Published Article / The quality of spin casting products and mould life are critically dependent on thermal conditions they undergo. In order to improve the performance of production and to optimise the spin-casting process, characteristics of the thermal process was firstly identified by means of the measurement and simulation. Furthermore the investigation of the developed control methods, including the thermal property substitute method and mixture method of the metal powder, was kept on the effect of air-cooling induced automatically from the spinning of the mould on the thermal process. <br>The air cooling system was developed to optimise the thermal process during casting, utilising a theoretical analysis of the air-flow characteristics in a cooling tube submerged in a silicon mould and the characteristics of convection heat transfer associated with the mould and cast part. A numerical simulation of the casting process was also adopted in the analysis. The effect of the developed system on the thermal process was determined experimentally and it was found that a system of aircooling, automatically induced from the spinning of the mould, is feasible in optimisation of the thermal process. <br>The developed control methods can be applied to the practice of spin casting individually or collectively according to the specific situations and requirements.

Doctor of Philosophy / Department of Biological and Agricultural Engineering / Donghai Wang / The depletion of petroleum feedstock along with significant concerns about health and environment lead to an interest in alternative green products. Soy protein (SP) adhesives have great potential as a renewable material for wood industries. The obstacle of applying SP-based adhesives is its relatively low water resistance. The overall objective was to enhance the water resistance of SP adhesives through protein and lignin interaction. An improvement of adhesion performance, flowability, and thermal properties of SP adhesives was achieved through the protein and lignin interaction and formation of protein and lignin copolymer. pH adjustment is a simple process to change protein folding and lignin properties. Cleavage of β-O-4 linkage was observed at pH 8.5 and pH 12, resulting in an increase in lignin active groups and the changes in lignin particle size and thermal properties. Cross-linking of protein with lignin took place via carbonyl, amino, and hydroxyl groups. Multiple-point and non-specific interactions between lignin and protein resulted in stronger lignin-protein networks and changes in properties, which improved wet adhesion strength of protein adhesives. In addition, lignin was depolymerized by laccase enzyme with the presence of mediator, TEMPO, to induce a formation of the strong lignin-protein network. The formation of the strong lignin-protein network increased the wet adhesion strength by 106% and the partial wood failure was observed after the three-layer wood test. A better performance was also observed on the three-cycle soaking test. The adhesion performance of SP adhesives was also greatly affected by lignin particle size and the protein to lignin ratio at pH 4.5. The wet adhesion strength of SP adhesives increased as lignin particle size decreased. The protein-lignin adhesive with protein to lignin ratio of 10:2 (w/w) at 12% solid content had the lowest contact angle and the highest wet adhesion strength of 4.66 MPa, which is 53.3% higher than that of 10% pure SP adhesive. Lignin-protein interactions, water resistance property, and glue line pattern had strong influences on an adhesion performance. Lignin and soy protein were modified at pH 4.5, 8.5 and 12. The maximum increase (620%) in water resistance was found at pH 12 with an addition of lignin. After the protein was unfolded (pH 8.5) and denatured (pH 12), it was refolded by shifting pH to 4.5. The better-wet adhesion performance was obtained at pH 4.5, 8.5-4.5 and 12 with rigid glue line. Shifting pH from 8.5 to 4.5 promoted lignin-protein interaction and increased adhesion performance. The protein-lignin adhesives using absolutely renewable materials and practical processes showed an excellent potential to replace the petroleum-based adhesives and fulfill the global demand for green products and technologies.

La télédétection thermique en temps réel de systèmes volcaniques actifs est une technique cruciale pour comprendre le comportement et l'activité éruptive de corps magmatiques chauds. Cette technologie repose sur la détermination de l'émissivité thermique du magma, un paramètre permettant d'identifier la température du magma. Nous avons utilisé une méthode directe pour obtenir des spectres dans la plage de nombres d’onde allant de 400 à 13000 cm-1; d’échantillons naturels volcaniques (volcan Erebus et Teide) et synthétiques (avec différents éléments). Ces matériaux ont été chauffés de la température ambiante à 2000K avec un laser CO2 et les données ont été collectées pendant toute la phase de chauffage avec un spectromètre IRTF.Nos résultats indiquent que l’émissivité d’une roche magmatique est affectée par les changements de composition et l’histoire thermique. Les mesures d'émittance montrent le rôle important du fer et de la vitesse de refroidissement du magma sur la réponse spectrale des compositions de type phonolitique. Ces observations sont importantes, car une méconnaissance des valeurs d’émissivité engendre des erreurs sur la détermination de la température et, donc à une interprétation erronée de la rhéologie et de l'efficacité thermique du corps magmatique. / Real time thermal remote sensing of active volcanic systems is a crucial technique for understanding the behavior and eruptive activity of hot magmatic bodies. Such technology relies on determining the thermal emissivity of the magma, a parameter to identify the temperature of magma. We used a direct method to obtain a spectrum in the wavenumber range from 400 to 13000 cm-1; the natural (volcano Erebus and Teide) and synthetic samples were heated up from room temperature to 2000K with a CO2 laser and data were collected during all the heating stage with a FTIR spectrometer.Our results thus indicate that thermal emissivity of magmatic rock is affected by changes in composition and thermal history. The emissivity measurements show the important role of the iron and the cooling rate on the spectral response of the phonolite composition. These are important observations since different emissivity will lead to different temperature determinations and hence, an erroneous interpretation on the rheology and thermal efficiency of the magmatic body.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24718号 / エネ博第461号 / 新制||エネ||86(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 宮内 雄平, 教授 大垣 英明, 准教授 中嶋 隆, 特定教授 檜木 達也 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

The effects of coating formulation on thermal characteristics of coating layers were systematically studied for xerographic toner fusion on coated papers. Model coatings were formulated using three types of ground calcium carbonate and one kaolin pigments, each mixed with 6, 10, 18, and 25 pph of styrene butadiene latex binder. Porosity was found to be a key parameter for coating thermal conductivity adjustment, and was determined by the latex concentration. The particle size distribution and morphology of pigments also affect the overall thermal characteristics of coating layers. Print qualities on model coated papers were evaluated by print gloss measurement, toner adhesion test, and pair-wise visual ranking, and it was proved that print gloss is reduced with increasing bulk thermal conductivity of coating layers. The coating layer consisted of Covercarb HP pigment and 10 pph of latex was found to have the best performance in the three print quality evaluation tests.

The effects of coating formulation on thermal characteristics of coating layers were systematically studied for xerographic toner fusion on coated papers. Model coatings were formulated using three types of ground calcium carbonate and one kaolin pigments, each mixed with 6, 10, 18, and 25 pph of styrene butadiene latex binder. Porosity was found to be a key parameter for coating thermal conductivity adjustment, and was determined by the latex concentration. The particle size distribution and morphology of pigments also affect the overall thermal characteristics of coating layers. Print qualities on model coated papers were evaluated by print gloss measurement, toner adhesion test, and pair-wise visual ranking, and it was proved that print gloss is reduced with increasing bulk thermal conductivity of coating layers. The coating layer consisted of Covercarb HP pigment and 10 pph of latex was found to have the best performance in the three print quality evaluation tests.

In vorliegender Arbeit wurden Synthese, Kristallstruktur und thermisches Verhalten von sauren und basischen Monofluorophosphate untersucht. Es wurden Salze mit Alkalimetall- und N-haltigen Kationen dargestellt und kristallographisch charakterisiert. Die Strukturen dieser Verbindungen wurden dann mit denen der isoelektronischen Hydrogensulfate verglichen. Mit Hilfe des Kationenaustausches und der Gefriertrocknung konnte ein erfolgreicher Syntheseweg fuer diese Verbindungen entwickelt werden. Die Gefriertrocknung hinderte die Abspaltung von HF und Kondensation des Phosphats und ermöglichte die Isolierung der Rohprodukte. Auf diesem Weg gelang die Darstellung der reinen Verbindungen in höherer Ausbeute, so daß es möglich wurde, die Substanzen mit unterschiedlichen Methoden zu untersuchen. Hergestellt und kristallographisch untersucht wurden folgende Verbindungen: - Hydrogenmonofluorophosphate mit × Alkalimetallkationen: Na, K, Rb, Cs × N-haltigen Kationen: NH4, NMe4, NH2Et2, NHEt3, [C(NH2)3], {HOC[NH(CH3)]2}, [H2N(CH2CH2)NH2], - basische Monofluorophosphate: Na2PO3F·10H2O und [C(NH2)3]2PO3F - gemischte Salze: Cs3(NH4)2(HPO3F)3(PO3F)2 und Na5[NMe4](PO3F)3·18H2O. Die Kristallstrukturen zeigen eine Vielzahl an Strukturtypen, definiert durch die Verknüpfung der verzerrten HPO3F Tetraeder über kurze O-H···O Wasserstoffbrückenbindungen zu Ketten, Dimere oder Tetramere. Diese sind ihrerseits über längere N-H···O und Ow-H···O Wasserstoffbrückenbindungen verknüpft. Kompliziertere Strukturmotive sind in den Strukturen der basischen Monofluorophosphate und der gemischten Salze zu finden. Allgemein werden nur Wasserstoffbrückenbindungen des Typs N-H...O und O-H...O gefunden, dagegen werden keine N-H···F Bindungen in den Strukturen beobachtet. Auch ist mehrheitlich keine Isotypie zwischen sauren und basischen Monofluorophosphaten einerseits und den entsprechenden Sulfaten andererseits zu finden. Isotyp sind nur die Strukturen [NMe4]HPO3F·H2O mit [NMe4]HSO4·H2O und Na2PO3F·10H2O mit Na2SO4·10H2O. Interessanterweise wurden genau in einer dieser isotypen Strukturen, nämlich der des Na2PO3F×10H2O, als Ausnahme zwei O-H···F Bindungen gefunden. Die O···F Abstände liegen im Bereich der Abstände der Ow···O Bindungen in der Struktur. Eine Erklärung für das seltene Auftreten von H-Brücken mit Fluor als Akzeptor ist eine fast vollständige Valenz des Fluors durch seine Bindung zum Phosphor. Mehrere Strukturen widerspiegeln diese Tatsache mit der Orientierung der P-F Bindung. Die Bindung wird nach inerten Stellen, wo kein Metall- oder Wasserstoffatom in der Struktur vorhanden ist, ausgerichtet, um ein weiteres Binden des Fluors (Metallkoordination, Wasserstoffbrückenbindung) zu vermeiden. Weiterhin wurde das thermische Verhalten der Verbindungen NaHPO3F, NaHPO3F·2.5H2O, CsHPO3F und [NHEt3]HPO3F untersucht. Dies erfolgte mit dem Ziel, Information über mögliche Phasenübergänge und die unterschiedlichen Zersetzungstypen zu bekommen. Sowohl der Kation wie auch die Anwesenheit von Kristallwasser haben Einfluß auf den thermischen Abbau. Die Na-Verbindungen zeigen eine Zersetzung über mehrere Schritte, die zu unterschiedlichen Endprodukten führt (Na3P3O9 für NaHPO3F und (NaPO3)n für das Hydrat). Im Vergleich dazu zersetzt sich CsHPO3F nach dem Schmelzen direkt zum Endprodukt, ohne stabile Zwischenprodukte zu bilden. Ähnlich verläuft der thermische Abbau der [NHEt3] Verbindung, die sich allerdings mit einem Masseverlust von 92,27%, also ohne Bildung eines signifikanten Endproduktes, vollständig zersetzt. Während des thermischen Abbaus wurde die Freisetzung von HF und H2O bei allen Verbindungen beobachtet, die sich aber bezüglich der Zersetzungstemperatur und -menge zwischen den Substanzen unterscheiden. Es wurden keine Phasenübergänge erster Ordnung beobachtet. Dies war insbesondere für CsHPO3F überraschend, da das isoelektronische Hydrogensulfat mehrere Phasenübergänge aufweist [2]. Das Ausbleiben von Phasenübergängen allgemein und auch für CsHPO3F wird folgendermassen erklärt. Während das Sulfat Bindungsmöglichkeiten an allen vier Ecken des SO4-Tetraeders hat, besitzt der (H)PO3F-Tetraeder nur eine begrenzte Flexibilität wegen der Anwesenheit von Fluor an einer Ecke. Fluor bevorzugt eine "isolierte" Position am Phosphor. Anhand der vorliegenden Ergebnisse kann die Schlußfolgerung gezogen werden, daß Fluor auf Grund seiner niedrigeren Valenz im Vergleich zu Sauerstoff andere strukturelle und funktionelle Charakteristika aufweist. Die Valenzunterschiede zwischen Sauerstoff und Fluor haben einen starken Einfluß auf das Wasserstoffbrückenbindungssystem in den Kristallstrukturen der Hydrogenmonofluorophosphate und folglich auf die "Nicht-Isotypie" zu den Hydrogensulfaten. / In this thesis, the crystal structures and thermal behavior of hydrogen monofluorophosphates and basic monofluorophosphates with alkali metal and N-containing cations were studied. A comparison to the analogous hydrogen sulfates showed interesting structural variations and differences in thermal behavior. Synthesis of the studied monofluorophosphates involved cation exchange and freeze drying. Freeze drying enabled the isolation of raw products by avoiding the escape of HF and consequent phosphate condensation. This method of preparation led to the synthesis of the hydrogen monofluorophosphates with the following cations: - the alkali metals: Na+, K+, Rb+, and Cs+, - N-containing cations: NH4+, [NMe4]+, [NH2Et2]+, [NHEt3]+, [C(NH2)3]+, {HOC[NH(CH3)]2}+, and [H2N(CH2CH2)NH2]2+, and the basic monofluorophoshates, Na2PO3F·10H2O and [C(NH2)3]2PO3F. The following mixed salts were also obtained with partial cation exchange: - Cs3(NH4)2(HPO3F)3(PO3F)2 - Na5[NMe4](PO3F)3·18H2O. In the crystal structures, the HPO3F tetrahedra were hydrogen-bonded to chains, dimers, and tetramers in the structures of the hydrogen monofluorophosphates. Extensive hydrogen bonding in the basic monofluorophosphates due to high amounts of crystal water led to more complicated structural motifs. Limitations on the bonding of fluorine were observed in each of the structures, whether it be metal coordination or hydrogen bonding. The valency of fluorine is filled by its bond to phosphorus and thus, generally, the fluorine atom does not participate in additional bonds. This explains why, for the most part, the hydrogen monofluorophosphates are not isostructural with the hydrogen sulfates. Only three atoms of the tetrahedron instead of four atoms are available for hydrogen bonding, which influences the crystal structure. This was further confirmed by the comparison of the decahydrates, Na2PO3F×10H2O and Na2SO4×10H2O, which are consequently isostructural based on two O-H×××F bonds formed in Na2PO3F·10H2O. These were the only hydrogen bonds found that involved fluorine as an hydrogen acceptor or donor. The investigations on the thermal behavior of NaHPO3F, NaHPO3F·2.5H2O, CsHPO3F, and [NHEt3]HPO3F found no first-order phase transitions. Stepwise decompositions were observed for the sodium salts, which was attributed to the formation of stable intermediates identified with simulated experiments. The Cs and [NHEt3] compounds demonstrated a direct decomposition postmelting. In general, the release of H2O from the melt occured at lower temperatures, while HF escaped at higher temperatures. The temperatures, at which this initially occured, and the first maximum observed were dependent on the cation and the presence of crystal water. The immediate decomposition of CsHPO3F after melting differs from that of the hydrogen sulfate, CsHSO4, which undergoes several phase transitions before decompositon. This suggests that the sulfate has more structural flexibility on the basis of the four oxygen corners of the tetrahedra. In comparison, the monofluorophosphate is limited in its bonding mobility due to the presence of fluorine on one of the tetrahedral vertices. Therefore, phase transitions are not observed prior to decomposition. It was concluded that fluorine functions differently in the crystal structures on the basis of its lower valency. Thus, the difference in valency between fluorine and oxygen affects the hydrogen bonding of the hydrogen monofluorophosphates and thus pervents the expected isotypy of the isoelectronic hydrogen monofluorophosphates and hydrogen sulfates.