PhD Thesis Topics potentially granted by a doctoral contract from October 2015 Research Group «Energy and Transfers » TITLE : PHD RESEARCH PROPOSAL (potentially granted by a doctoral contract) 2015 www.lemta.fr « Semiconductors for thermoelectricity : nanostructuration, interfaces et composition » SUPERVISORS : Surname, Name : Konstantinos TERMENTZIDIS, David LACROIX Email & phone : [email protected] (00 33 3 83 68 46 86) [email protected] (00 33 3 83 68 46 88) Postal address : LEMTA - Université de Lorraine - CNRS UMR 7563 Faculté des Sciences et Technologies, BP 70239, F-54506 VANDOEUVRE CEDEX CONTENT OF THE WORK : Atomistic and numerical simulations, Modeling, Theory ABSTRACT : The purpose of this PhD research is to improve our knowledge of electronic and heat transport in nanowires and composite materials with nanoinclusions designed for thermoelectricity applications. This implies the modeling of semiconductor materials with atomistic simulation tools (ab-initio, molecular dynamics, Monte Carlo methods) which are relevant and reliable at these nanoscales. COLLABORATIONS : Institut Jean Lamour (teams 102 and 208) : Laurent CHAPUT and Nicolas STEIN Technological Educational Institution, TEI of Sterea Ellada (Greece) : Xanthippi ZIANNI RESEARCH GROUP : THERMAL TRANSPORT IN MICRO-NANO SCALE The group is composed by Engineers and Physicists of Condensed Matter Physics. Their main interesting is nanostructured semiconductors materials for energy applications. Recent advances in the field of nano-fabrication technologies allow today the synthesis of nanostructures (nanowires, nano-objects, superlattices ...) that can be integrated in micro-electronic devices, thermoelectric, photovoltaic devices. However, the heat transport in these systems is strongly affected by the interfaces. To increase the reliability, the life-time and to decrease the cost of these devices, controlling heat flow is a necessity. In our group, we develop theoeretical models, simulation tools (atomistic and mesoscopic) and experimental devices dedicated to the exploration of new phenomena observed at very small scales. The main numerical and experimental tools used are: • The simulation ab initio (VASP) and molecular dynamics (LAMMPS) for the calculation of transport properties in nano-scale, • The simulation of the Boltzmann equation by statistical method (Monte Carlo) for the description of heat exchange at the meso-scale (between the atomistic and continuum models), • The thermal local probe microscopy AFM and the SThM (Scanning Thermal Microscopy). DETAILED PHD RESEARCH PROPOSAL State of the art: Thermoelectric effects allow the conversion of a temperature difference into a voltage (Seebeck effect) and conversely (Peltier effect). Despite these phenomena which were discovered at the beginning of the XiXth century, the weak efficiency of thermoelectric materials and their cost have limited the development of this technology. However, during the past decade the thermoelectricity has been reconsidered as a potential alternative for energy production with the emergence of new materials designed at the nanoscale with tailored properties. New nano-fabrication techniques allow the increase of the Figure of Merit (ZT ∝ ,k)which characterizes the thermoelectric efficiency. As it can be seen lowering the thermal conductivity (k) and keeping constant the electric one ( ) make thermoelectric materials more efficient. Thus, understanding how electrons and phonons are transported in small scale objects (size below 1µm) is a major issue for the development of new thermoelectric materials, especially in order to promote renewable energies. Therefore, the objective on this research is to model accurately the thermal properties of these materials with atomistic simulation tool. Research program: In order to improve thermoelectric materials ones has to know which parameters can be tuned in order to increase their efficiency. In the frame of this work a “bottom-up” approach will be considered. It starts at the atomic scale with ab-initio calculations and molecular dynamics simulations and goes to the micron scale with the resolution of the Boltzmann transport equation with Monte Carlo techniques. Thus, it is a multi-scale modeling with dedicated numerical simulation tools. In this work, core-shell nanowires and composite materials made of Bi2Te3 (Bismuth Telluride) will be considered since they are good candidates for high thermoelectric efficiencies. In order to study these core-shell objects (Figure 1-left), or the composite materials (Figure 1-right) several parameters have to be considered: • First, the interfaces between the two semiconductors (Bi and Te) requires an accurate modeling of the phonon flow. This could be done with ab-initio tools such as VASP or with Molecular Dynamics with the LAMMPS code. Kaptiza thermal resistance, phonon dispersion properties and lifetimes can be addressed with these simulation tools. • Secondly, phonon confinement effects in the nanowires must be considered in order to appraise thermal conductivity. This can be done with Molecular Dynamics or Monte Carlo simulations. Several parameters, such as: the roughness of the interface, the core-shell size ratio, the nanowire length, the doping level or the material organization (Bi/Te or Te/Bi core-shell) can be modeled with these tools. • Lastly, the use of Bi2Te3 nanowires, embedded into a polymer matrix, in order to build a p-n junction is expected. This part of the work will be done in collaboration with the team 208 of the IJL, where people have recognized experimental skills in the fields of the nanofabrication and the characterization of thermoelectric devices. Summary: The PhD candidate will integrate an active team in the field of nanosciences. Within the PhD thesis, he will study the impact of (i) different stoichiometries of nanowires composed by Bismuth and Telluride (BixTey) or with alternate layers of the two materials (superlattice nanowires) and (ii) the nanoinclusion geometry in a host matrix. Their thermal and electrical properties will be appraised. The team has experience in such systems, (i) for their thermal properties [D. Lacroix et al. Phys. Rev. B 2005 & Appl Phys Lett. 2006, K. Termentzidis et al Phys. Rev. B 2009, Nanotechnology 2014 & J. Phys. Cond. Matter 2014] and (ii) for their thermoelectric properties [K. Termentzidis et al J. Appl. Phys. 2013]. The PhD candidate will use different simulations methods: ab-initio calculations, Molecular Dynamics and Monte-Carlo computing. He will predict the behavior of thermoelectric materials at the nano and microscale. The Scientific Operation Group THOMAS of LEMTA laboratory has the know-how of all the methods mentioned above. One of the challenges of this thesis would be the integration of electron-phonon interactions to the existing “single carriers” heat transport theories currently available. This PhD thesis will give us the opportunity to collaborate with the groups 102 and 208 of Jean Lamour Institute. The 208 group has recognized competences at international level in the fabrication, characterization and integration of BiTe alloys for thermoelectric devices, while the 102 for his experts with DFT calculations. The scientific collaboration with these two groups as well with Professor Xanthippi Zianni (National Center of Scientific Research, Greece) will improve our knowledge in this domain, giving us a global vision of all scientific aspects; namely, from the theoretical point of view (modeling and simulations) to the experimental one (characterization and integration of such materials into thermoelectric devices). Establishing this bridge between simulations and experiment will drive us to materials with tailor thermoelectric properties eg. nanostructuration is the best way to increase the ZT, while decreasing mainly the thermal conductivity. Figure 1- (left) Schematic representation of Bi-core, Te-shell nanowire with rough interfaces (right) Three configurations for core/shell silicon nanowires. PhD RESEARCH PROPOSAL TITLE : (potentially granted by a doctoral contract) 2015 www.lemta.fr Stability of the two-phase displacement in porous media studied by MRI techniques SUPERVISORS : Director of thesis : Irina Panfilova [email protected] 03.83.59.55.96 Co-director : Sébastien Leclerc [email protected] 03.83.68.43.59 [email protected] [email protected] 03.83.59.56.96 03.83.59.56.11 Consultants : Maude Ferrari Didier Stemmelen Postal Address : LEMTA – Université de Lorraine – CNRS UMR 7563 2 Avenue de la Forêt de Haye, TSA60604, F-54518 VANDOEUVRE CEDEX Professional web page of personnel : http://lemta.univ-lorraine.fr/data/pages_pro/I.Panfilova.pdf CONTENT OF THE WORK : Experimental study, numerical modeling ABSTRACT : Modeling the stability of a two immiscible liquids flow under the simultaneous effect of gravity, viscosity and superficial tension is a problem widely discussed in the scientific community. The complex geometry of the porous space and the viscous and capillary forces cause the deformation of the displacement front, its fragmentation in form of droplets and a further deceleration or total immobilisation of these droplets. The objective of this research is to get the kinetic parameters of these processes by an experimental study based on the MRI technology and to perform numerical modeling at the pore scale. The developed model will be applied to simulate the enhanced oil recovery, where the technology often causes a deformation and dispersion of the displacement front. COLLABORATIONS : DETAILED PHD RESEARCH PROPOSAL : This study concerns immiscible two-phase flow in porous media. The complex geometry of the porous space, the difference in the properties of fluids and capillary force cause a deformation of the displacement front. The interaction of two immiscible liquids provokes the trapping of one phase in the other one. We consider the case where the dimensions of the drops are comparable with the pore size. The movement of drops is either strongly decelerated or stopped by the capillary force (Fig.1), which presents the main interest in our study. Fig.1 Movement and trapping of droplets in porous media Fig.2 600 MHz WB spectrometer We are considering a series of experiments using MRI technique (Fig.2) where we aim to visualize the propagation and mixing of liquids in porous media. We are especially interested in the deformation of the displacement front during its progress in the porous sample and in the formation of the trapped drops. At the same time, for the modeling at the pore scale, we will use a simulation software created in our group which models a multi-phase flow in a pore network (capillary network model of porous medium). This code is well adapted to unstable two-phase displacements. PROPOSED RESEARCH : Background Innovative experimental techniques are used in LEMTA such as Magnetic Resonance Imaging (MRI), traditionally used in medicine, and Nuclear Magnetic Resonance (NMR) Spectroscopy. These techniques are exploited, for instance, for quantitative analysis of flow in opaque materials such as porous media. The study of liquid flow in porous media is part of the “Observe in the opaque” action, which started in 2002 with its launch by D. Stemmelen (CR1 CNRS - LEMTA) with technical assistance of S. Leclerc, Fr. Xu, J.C. Perrin and others specialists of NMR and MRI. Topic development The study of two-phase flow in porous media is of considerable interest in the petroleum industry (estimation of exploitable reserve, optimization of the recovery techniques…) but also in the sector of chemical industry (catalytic reactors, separation, extraction) or in the hydrogeology domain (pollution of aquifers by NAPL). This explains the importance of the studies aiming to improve the description of multi-phase flow in porous media. Notably, the simultaneous flow of two immiscible fluids (water-oil) in porous media is not always well described by the Darcy's generalized law, which only takes into account water/oil saturation as additional descriptive variable. This has a substantial impact on the modeling of the two-phase flow stability under the simultaneous effect of the force of gravity, viscosity and superficial tension. Objective of project The overall purpose of this study is to determine kinetics of the process of phase trapping during two-phase flow. The phase saturations and the menisci concentration in the zone of the front deformation will allow us to complete the vector menisci model proposed in [1]. This model takes into account the vector nature of capillary forces. This will lead to an improvement of the description of the theory of oil recovery and hydrogeology. Preliminary results The experiments allowing one to visualize the distribution of fluids in 3D real porous medium (micro-tomography X, acoustical methods, PET-scan...) are not numerous. Among the known techniques, Magnetic Resonance Imagery (MRI) allows to make non-invasive measurements (2D, or even 3D mapping) of the concentration of hydrogen nuclei in the liquid phase in a porous medium. These hydrogen nuclei can belong to molecules of water or other liquids (oil for example). A preparatory work done in the laboratory showed that MRI cartography of longitudinal relaxation time T1 allows, with a prior calibration, to measure the phase saturation in a quite accurate way. The measurements by Magnetic Resonance Imaging (MRI) of fluid flow within granular porous media were presented in the thesis of W.Salameh (LEMTA, 2010). This study has shown the possibility of visualization of velocity field in porous media and accurate measurements of interstitial and averaged velocities in packed beds [2]. 3 master thesis (A. Darishev, A. Pakzad, 2011; B. Kabiwa, 2012; G. Carron, E. Maxant, 2013) were performed in order to validate the analysis of two-phase fluid flow in porous media by MRI technique. In these experiments the displacement of oil by water flooding was studied in porous medium formed by the polystyrene beads of average particle size 0.5 mm. The values of phase velocities and saturations were measured in longitudinal and transverse sections at different time steps. Furthermore, fluids distributions in porous samples during the experiments were mapped. Research methodology By using MRI techniques, our aim is to improve the description of two-phase flow in porous media. We will be using a mix of water and octanol. The porous media model will be first a stack of mono-dispersed beads (with a diameter in the order of a hundred microns) before envisaging real porous medium (sandstone). We plan to realize the experiments of imbibition-drainage in the porous media in conditions of injection with very weak capillary number (Ca<<1). In these experiments, the front of displacement (water - octanol) is deformed due to viscous instabilities and capillary forces. It forms islets of octanol trapped in porous structure by capillarity. This twophase zone (front of dispersion) can be observed by MRI. We will also be able to analyze the effect of gravity, which plays a stabilizing role for the displacement front. The model porous medium will consist of a glass column filled with randomly packed spherical polystyrene beads for the drainage process and with borosilicate glass beads for imbibition. At first, the column is flooded with octanol. It will be subsequently attached to two reservoirs and placed in the magnet. A three dimensional image of the porous space will be first acquired; in all experiments the 1H species associated with the water or hydrocarbon are imaged. MRI provides three dimensional images, able to distinguish the solid, hydrocarbon, and aqueous phases, as well as velocity maps of the mobile aqueous and octanol phases. Water will then be injected into the column from the bottom with volumetric flow rate corresponding to a superficial velocity of low Ca, until the irreducible hydrocarbon saturation, Sir, is obtained in the form of octanol droplets entrapped in the porous space by capillary forces. During the experiment, we will acquire a number of longitudinal and transversal images. Saturation will be defined as the percentage of the pore volume occupied by octanol. Finally, a 3D image of the distribution of octanol droplets within the bed will be acquired using a T1-weighting method [3]. We will also use MRI velocimetry techniques in the case of liquid-liquid flow in porous medium. We expect to measure the velocity of each phase in porous medium independently of the other phase. It would constitute a considerable advance in the description of two-phase liquid-liquid flow in porous medium and a redefinition of the models of relative permeability functions. To model numerically a two-phase flow on pore scale, we are going to apply a software simulating multiphase flow in pore networks. This code is well adapted to the two phase flow with phase structures of meniscus type. The numerical simulations will be compared with the experimental studies. Another code based on Comsol Multiphysics and using the diffuse interface method can be applied to model the flow of drops in porous media. The simulation results based on stochastic distributions of droplets will allow us obtain the (macroscopic) parameters of the fragmentation and coalescence kinetics, as well as the position of meniscus and droplets. The perspectives of application of this study concern the phenomena strongly governed by capillary effects, such as the displacement of oil by water or the capillary fringe in the aquifers. [1] Panfilova I. and Panfilov M. Phenomenological meniscus model for two-phase flow through porous media. Transport in Porous Media, Special Issue on Multiphase Flow and Transport in Porous Media, v. 58, 1, pp. 87-119 (2005). [2] Salameh W., Leclerc S., Stemmelen D., Escanyé J.M. NMR imaging of water flow in packed beds. Diffusion Fundamentals, 14 (5) 1-5, (2010). [3] Johns M. L. and Gladden L.F. Magnetic Resonance Imaging Study of the Dissolution Kinetics of Octanol in Porous Media, Journal of Colloid and Interface Science 210, 261–270 (1999) NB : The laboratory has a privileged access to two MRI installations: - 100 MHz imager with horizontal bore (400 mm of diameter) - 600 MHz NMR spectrometer with a vertical bore (89 mm) and equipped with a micro-imaging system. PHD RESEARCH PROJECT (potentially granted by a doctoral contract) 2015 www.lemta.fr TITLE : NMR and MRI investigation of water transport through multilayer PEMFC components. Institution University of Lorraine / LEMTA Laboratory / CNRS PhD supervisor Prof. Olivier Lottin Co-supervisor Dr. Jean-Christophe Perrin Contact e-mail : [email protected] phone : +33 (0)3.83.59.55.86 activities of the research group : http://lemta.univ-lorraine.fr/pac.html Mailing address 2 avenue de la Forêt de Haye, TSA60604 54518 Vandoeuvre Cedex, France International context The quest for more sustainable energy has become a worldwide priority. During the past decades, the global demand for energy has exploded, raising the need for highly efficient energy conversion devices. Today, hydrogen has gained importance as an energy carrier in future transport applications and fuel cells have reached a state-of-the-art that makes them highly attractive for car propulsion. Groups of researchers around the world are carrying out the environmental and economic assessments of the entire hydrogen supply chain and it is generally believed that, when combined with the right energy sources, fuel cells, and more particularly polymer electrolyte membrane fuel cells (PEMFCs), have the highest efficiencies and lowest emissions of any vehicular power source. Fundamental and technological research in the field of PEMFC systems is intense and, in the past years, more than 35% cost reduction has been achieved in their fabrication. In PEMFCs, hydrogen and oxygen react to form water and, due to the separation of the anodic and cathodic processes, electrical energy. Protons migrate through the membrane (PEM) and recombine with oxygen on the surface of the cathodic catalyst where oxygen is reduced and forms water (Figure 1). The electrolyte of the PEMFC is usually a polymer membrane composed of poly(tetrafluoroethylene) backbones with sulfonate-terminated side chains, like Nafion®. To reach the target for transportation fuel cell of $30/kW to compete with the conventional technology of internal-combustion engines, breakthroughs in material development, acquisition of fundamental knowledge, and development of experimental methods are still needed. More specifically, the development of new methods to investigate water management in PEMFC materials will provide insights into a number of critical phenomena that occurs in running fuel cells. These methods have the potential to provide critical feedback for validating models of water transport phenomena for fuel cell research and development. MEA bipolar plate PEM catalyst coating bipolar plate GFC : Gas Flow Channel O2 H2 PEM : Proton Exchange Membrane GDL : Gas Diffusion Layer H2O MEA : Membrane Electrode Assembly MPL : Micro Porous Layer GFC sealing gasket GDL+MPL sealing gasket Figure 1. Proton Exchange Membrane Fuel Cell (PEMFC) components. Scientific project This project aims at studying the properties of complex assemblies composed of the ionomer membrane and one or more elements such as the catalyst layer (electrode) and/or the gas diffusion layer. The main experimental technique will be MRI (Magnetic Resonance Imaging) and NMR (Nuclear Magnetic Resonance) spectroscopy. The experimental methodology will be based on the recent advances made in our group in the imaging of water profiles through a PEM membrane with both high spatial and temporal resolutions [Figure 2(a) and (b) and ref(1)]. Figure 2 (a) Experimental setup developed for the MRI of water distribution in the thickness of a PEM. The 2D NMR probe is placed under the cell containing the membrane exposed to air flows with controlled hygrothermal conditions. t<0 RH ~ 0% RH = 80% membrane RH ~ 0% RH ~ 0% membrane y 1L/min 1L/min t>0 T = 24°C (b) Water profiles measured by MRI through a 250 µm thick Nafion membrane. Acquisition time = 70 seconds/profile. Spatial resolution = 6 µm / point. The study will be focused on the observation of water behavior in the membrane when its interfaces are exposed to different phenomena: - inhomogeneities in gas supply due to the electrode; - mass transfer resistances due to the GDL or the GDE (gas diffusion electrode); - electrochemical reaction with water formation at the membrane / electrode interface. The measurements will be systematically compared to the reference case (Nafion membrane exposed to controlled hygrothermal conditions) and used to develop a coherent modeling for water transport through the multilayer. The experimental methodology will be also exploited to characterize PEMs after long runs in fuel cell conditions, the final objective being the development of a new versatile diagnostic tool of aged membranes. References 1) M. Klein, J.-C. Perrin, S. Leclerc, L. Guendouz, J. Dillet, O. Lottin. Spatially and temporally resolved measurement of water distribution in Nafion using NMR imaging, ECS Transactions, 58 (1) 283-289 (2013). Related references: 2) J.-C. Perrin, M. Klein, S. Leclerc, L. Guendouz, J. Dillet, O. Lottin. NMR Investigation of Water Diffusion in a Nafion membrane Under Traction, ECS Transactions, 58 (1) 781-788 (2013). 3) M. Klein, J.-C. Perrin, S. Leclerc, L. Guendouz, J. Dillet, O. Lottin. Anisotropy of water selfdiffusion in a Nafion membrane under traction, Macromolecules, 46, 23, 9259-9269 (2013). 4) M. Klein, J.-C. Perrin, S. Leclerc, L. Guendouz, J. Dillet, O. Lottin. NMR Study of the anisotropic transport properties of uniaxially stretched membranes for fuel cells, Diffusion Fundamentals 18-7 (2013) 1-4. PhD thesis (Mathieu Klein, 2014) [non-definitive version] : https://docs.google.com/viewer?a=v&pid=sites&srcid=ZGVmYXVsdGRvbWFpbnxqZWFuY2hyaXN0b3BoZXBlcnJpbnxne DoxMTYyMTRmYmY0YTZjMDdk Application procedure Informal inquiries can be made to Dr Jean-Christophe Perrin ([email protected]) with a copy of your curriculum vitae and cover letter. Applications should be received and complete by 29 May 2015. Research Group «Mechanics of Materials and Structures » Research Group «Fluid, Reactive and Multiphase Media »
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