Mass spectrometry and Monte Carlo method mapping of nanoparticle ligand shell morphology

Janus, patchy, stripe-like, or random arrangements of molecules within the ligand shell of nanoparticles affect many properties. Among all existing ligand shell morphology characterization methods, the one based on mass spectroscopy is arguably the simplest. Its greatest limitation is that the results are qualitative. Here, we use a tailor-made Monte Carlo type program that fits the whole MALDI spectrum and generates a 3D model of the ligand shell. Quantitative description of the ligand shell in terms of nearest neighbor distribution and characteristic length scale can be readily extracted by the model, and are compared with the results of other characterization methods. A parameter related to the inter-molecular interaction is extracted when this method is combined with NMR. This approach could become the routine method to characterize the ligand shell morphology of many nanoparticles and we provide an open access program to facilitate its use.

Simulated annealing study of the disordered quantum magnet LiHoxEryY1-x-yF4

Thermal and quantum phase transitions of some rare earth compounds (LiErF4, LiYbF4, LiGdF4 and LiTmF4) are established using the mean field theory. These preliminary calculations allowed evidencing the existence of a novel high-field antiferromagnetic phase in LiErF4, and a still unexplained symmetry breaking in LiGdF4. But the discrepancies with experimental results impel a more sophisticated method. We then present analytical and numerical evidence for the validity of an effective approach to the description of the dipolar coupled antiferromagnet LiErF4. We show that the approach, when implemented in mean field calculations, is able to capture both the qualitative and quantitative aspects of the physics of LiErF4 at small external field and low temperature, yielding results that agree with those obtained in the full Hilbert space using mean field theory. This model nevertheless still fails to describe the LiHoF4 system and needs to be improved. We finally use this toy model as a basis for classical Monte Carlo simulations of LiErF4, which allows the calculation of thermodynamical quantities of the system, as well as the evolution of the order parameters as a function of field H and temperature T. These calculations yield results that are much closer to the experiments than those based on the mean field approximation. Although the theoretical critical temperature is still overestimated by 34%, the critical exponents computed from this effective model correspond to those found experimentally.

2012

Advanced analytical electron microscopy applied to Solid Oxide Cell materials and their degradation

Stéphane François Jean Poitel

Electron microscopy offers a wide range of techniques to study materials. Environmental Scanning Electron Microscopy (ESEM), in particular, allows the characterisation of samples at high-temperature using a laser heating stage, and under various gaseous atmospheres leading to direct observation of the sample surface morphology dynamics in conditions that are close to those in real operating devices (i.e. at high temperature in various gases). Solid Oxide Fuel Cells (SOFC) operating around 800°C in both oxidising and reducing gases, with proven co-generation efficiencies of 90%, offer very promising solutions in the ongoing energy transition. However, production costs and materials degradation in those demanding operating conditions remain significant barriers to their large-scale deployment. Studying SOFC materials' degradation through a combination of ESEM with other advanced microscopy techniques fulfilled the double aim of demonstrating the power of an ESEM and improving the understanding of SOFC materials' degradation during operation. Two materials from the SOFC stack were selected for degradation case studies at around 800°C in oxidising/reducing gases: coated ferritic steel interconnect and Ni-YSZ anode. The objectives were to explore the parameters' influence (temperature, heating ramp, pressure, gas exposure...), set the boundaries and define the guidelines of the ESEM technique while demonstrating its capabilities. The two different materials sets were selected for their relevance both for the SOFC field and for their different specific characteristics allowing a wide range of experiments to be explored. A specific method for the study of the oxidation of coated steel was developed combining ESEM, Focused Ion Beam (FIB) and Scanning Transmission Electron Microscopy (STEM). Post-test segmentation of the in-situ observed images demonstrated the possibility to obtain quantitative data. FIB sample preparation from the exact site of ESEM observation allowed to correlate the underlying microstructure with the in-situ surface observation. Applying this method, oxidation mechanisms of several coatings were characterised and specific behaviours observed and explained such as the appearance of oxide ridges and the behaviour of a cerium barrier layer in case of cobalt-cerium coated steel. The heating ramp speed and the oxidation temperature were demonstrated to be crucial parameters to obtain the desired microstructure. The nitriding pretreatment of interconnect was investigated too and shows promising results for improving the steel oxidation resistance. Another combination of techniques was developed for the study of the Ni-YSZ anode by complementing the ESEM observation with continuous Mass Spectrometer (MS) acquisition. The first reduction of the NiO-YsZ anode was analysed under gas flows of hydrogen and hydrocarbons. Redox cycling effect on the anode microstructure was investigated and the resulting observations were in line with models from the literature for the reduction and re-oxidation kinetics. Finally, the demonstration of an active solid oxide cell in the microscope operating at more than 700°C under mixed gas paves the way to further possible studies approaching the device's observation in real operating conditions. Limitation of the ESEM techniques are discussed and recommendations for further improvements and perspectives given.

EPFL2020

Advanced analytical electron microscopy applied to Solid Oxide Cell materials and their degradation

Stéphane François Jean Poitel

EPFL2020