-rate, defined as the ratio of the applied current and the rated cell capacity in Ah, the electrical loss time has a direct linear correlation to efficiency, and that the electrical loss time allows a direct power capability comparison of various battery cell chemistries and systems. The power capability, specific energy, and energy density of the industry relevant Li-ion battery cells based on electrical loss time approach are summarized and the following conclusions made. Today prismatic cells reach the maximum specific energy of small cylindrical cells, at the same time showing a little bit better power capability, than the investigated high energy cylindrical cells.
Authors: Leila Momenzadeh, Behdad Moghtaderi, Xian Feng Liu, Scott William Sloan, Irina V. Belova, Graeme E. Murch
Abstract: In this study, the phonon-based thermal conductivity of magnesite (MgCO3) and dolomite (CaMg(CO3)2) is calculated and compared with an earlier recent calculation on calcite (CaCO3). Equilibrium molecular dynamics simulation by way of the elegant Green-Kubo formalism is used for calculating the thermal conductivity. The thermal conductivity is investigated over a wide temperature range (from 200 K to 800 K) for all of the above mentioned materials. The most reliable potential parameters are used for characterising the interatomic interactions. In all of the models, two independent mechanisms are considered. The first is temperature independent, which is relevant to the acoustic short-range and optical phonons, and the other is temperature dependent, which is linked to the acoustic long-range phonons. In the study, the heat current autocorrelation function (HCACF) is calculated over the averages of the NPT, NVT and NVE ensembles in the x- and z- directions. In addition, it is shown that the optical, acoustic short- and long-range phonon modes are the main contributors to the decomposition model of the thermal conductivity. In a further investigation, the effects of the computational cell sizes on the thermal conductivity are investigated with five different simulation blocks containing 30, 240, 810, 1920 and 6480 atoms. Finally, this research provides a comparison of the thermal conductivity from this study and experimental studies: they are in good agreement.
Authors: Fabian Hergemöller, Nicolaas A. Stolwijk
Abstract: In this paper some recent progress in the area of Monte Carlo simulation of diffusion via the interstitialcy mechanism in a randomly ordered binary alloy is reviewed. Topics discussed include the calculation of tracer correlation factors fA and fB as a function of composition and jump frequency ratio wA/wB and interstitialcy correlation factors fI; which play a crucial role in the interpretation of ion-conductivity data. The percolation behavior of fI when wA ≪ wB is analysed in detail and limits of the tracer diffusivity ratios bD A/bD B for alloy compositions below the percolation threshold are presented. Allowance for non-collinear jumps (partly) replacing concurrent collinear site exchanges leads to a reduction of diffusion correlation effects. This goes along with a shift of the diffusion percolation threshold to lower concentrations of the (more) mobile component B. Even stronger changes of mass and charge transport compared to an exclusively collinear interstitialcy scheme are observed for additional contributions of direct interstitial jumps. It is remarkable that for both extensions of interstitialcy-mediated diffusion the Haven ratio appears to be greater than unity in certain composition ranges poor in B.
Authors: Gary S. Collins
Abstract: Using the method of perturbed angular correlation of gamma rays, diffusional jump-frequencies of probe atoms can be measured through relaxation of the nuclear quadrupole interaction. This was first shown in 2004 for jumps of tracer atoms that lead to reorientation of the local electric field-gradient, such as jumps on the connected a-sublattice in the L12 crystal structure. Studies on many such phases using the 111In/Cd PAC probe are reviewed in this paper. A major finding from a 2009 study of indides of rare-earth elements, In3R, was the apparent observation of two diffusional regimes: one dominant for heavy-lanthanide phases, R= Lu, Tm, Er, Dy, Tb, Gd, that was consistent with a simple model of vacancy diffusion on the In a-sublattice, and another for light-lanthanides, R= La, Ce, Pr, Nd, that had no obvious explanation but for which several alternative diffusion mechanisms were suggested. It is herein proposed that the latter regime arises not from a diffusion mechanism but from transfer of Cd-probes from In-sites where they originate to R-sites as a consequence of a change in site-preference of 111Cd-daughter atoms from In-sites to R-sites following transmutation of 111In. Support for this transfer mechanism comes from a study of site-preferences and jump-frequencies of 111In/Cd probes in Pd3R phases. Possible mechanisms for transfer are described, with the most likely mechanism identified as one in which Cd-probes on a-sites transfer to interstitial sites, diffuse interstitially, and then react with vacancies on b-sites. Implications of this proposal are discussed. For indides of heavy-lanthanide elements, the Cd-tracer remains on the In-sublattice and relaxation gives the diffusional jump-frequency.
Authors: Le Zhou, Yong Ho Sohn
Abstract: Heusler NiMnGa alloys are often categorized as ferromagnetic shape memory alloys or magnetocaloric materials, which are important for both practical applications and fundamental research. The NiMnGa alloys undergo a series of diffusion and diffusionless transformation from high temperature to low temperature. Among these transformation, martensitic transformation from austenitic phase to martensitic phase is critical in determining the properties of the alloys. Although martensitic transformation is considered diffusionless, diffusion also has important applications in the research of NiMnGa alloysDiffusion couples along with equilibrium alloys have been used to determine the ternary phase diagrams in NiMnGa alloys. Phase diagrams are important in selecting NiMnGa alloys, in particular two-phase NiMnGa alloys for practical applications. Furthermore, the diffusion couples effectively assist in the determination of compositions that exhibit martensitic transformation temperature near room temperature. Diffusion coefficients have been assessed for NiMnGa alloys. Tracer diffusivity of Ni, Mn and Ga was reported in a wide temperature range and followed Arrhenius behavior. Two different activation energies were obtained, corresponding to B2 and L21 crystal structure, respectively. Interdiffusion coefficients for NiMnGa alloys with B2 crystal structure are measured, which showed that Ni diffuses the fastest, followed by Mn then Ga. The diffusion coefficients provide useful information for fabricating NiMnGa alloys through diffusional process.A combinatorial approach involving diffusion couples and advance characterization has been developed to investigate the mechanical properties, microstructure and crystallography of NiMnGa alloys rapidly and systematically over a large compositional range. The composition-dependent modulus and hardness for NiMnGa alloys was extracted from the diffusion couples with the help of nanoindentation. Martensitic phases with non-modulated and various modulated crystal structures, and austenitic phase were identified in the interdiffusion zones by transmission electron microscopy. The results demonstrate the capability of using diffusion couples to speed up the discovery of new NiMnGa alloys or other similar alloys showing martensitic transformation.
Authors: Jörg Kärger, Rustem Valiullin
Abstract: Nanoporous materials find widespread application in material upgrading by separation (“molecular sieving”) and catalytic conversion. Mass transfer in these materials is a key phenomenon deciding about their technological performance. This chapter deals with the application of measurement techniques which are able to follow the diffusive fluxes of the guest molecules in such materials over “microscopic” distances, including the pulsed field gradient (PFG) technique of Nuclear Magnetic Resonance (NMR) and the techniques of microimaging by interference microscopy (IFM) and by IR microscopy (IRM). Microscopic measurement is a prerequisite for attaining unbiased information about the elementary steps of mass transfer and about their role within the overall process of technological exploitation. We dedicate this treatise to the memory of our dear and highly esteemed colleague Nicolaas Augustinus Stolwijk, notably in recognition of his manifold activities in the field of diffusion, distinguished by their impressively high standard in connecting the message of various techniques of measurement and in combining them to comprehensive views on quite intricate subjects.

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