The project elaborated in frame of engineering studies is submitting the study of thermal properties of holding mixtures using different types of sand. Were tested a total of 5 sands: zirkon, ŠH22, chromite, olivine and dunite. Molding compounds were tested for thermal capacity, thermal conductivity and heat accumulation. The highest heat capacity was achieved in dunite sand. The largest heat accumulation had mixture with chromite sand and the best thermal conductivity was found in a mixture with olivine sand.

Lithium-Ionen-Batterien besitzen ein ausgezeichnetes Potential für die Energiespeicherung. Das derzeit dominierende Anodenmaterial in Lithium-Ionen-Batterien mit einer Energiespeicherkapazität von 339 mAh/g ist Graphit. Als Alternative hierfür bieten sich Lithiumsilicide und Lithiumstannide an. Diese Materialien zeichnen sich durch eine viel größere Speicherkapazität und geringere Selbstentladungspotentiale aus. Für die kommerzielle Anwendung dieser beiden Systeme in Lithium-Ionen-Batterien werden grundlegende und verlässliche thermodynamische Daten benötigt. Derzeit ist die Existenz von sieben Lithiumsiliciden sicher nachgewiesen. Dazu zählen die sechs stabilen Phasen Li17Si4, Li16.42Si4, Li13Si4, Li7Si3, Li12Si7, die Hochdruckphase LiSi und die metastabile Phase Li15Si4. Für die ersten fünf genannten Phasen wurden in der ersten Förderperiode des Schwerpunktprogrammes 1473 Wärmekapazitäten und Standardentropien bestimmt. Bei den Lithiumstanniden sind derzeit sieben Phasen gesichert belegt. Allerdings existiert für keine Phase der Lithiumstannide ein verlässlicher thermodynamischer Basisdatensatz. Aus diesem Grund wurden für die beiden zuletzt genannten Lithiumsilicide (Li15Si4 und LiSi), sowie für die Lithiumstannide Li17Sn4, Li7Sn2, Li13Sn5 und Li7Sn3 die fehlenden thermodynamischen Daten experimentell bestimmt. Die hergestellten Phasen wurden zunächst mittels Röntgenbeugung, thermischer und chemischer Analyse charakterisiert. Ein Schwerpunkt dieser Arbeit lag auf der experimentellen Bestimmung der Wärmekapazitäten in einem Temperaturbereich von 2 K bis zur jeweiligen Zersetzungstemperatur der untersuchten Verbindungen. Hierfür wurden zwei unterschiedliche Kalorimeter verwendet: ein Physical Property Measurement System (Quantum Design) von 2 K bis 300 K und eine DSC 111 (Setaram), beginnend ab 300 K. Die experimentellen Daten konnten mit Messunsicherheiten von 1 % bis 2 % über 20 K und bis zu 20 % unterhalb von 20 K angegeben werden. Die Messungen bei niedrigen Temperaturen erlauben zudem die Berechnung der Standardentropien, sowie die Bestimmung von elektronischen Beiträgen und Gitterschwingungsbeiträgen zur Wärmekapazität. Weiterhin ist Fokus dieser Arbeit die Bestimmung der Standardbildungsenthalpien der Lithiumsilicide und Lithiumstannide auf Basis von Wasserstoffsorptionsmessungen mittels einer Sieverts-Apparatur. Hierfür wurden erstmals Messungen an den Lithiumsiliciden ausgehend von Li17Si4, LiH:Si (Li:Si = 17:4), Li16.42Si4 und LiSi durchgeführt. Für die Lithiumstannide dienten als Ausgangsmaterial Li17Sn4, LiH:Sn (Li:Sn =17:4), sowie Li7Sn2 und LiH:Sn (Li:Sn = 7:2). Die Anwendung des van´t-Hoff-Plots resultierte in Messunsicherheiten von mindestens 10 %. Aus diesem Grund wurde eine alternative Auswertemethode gewählt, bei der die ermittelten Wärmekapazitäten und Standardentropien mit den Gleichgewichtsdrücken aus den Wasserstoffsorptionsmessungen miteinander verknüpft werden. Auf diese Weise konnten Standardbildungsenthalpien für die untersuchten Phasen mit Fehlern kleiner 1 % ermittelt werden. Aus den Ergebnissen dieser Arbeit resultierte ein vollständiger, gesicherter thermodynamischer Datensatz für das System Li-Si. Das berechnete Li-Si-Phasendiagramm ist im sehr guten Einklang mit experimentellen literaturbekannten Daten. Für die Lithiumstannide erfolgte eine Validierung der ermittelten thermodynamischen Werte. Die in dieser Arbeit erzielten Ergebnisse liefern einen wesentlichen Beitrag zur Verbesserung der Datenbasis für thermodynamische Berechnungen und für das Verständnis von Phasensequenzen und Gleichgewichten beim Einsatz von Lithiumsiliciden bzw. Lithiumstanniden als Anodenmaterialien in Lithium-Ionen-Batterien.

Decisions made at the early stage of building design can significantly influence theenvironmental, energy and economic performance of buildings. Future homeowners anddevelopers often have to make decisions concerning the design and specification of thebuilding. These choices are usually governed by functionality, aesthetics, cost, materialavailability, etc. Except for decisions related to long-term performances, they are relativelyeasy and straightforward to make. Long-term performance assessments that consider theimpact of a product over its lifetime, requires thorough research. Due to the lack of studies onthe long-term benefits and performance of different building design options, homeowners anddevelopers often base their decisions on short-term financial benefits, ignoring long-termbenefits. This may lead to incorrect decisions that are difficult to correct.Within this context, the aim of this study is to compare the long-term economic viability ofdifferent external timber wall construction types. By doing so, our goal is to address the lackof techno-economic studies within the construction industry and thus, to assist the decisionmakingof Swedish homeowners and developers. We evaluate the economic performance ofthree wooden wall construction alternatives—that of IsoTimber, cross-laminated timber(CLT), and timber frame walls—via thirteen wall assembly scenarios and two case housesfrom Bysjöstrand eco-village, Sweden. The scenarios account for variations in wall type andwall thicknesses. Our study utilizes an approach based on life cycle costing (LCC) andconsiders the capital cost and the present value of heating cost. The latter is calculated for 1m2of heated area of each case houses over a 40-year period. Indoor Climate and Energy software(IDA ICE) is used to estimate the heating energy use and the Bidcon program to estimate thematerials and labor costs for all cases. The study considered reasonable economic parameters,but to see their impact on the results and feasibility of wall constructions improving, sensitiveanalysis has been done using different values.The main finding of this thesis is that timber frame wall construction is the most economicchoice in the long term. In contrast, IsoTimber wall is the least economic choice, in general,and for two-story homes, in particular. Moreover, the present value total cost for IsoTimber intwo-story building is 5% higher than for a single-story building that has a similar U-value. Incontrast, it is 3% and 7% lower for CLT and timber frame walls respectively. Also, the resultsindicate that although the present value heating cost decreases with increasing wall thickness,this increase is considerably smaller than the increase in the capital cost. Finally, assumedeconomic factors affect the results greatly, but in general, improving the U-value of CLT wallconstruction might be the most profitable then timber frame comes after, and then IsoTimbercomes in the last. Along with, return economic benefit from the improvement of all studiedwall constructions in single-story building is higher than the benefit in two-story building.

Lithiumeisen(II)-phosphat ist ein vielversprechendes und umweltfreundliches Kathodenmaterial für den Einsatz in Lithium-Ionen-Batterien (LIB), das eingehend im Hinblick auf seine thermodynamischen- und Oberflächeneigenschaften untersucht wurde. Zur Bestimmung der mittleren molaren Mischungsenthalpie von LiFePO4 und FePO4 wurde die Methode der isothermen Titrationskalorimetrie für die Untersuchung heterogener Stoffsysteme optimiert. Die Ergebnisse konnten mit elektrochemischen Gleichgewichtszellspannungsmessungen validiert werden. Ferner wurde die Oberflächenspannung von reinem LiFePO4 experimentell mit Hilfe der Kapillar-Aufstiegsmethode an Pulvern ermittelt. Ein weiterer Forschungsschwerpunkt stellte experimentelle Bestimmung der Wärmekapazität von phasenreinem orthorhombischen FePO4 dar. Des Weiteren wurde der Ablauf der hydrothermalen LiFePO4-Synthese ausgehend von Li3PO4 und Vivianit anhand von in-situ Messungen der elektrolytischen Leitfähigkeit und thermodynamischen Modellierungen aufgeklärt.

There is growing demand for a more efficient use of polymers that originate from renewable feedstocks due to the depleting supply of fossil fuels, based on economic and environmental reasons. As a result, lignin has attracted renewed interest as a resource for various bioproducts. Lignin is a natural biopolymer with a high carbon content and is composed of aromatic moieties, with a high level of polar functionalities. This makes it a unique precursor for certain high-value applications, such as in biofuels, bioplastics, composite materials, carbon fibers and activated carbons and as a source of phenolic monomers and fine chemicals. Industrial lignins are formed as byproducts of pulping processes (such as kraft, sulfite or alkaline pulping) or result from the biorefining process, where carbohydrates are used for sugar production. Lignin’s intrinsic structure is significantly modified during the processing of lignocellulose, resulting in the formation of more diverse, condensed and less reactive raw materials. Since molecular mass and polydispersity are the most important parameters affecting the chemical reactivity and thermal properties of lignin, additional process steps to improve the quality of crude technical lignins, including kraft lignin, are needed. Solvent extraction is a potentially useful technique for further improving the polydispersity of technical lignins. This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating value, and thermal and sorption properties of industrial hardwood and softwood kraft lignins. The purpose was to understand the correlation between certain structural features in the lignin fractions and their properties to select the appropriate solvent combinations for specific applications of lignin raw materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations were used to separate both spruce and eucalyptus kraft lignins into fractions with lower polydispersities. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material were characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and 31P NMR spectroscopy. The thermal properties of the lignin samples were studied by thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) were obtained through the direct measurement of weight changes during the analysis, while the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The sorption properties of fractionated kraft lignins were studied with respect to methylene blue dye. Additionally, lignin fractions with different molecular weights (and therefore various chemical structures) that were isolated from both softwood and hardwood kraft lignins were incorporated into a tunicate cellulose nanofiber (CNF)-starch mixture to prepare 100% bio-based composite films. The aim was to investigate the correlation between lignin diversity and film performance. The transmittance, density and thermal properties of the films were investigated, as were their mechanical properties, including the tensile stress and Young’s modulus. This part of the study addressed the importance of lignin diversity on composite film performance, which could be helpful for tailoring lignin applications in bio-based composite materials based on the material’s specific requirements.

Im Mittelpunkt der Arbeit stehen Alanate und Aluminiumhydride der Übergangs- und Erdalkalimetalle in Bezug auf ihre Synthese, ihre thermodynamischen Eigenschaften, ihre Zersetzungsreaktionen und ihre potentielle Eignung für reversible Wasserstoffspeicheranwendungen. Es konnten für CeAlH6, Mg(AlH4)2, Ca(AlH4)2, Sr(AlH4)2, CaAlH5 und SrAlH5 die Wärmekapazitätsfunktionen sowie die absoluten Entropien und Bildungsenthalpien bei 298,15 K bestimmt werden. Weiterhin wurden Methoden zur Näherung der genannten thermodynamischen Daten evaluiert und mit den ermittelten Werten aktualisiert und erweitert. Außerdem wurde die im Bereich der komplexen Hydride übliche Annahme, dass sich die bei der Synthese gebildeten Nebenprodukte LiCl und NaCl gegenüber den Hydriden inert verhalten, überprüft. Es konnte gezeigt werden, dass die Annahme hinsichtlich der Eigenschaften und Zersetzungsreaktionen von Mg(AlH4)2, Ca(AlH4)2 und Sr(AlH4)2 Bestand hat. In Bezug auf die Dehydrierung von CaAlH5 und SrAlH5 ist sie jedoch ungültig, wenn die Probe LiCl enthält.

In recent years we may observe a growth in construction of passive houses and low energy houses using lightweight constructions such as modern wooden houses. It is assumed that wooden houses keep overheating more comparing to brick houses during summer period. Due to the lack of research in this field the paper investigates the influence of internal thermal storage mass in passive houses constructions on their summer thermal stability under the Czech climatic conditions. Only sensible heat accumulation without a usage of phase change materials is examined. Differences between wooden houses comparing to brick-built houses are emphasized. Objects of research are mostly residential passive houses in low energy building standards. However, the results of research might be applied to different types of buildings as well. The first section outlines theoretical fundamentals. For the research itself various scientific research methods were used, such as basic mathematical calculations, experimental temperature measurement of two buildings (detached house in Dubňany and in Moravany) and numerical simulations. Own tribute to the research was first of all discussion on the topic of thermal accumulation and structures heat capacity calculation. Experimental measurements outlined conclusive evidence about the importance of internal thermal storage mass in respect of interior summer overheating. The research confirmed that the highest interior temperature reached is mostly influenced by solar gains through unshaded windows. However, the influence of internal thermal storage mass is not remote. If we compare standard timber-framed wooden house to the hole ceramic bricks-built house, the wooden house will overheat by 0,5°C more during a standard day. Wider spread in the maximum temperature reached was measured for lightweight consturctions wooden houses without any internal thermal storage mass. Therefore, such structures should have an additional layer of thermal storage mass.

Sr₃Ru₂O₇ is a quasi-two-dimensional metal and has a paramagnetic ground state that is heavily renormalised by electron-electron correlations and magnetic exchange interactions. Inextricably linked to this renormalisation is the metamagnetism of Sr₃Ru₂O₇ - a rapid rise in uniform magnetisation over a narrow range of applied magnetic field. Knowledge of the zero-field physics is essential to any description of the metamagnetism. Light may be shed on the enigmatic ground state of Sr₃Ru₂O₇ by doping the crystal lattice with foreign cations: this is the primary purpose of the original research referred to in this thesis, in which studies of some of the electronic properties of crystals of cation-doped Sr₃Ru₂O₇ are reported. Single crystals of Sr₃(Ru[subscript(1-x)]Ti[subscript(x)])₂O₇ and Sr₃(Ru[subscript(1-x)]Cr[subscript(x)])₂O₇ have been synthesised in an image furnace and some of the properties of these crystals have been measured. Evidence that indicates the emergence of a spin density wave as a function of Ti-doping in Sr₃(Ru[subscript(1-x)]Ti[subscript(x)])₂O₇ is presented. Time-dependent magnetic irreversibility has been observed in samples of Sr₃(Ru[subscript(1-x)]Cr[subscript(x)])₂O₇, thus hinting at the involvement of the RKKY mechanism in these materials. Regarding cation doping out of the conducting RuO₂ planes, samples of (Sr[subscript(1-y)]La[subscript(y)])₃Ru₂O₇ have been grown and investigated. Both the Sommerfeld coefficient and the Fermi liquid A coefficient of (Sr[subscript(1-y)]La[subscript(y)])₃Ru₂O₇ are found to decrease as a function of y (0 ≤ y ≤ 0.02); these observations point towards a reduction in the thermodynamic mass of the Landau quasiparticles. Results from magnetoresistance and magnetisation measurements indicate that the metamagnetism of the (Sr[subscript(1-y)]La[subscript(y)])₃Ru₂O₇ series probably cannot be explained by a rigid band-shift model. Also, some aspects of these data imply that the metamagnetism cannot be fully accounted for by a spin fluctuation extension to the Ginzburg-Landau theory of uniform magnetisation.

We have developed a new modulation calorimetry technique using RF-Field heating. This technique eliminates temperature gradients across the sample leading to a higher precision in evaluating the heat capacity compared to the previous techniques. A frequency scan was carried out on a 8CB+aerosil sample showing a wide plateau indicating the region of frequency independent heat capacity. A temperature scan was then performed through the first-order nematic to isotropic and second order smectic-A to nematic transitions and was shown to be consistent with the previous work. The amplitude of the RF heating power applied to the sample depends on the permittivity and the loss factor of the sample. Since the permittivity of a dielectric material has a strong temperature dependence in liquid crystals, new information is obtained. The heat capacity measurements have a relative resolution of better than 0.06%, and the phase shift a resolution of 0.03%, were shown to be significant improvements over traditional heating methods. We then applied this new RF calorimetry on bulk and aerosil 8CB dispersions. For the bulk 8CB, the step-like character of smectic-A to nematic transition, and first order nematic to isotropic transitions indicated the strong dominance of the permittivity and the loss factor of the material. For the 8CB+aerosil samples at different silica density, our data were consistent with the previous work and provides clear evidence for the coupling between the smectic-A and nematic phases. We have undertaken a combined T-dependent optical and calorimetric investigation of CCN47+aerosil samples through the I-N transition over a range of silica densities displaying the double I-N transition peak. This work offers compelling evidence that the I-N transition with weak quenched random disorder proceeds via a two-step process in which random-dilution is followed by random-field interactions on cooling from the isotropic phase, a previously unrecognized phenomena.

L'augmentation de la concentration de dioxyde de carbone (CO2) dans l'atmosphère depuis la révolution industrielle a conduit à l'augmentation de la température moyenne du globe. Pour limiter l’accroissement des températures atmosphériques moyennes, la quantité de dioxyde de carbone émise dans l'atmosphère doit être réduite. Une des solutions envisagée sur les sources fixes est le captage et le stockage du CO2. Ce procédé d’absorption/désorption, bien connu dans le traitement du gaz naturel, est onéreux et peu efficace pour le traitement du gaz des sources fixes et doit être optimisé. La solution proposée s’appuie sur l’utilisation de solvants démixants, présentant une séparation de phase équilibre liquide-liquide (LLE) en solution aqueuse en fonction de la température. Ce manuscrit présente une étude réalisée pour la famille des alkyl-pipéridines connues pour ses séparations de phase. Cette étude permettra d’évaluer l’influence de la taille, de la positionet du nombre de substituants sur les propriétés thermodynamiques d’intérêt pour le procédé. Pour étudier les LLE des solutions aqueuses démixantes, en particulier dans le cas des solutions chargées en gaz, deux instruments ont été mis au point. Il a été possible de démontrer que les changements opérés sur les diagrammes de phase des amines sont liés aux réactions chimiques mises en jeu lors de la dissolution du CO2. Pour les alkyl-pipéridines tertiaire on observe la température de démixtion diminue avec l’addition de CO2, allant avec la formation de carbonates. Avec les alkyl-pipéridines secondaires la température de démixtion augmente, ce qui est lié à la présence en solution de carbamates qui stabilisent la solution aqueuse. Le comportement des amines secondaires très encombrées, qui ne peuvent donc pas formées de carbamates, est similaire à celui des amines tertiaires, ce qui est cohérent avec les conclusions précédentes. Une étude approfondies des propriétés thermodynamiques d’excès (VE, CpE et HE) des alkyl-pipéridines en solution aqueuse a également permis de démontrer des relations structure - propriétés. La position du substituant sur le cycle pipéridine a une influence considérable et prévisible sur l’intensité des propriétés d’excès, alors que la nature de l’amine (secondaire ou tertiaire) va influencer la position de l’extremum de cette propriété. Enfin, une modélisation thermodynamique rigoureuses des solubilités et des enthalpies de dissolution du CO2 dans les solutions aqueuses de pipéridines a permis de déterminer les constantes de formation des carbamates dans les solutions aqueuses de 3- et 4-méthylpipéridines. / The increase of carbon dioxide (CO2) concentration in the atmosphere, since the industrial revolution has led to the rise in the average global climate temperature. To prevent the escalation of global climate temperatures the amount of CO2 emitted into the atmosphere must be reduced. One solution is carbon capture and sequestration which removes CO2 from fixed sources. The absorption/desorption cycle is well known for the treatment of acid gas, but is expensive and not as efficient for the treatment of gas from fixed/industrial sources. A solution to this problem is the use of aqueous demixing amine solvents which present a liquid-liquid phase equilibrium (LLE) as a function of temperature. This manuscript presents a study done to measure the LLE and thermodynamic properties of the alkyl piperidine family, which can be used for carbon capture processes. This work evaluates the effect of the size, position and number of alkyl substituents on the thermodynamic properties of interest in the carbon capture process. To study the LLE of aqueous demixing solutions, particularly gas loaded solutions, two novel apparatuses were developed. The results demonstrate that the changes in the amine phase diagrams are related to the chemical reactions involved with dissolution of CO2. The tertiary alkyl piperidines displayed reduced demixing temperature with the addition of CO2 due to the formation of carbonate species. The secondary alkyl piperidines display an increasing demixing temperature which is related to the formation of carbamate species which stabilizes the solution. Secondary alkyl piperidines that are severely sterically hindered, which cannot produce carbamates, behave similarly to the tertiary amine which is coherent with the preceding conclusion. The structure property relationship concerning the excess thermodynamic properties (VE, CpE et HE) of aqueous solutions were studied in depth. This revealed that the position of the substituents on the cyclic ring has a considerable and obvious influence on the intensity of the excess properties, along with the class of the amine, whether secondary or tertiary, will influence the positions of the extrema of the excess property. To conclude, a rigorous thermodynamic model based on the CO2 solubility and the enthalpy of solution for CO2 in aqueous solutions of alkyl piperidine, allowed for the determination of the carbamate formation constants of 3- and 4-methylpiperidine.