Flexible metal-organic frameworks (MOFs) are capable of changing their crystal structure as a function of external stimuli such as pressure, temperature, and type of adsorbed guest species. DUT-49 is the first MOF exhibiting structural transitions accompanied by the counterintuitive phenomenon of negative gas adsorption (NGA). Here, we present high pressure in situ ¹²⁹Xe NMR spectroscopic studies of a novel isoreticular MOF family based on DUT-49. These po-rous materials differ only in the length of their organic linkers causing changes in pore size and elasticity. The series encompasses both, purely microporous materials as well as materials with both, micropores and small mesopores. The chemical shift of adsorbed xenon depends on xenon-wall interactions and thus, on the pore size of the material. The xenon adsorption behavior of the different MOFs can be observed over the whole range of relative pressure. Chemical shift adsorption/desorption isotherms closely resembling the conventional, uptake-measurement based isotherms were obtained at 237 K where all materials are rigid. The comparable chemical environment for adsorbed xenon in these isoreticular MOFs allows establishing a correlation between the chemical shift at a relative pressure of p/p₀ = 1.0 and the mean pore diameter. Furthermore, the xenon adsorption behavior of the MOFs is studied also at 200 K. Here, struc-tural flexibility is found for DUT 50, a material with an even longer linker than the previously known DUT-49. Its structural transitions are monitored by ¹²⁹Xe NMR spectroscopy. This compound is the second known MOF showing the phenomenon of negative gas adsorption. Further increase in the linker length results in DUT-151, a material with interpenetrated network topology. In situ ¹²⁹Xe NMR spectroscopy proves that this material exhibits another type of flexibility compared to DUT-49 and DUT-50. Further surprising observations are made for DUT-46. Volumetric xenon adsorption measurements show that this non-flexible microporous material does not exhibit any hysteresis. In contrast, in situ ¹²⁹Xe NMR spectroscopically detected xenon chemical shift isotherms exhibit a hysteresis even after longer equilibration times than in the volumetric experiments. This indicates kinetically hindered re-distribution processes and long-lived metastable states of adsorbed xenon within the MOF persisting at the time scale of hours or longer.

This master's thesis is focused on in situ observation of the negative electrode of the lead acid accumulator using atomic force microscopy AFM. Discussed topics are lead acid accumulator, atomic force microscopy, cyclic voltammetry and current knowledge of the in situ observation of the lead acid accumulator using AFM. The main task of this project is assembling the experimental cells, make in situ observation of the negative electrode surface of the lead acid accumulator. In the end evaluate if this method is suitable for the lead acid battery observation.

Fluorescenční in situ hybridizace (FISH) je široce používaná metoda pro detekci určité sekvence DNA na chromozomech. Cílem práce je porovnání tří různých chemických sloučenin (formamidu, ethylenkarbonátu a sodných kationtů) používaných ve směsích pro in situ hybridizaci. Složení těchto směsí ovlivňuje renaturaci DNA a je důležité porovnat jejich fyzikální vlastnosti. Práce je rozdělena do dvou hlavních částí. První část se zabývá otázkou termodynamických parametrů používaných pro experimenty FISH, jako je teplota tání, entalpie přechodu DNA ze dvoušroubovice na vlákno nám dává přehled o energii potřebné k tomto přechodu a interakcích mezi bázemi a každou složkou směsi. Kromě toho hodnoty entropie určují poř uvnitř směsi - systém DNA. Druhá část porovnává intenzitu fluorescenčního signálu při optimalizovaných teplotách tání sondy použité pro in situ hybridizaci. Jako sonda byla použita sub-telomerní repetice X43.1, která je umístěna na Y chromozomu rostlinného modelového organismu Silene latifolia. Směs obsahující formamid má nejlepší výkon při delším postupu hybridizace, zatímco ethylenkarbonát poskytuje vyšší intenzitu signálu, a proto je vhodnější pro rychlé FISH protokoly.

In this thesis we study the interaction of helium, neon, argon and gallium ions with graphene. The graphene structure is contaminated with gallium ions during the graphene processing by focused gallium beam (FIB). The graphene properties are affected, e.g. reducing the electrical conductivity. The aim of this thesis is to verify the effect of selected ion beams on the graphene structure and select suitable ion beam for sputtering. Furthermore, the modification of standard heating stage used in LEIS instrument (Qtac 100) was designed and implemented. The LEIS instrument is connected to the complex UHV system for deposition and analysis of nanostructures – SPECS. This modification allows analysis of selected nanoparticles on suitable substrate at the elevated temperature.

Cílem diplomové práce je popsat oxidaci nanotrubic sulfidu wolframičitého za zvýšených teplot v přítomnosti vodní páry. Na jejich povrchu se nejprve vytvoří nanočástice oxidu wolframu, ze kterých potom vyrůstají nanodráty. Na základě in-situ experimentů v rastrovacím elektronovém mikroskopu je navržen mechanismus reakce a ten je zjednodušeně popsán analyticky. Ukazuje se, že elektronový svazek má zásadní vliv na reakci.

The dissertation thesis is focused on thermal insulating properties of reflective insulation under boundary conditions typical for low-energy buildings. In the introductory part of this thesis the attention is focused on the heat transfer process. There is described primarily heat transfer by radiation. There is also described the reflective insulation and the methods of determination their thermal performance. The remaining part of the thesis deals with the analysis of the results obtained in experimental measurements. Measurement results are compared with the calculation model. Conclusions for technical practice including possibilities of further research are summarized in the final section.

This thesis is divided into three main sections that deal with optical and magnetic thin films properties and their measurements techniques. Principles of the spectroscopic reflectometry and measurements of optical properties are described in the first part. Results of imaging reflectometry are most important. This technique is based on in situ monitoring of optical properties of SiO2 thin films during etching over the area cca 10 × 13 mm2. In next section magnetic properties of thin films and new apparatus built on the Institute of Physical Engineering of BUT are shown. Magnetic properties were observed by longitudinal magneto-optical Kerr effect. The construction of the device is based on a light beam with rectilinear polarization reflected from magnetic material with turned polarization. For investigation of local magnetic properties of microstructures a microscope objective focusing laser beam on the sample is used. The last part of the thesis is aimed on improving of a spin valve structure Co/Cu/NiFe. This work was done within the frame of the Erasmus project in Laboratoire Louis Néel in Grenoble. The goal was to achieve the value of GMR (Giant Magnetoresistance) as high as possible by changing of deposition parameters. This value describes the rate of resistances in different mutual directions of magnetization in trilayers.

Sous irradiation, les flux de particules (neutrons, ions, électrons) créent des défauts ponctuels (lacunes et interstitiels) qui génèrent des défauts étendus (boucles de dislocation, cavités) responsables de la fragilisation des matériaux. L'aluminium est un matériau de faible masse et de faible énergie seuil de déplacement (Ed=16-19 eV) ce qui permet de créer les nanodéfauts étendus directement sous irradiation aux électrons dans un microscope électronique à transmission haute résolution (HRMET). Cet instrument permet non seulement de caractériser finement les nanodéfauts mais également d'étudier leur évolution in situ sous irradiation, ceci en fonction de la température, du taux de dommage et d'une pression partielle d'hydrogène. Nous avons constaté un effet important de la pression partielle d'hydrogène sur la cinétique de formation des boucles de dislocation et des cavités. Parallèlement, nous avons mis en place une modélisation multi-échelle des effets de taille finie et de discrétisation du réseau sur la morphologie d'équilibre des cavités à partir de calculs ab initio des énergies de surface et de liaison de petits amas lacunaires et des amas mixtes lacune-hydrogène. La caractérisation expérimentale des morphologies des cavités en fonction de leur taille met en évidence trois formes régulières : une forme de croix bordée par des surfaces {100}, une forme d'octaèdre non tronqué bordée par des surfaces {111} et une forme d'octaèdre tronqué, bordée par les surfaces {111} et {100} ainsi qu'un effet de taille finie entre ces formes prédit par le modèle. De même, la mesure des fluctuations morphologiques d'une cavité au cours de sa croissance ou de sa décroissance en taille révèle le rôle déterminant des nombres magiques fixés par la géométrie et la discrétisation du réseau. A partir du modèle thermodynamique des cavités et d'une caractérisation expérimentale de la densité volumique et de la distribution en taille des nanodéfauts, nous proposons un modèle de germination des cavités sous irradiation. Nous en déduisons une taille du germe critique et un taux de germination des cavités en fonction de la température et du taux de dommage, qui sont comparés aux valeurs expérimentales correspondantes extraites des observations in situ. Enfin, nous discutons de l'effet de l'hydrogène sur la stabilité des amas mixtes lacune-hydrogène et sur la cinétique de germination des cavités. / Under irradiation, flows of particles (neutrons, ions, electrons) induce ponctual defects (vacancies and interstitials) which generate extended defects (dislocation loops, cavities) that are responsible for materials weakening. Aluminum is a low mass material with a low displacement energy (Ed=16-19 eV) which allows the creation of extended defects directly under electron irradiation in a high resolution transmission electron microscope (HRTEM). This instrument allows not only a fine characterization of nanodefects but also to study their evolution in situ under irradiation, depending on temperature, damage rate and a partial pressure of hydrogen. We noticed an important effect of the hydrogen partial pressure on the kinetic of formation of the cavities and dislocation loops. Simultaneously, we developped a multiscale modelisation of finite size effets and structure discretisation on equilibrium shapes of cavities based on binding and surface energies determined by ab initio calculation of small vacancy clusters and mixted hydrogen vacancy clusters. Experimental characterization of cavity shapes according to the cavity radius reveals three regular shapes : a cross shape bounded by {100} surfaces, an octahedral non-truncated shape bounded by {111} surfaces and an octahedral truncated shape, bounded by {100} and {111} surfaces as well as the determination of a finite size effect predicted by the model. Also, measurements of cavity shape dispersion during its growth and decrease showed a dominant effet of magic numbers, fixed by geometry and frustration of the structure. Based on a thermodynamic model and a fine experimental characterization of volumic density, we propose a nucleation model of cavities under irradiation. We deduce from this model a critical cluster size and a rate of cavity nucleation depending of temperature and damage, which are compared to the corresponding experimental values extracted from in situ observations. Finally, we discuss the effect of hydrogen on the stability of vacancy-hydrogen clusters and on the kinteic of cavity nucleation.

Dans le cadre de la réduction des émissions de gaz à effet de serre, une des approches possibles consiste en l’utilisation de membranes pour séparer le CO2 de mélanges gazeux. Durant ce travail de thèse, la séparation CO2 / N2 dans des conditions de post-combustion a été étudiée pour des membranes à matrice mixte composées de matériaux organométalliques poreux, les MOF, insérés dans des polymères. Plus spécifiquement, la thèse porte sur la caractérisation de ces membranes à l’aide des spectroscopies vibrationnelles (IR et Raman). Différentes membranes polymériques et membranes à matrice mixte basées sur des polymères commerciaux comme le Matrimid ou le PEBAX ou des nouveaux polymères comme le PIM-1 ou 6FDA-DAM plus performants ont ainsi été étudiées. La spectroscopie Raman a d’abord été utilisée pour contrôler l’homogénéité des membranes et la bonne dispersion du MOF au sein du polymère à l’aide du Raman. Les interactions entre le polymère et le MOF ont également été étudiées à l’aide des spectroscopies IR in situ et Raman, notamment pour des composites modèles permettant de maximiser les interactions entre les deux composés. La deuxième partie du travail a été axée sur la caractérisation spectroscopique (IR operando) de ces membranes dans les conditions de post-combustion, simultanément à la mesure de leurs performances en séparation. Un système de mesures dédié a donc été spécialement développé. Cette méthodologie permet de comparer directement les données d’adsorption et de séparation des membranes. En développant une nouvelle approche couplant les aspects cinétiques et thermodynamiques de l’adsorption et de la perméation, les données expérimentales ont été modélisées afin de déterminer les paramètres d’adsorption et de diffusion des différentes membranes. / In the frame of the abatement of greenhouse gases, one of the possible approaches concern the use of membranes to separate CO2 from gas mixtures. During this PhD work, CO2 / N2 separation in post-combustion conditions has been studied for Mixed Matrix Membranes constituted by porous organometallic materials, MOFs, inserted into polymers. More specifically, this work aims at the characterization of these membranes using vibrational spectroscopies (IR and Raman). Different membranes, purely polymeric or Mixed Matrix Membranes, based on commercial polymers such as Matrimid or PEBAX as well as new polymers such as PIM-1 or 6FDA-DAM have been studied. Raman spectroscopy was first used to control the homogeneity of the membranes and the good dispersion of the MOF within the polymer. The interactions between the polymer and the MOF were also studied using IR in situ and Raman spectroscopies, notably for composites allowing maximizing the interactions between the two components. The second part of the work focused on the characterization of these membranes under operating post-combustion conditions, simultaneously with the measurement of their separation performance. For this purpose, a specifically designed measurement system has been developed in order to be able to test the membranes using IR operando. This methodology allows the direct comparison of adsorption and separation data. By the development of a new approach coupling kinetic and thermodynamic aspects of adsorption and permeation, experimental data were modelled to determine adsorption and diffusion parameters of the various membranes.

The doctoral thesis deals with an experimental study of several diagnostic techniques intended for plasma diagnostics and diagnostics of thin films during reactive sputter deposition. A relatively novel probe diagnostic technique called Floating harmonic probe for measurement of the ion density and electron tem- perature in technological low-temperature plasma is studied. A Langmuir probe is commonly used, however, its application in conditions where non-conducting films are being deposited can be problematic or unreliable. The floating harmonic probe measurement technique deals with this inherent problem of the Langmuir probe. The Floating harmonic probe results are compared to those obtained by a classical Langmuir probe in non-reactive DC continuously driven discharge, and its applicability in reactive regime during deposition of iron oxide thin films is proved. The work deals also with a modification of the Floating harmonic probe called Phase Delay Harmonic Analysis Method which is intended for diagnostics of pulsed driven discharges. The second part of the thesis is devoted to a new proposed method for in-situ diagnostics of thin films. This method monitors the capacitance and resistance of a thin film during deposition up to the frequencies in the kHz range. This new method could be used for...