京都大学 / 新制・課程博士 / 博士(医学) / 甲第24789号 / 医博第4981号 / 新制||医||1066(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 江木 盛時, 教授 湊谷 謙司, 教授 花川 隆 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

In den vergangenen Jahren wurden stetig wachsende Produktionskapazitäten von Biokunststoffen aus nachwachsenden Rohstoffe nverzeichnet. Trotz großer Produktionskapazitäten und einem geeigneten Eigenschaftsprofil findet Stärke nur als hydrophile, mit Weichmachern verarbeitete thermoplastische Stärke (TPS) in Form von Blends mit z. B. Polyestern Anwendung. Gleiches gilt für Kunststoffe auf Proteinbasis. Die vorliegende Arbeit hat die Entwicklung von Biokunststoffen auf Stärkebasis zum Ziel, welche ohne externe Weichmacher thermoplastisch verarbeitbar und hydrophob sind sowie ein mechanisches Eigenschaftsprofil aufweisen, welches ein Potenzial zur Herstellung von Materialien für eine Anwendung als Verpackungsmittel bietet. Um die Rohstoffbasis für Biokunststoffe zu erweitern, soll das erarbeitete Konzept auf zwei industriell verfügbare Proteintypen, Zein und Molkenproteinisolat (WPI), übertragen werden. Als geeignete Materialklasse wurden Fettsäureester der Stärke herausgearbeitet. Zunächst fand ein Vergleich der Säurechlorid-Veresterung und der Umesterung von Fettsäurevinylestern statt, woraus letztere als geeignetere Methode hervorging. Durch Variation der Reaktionsparameter konnte diese optimiert und auf eine Serie der Fettsäurevinylester von Butanoat bis Stearat für DS-Werte bis zu 2,2-2,6 angewandt werden. Möglich war somit eine systematische Studie unter Variation der veresterten Fettsäure sowie des Substitutionsgrades (DS). Sämtliche Produkte mit einem DS ab 1,5 wiesen eine ausgprägte Löslichkeit in organischen Lösungsmitteln auf wodurch sowohl die Aufnahme von NMR-Spektren als auch Molmassenbestimmung mittels Größenausschlusschromatographie mit gekoppelter Mehrwinkel-Laserlichtstreuung (GPC-MALLS) möglich waren. Durch dynamische Lichtstreuung (DLS) wurde das Löslichkeitsverhalten veranschaulicht. Sämtliche Produkte konnten zu Filmen verarbeitet werden, wobei Materialien mit DS 1,5-1,7 hohe Zugfestigkeiten (bis zu 42 MPa) und Elastizitätsmodule (bis 1390 MPa) aufwiesen. Insbesondere Stärkehexanoat mit DS <2 sowie Stärkebutanoat mit DS >2 hatten ein mechanisches Eigenschaftsprofil, welches insbesondere in Bezug auf die Festigkeit/Steifigkeit vergleichbar mit Verpackungsmaterialien wie Polyethylen war (Zugfestigkeit: 15-32 MPa, E-Modul: 300-1300 MPa). Zugfestigkeit und Elastizitätsmodul nahmen mit steigender Kettenlänge der veresterten Fettsäure ab. Ester längerkettiger Fettsäuren (C16-C18) waren spröde. Über Weitwinkel-Röntgenstreuung (WAXS) und Infrarotspektroskopie (ATR-FTIR) konnte der Verlauf der Festigkeiten mit einer zunehmenden Distanz der Stärke im Material begründet werden. Es konnten von DS und Kettenlänge abhängige Glasübergänge detektiert werden, die kristallinen Strukturen der langkettigen Fettsäuren zeigten einen Schmelzpeak. Die Hydrophobie der Filme wurde anhand von Kontaktwinkeln >95° gegen Wasser dargestellt. Blends mit biobasierten Polyterpenen sowie den in der Arbeit hergestellten Zein-Acylderivaten ermöglichten eine weitere Verbesserung der Zugfestigkeit bzw. des Elastizitätsmoduls hochsubstituierter Produkte. Eine thermoplastische Verarbeitung mittels Spritzgießen war sowohl für Produkte mit hohem als auch mittlerem DS-Wert ohne jeglichen Zusatz von Weichmachern möglich. Es entstanden homogene, transparente Prüfstäbe. Untersuchungen der Härte ergaben auch hier für Stärkehexanoat und –butanoat mit Polyethylen vergleichbare Werte. Ausgewählte Produkte wurden zu Fasern nach dem Schmelzspinnverfahren verarbeitet. Hierbei wurden insbesondere für hochsubstituierte Derivate homogenen Fasern erstellt, welche im Vergleich zur Gießfolie signifikant höhere Zugfestigkeiten aufwiesen. Stärkeester mit mittlerem DS ließen sich ebenfalls verarbeiten. Zunächst wurden für eine Übertragung des Konzeptes auf die Proteine Zein und WPI verschiedene Synthesemethoden verglichen. Die Veresterung mit Säurechloriden ergab hierbei die höchsten Werte. Im Hinblick auf eine gute Löslichkeit in organischen Lösungsmitteln wurde für WPI die Veresterung mit carbonyldiimidazol (CDI)-aktivierten Fettsäuren in DMSO und für Zein die Veresterung mit Säu-rechloriden in Pyridin bevorzugt. Es stellte sich heraus, dass acyliertes WPI zwar hydrophob, jedoch ohne Weichmacher nicht thermoplastisch verarbeitet werden konnte. Die Erstellung von Gießfolien führte zu Sprödbruchverhalten. Unter Zugabe der biobasierten Ölsäure wurde die Anwendung von acyliertem WPI als thermoplastischer Filler z. B. in Blends mit Stärkeestern dargestellt. Im Gegensatz hierzu zeigte acyliertes Zein Glasübergänge <100 °C bei ausreichender Stabilität (150-200 °C). Zeinoleat konnte ohne Weichmacher zu einer transparenten Gießfolie verarbeitet werden. Sämtliche Derivate erwiesen sich als ausgeprägt hydrophob. Zeinoleat konnte über das Schmelzspinnverfahren zu thermoplastischen Fasern verarbeitet werden. / In recent years, a steadily growing production capacity of bioplastic based on renewable resources was noticed. Despite its huge production capacities and an appropriate property profile (ubiquitous occurrence, easy extraction), starch is only applied in addition of plasticizers in a hydrophilic, thermoplastic form in blends with e. g. polyesters. The same applies to bioplastics based on proteins. The actual study has the aim to develop starch-based bioplastics, which are hydrophobic, thermoplastic without the addition of any plasticizer and have mechanical properties to be a suitable alternative material in the area of food packaging. To obtain a variation of the raw materials for bioplastics, the concept shall be applied to two types of industrial available proteins, whey protein isolate (WPI) and Zein. Fatty acid esters of starch came out to be a suitable class of materials. Initially, the methods of esterifying acid chlorides and the transesterification of fatty acid vinyl esters were compared with the latter being more appropriate. Reaction parameters of this method were optimized and it was applied to a complete series of vinyl ester reagents (butanoate to stearate), leading to degree of substitution (DS)-values up to 2.2-2.6. With that, a systematic study of the variation of the fatty acid ester chain as well as the DS became possible. It came out that all products with a DS >1.5 showed a well-marked solubility in organic solvents, whereby solution NMR-studies as well as measurements of the molecular weight distributions by using size exclusion chroma-tography with multi-angle laser light scattering (SEC-MALLS) were possible. The different solution behavior was studied by dynamic light scattering (DLS). All soluble products could be formed into films via casting, where materials with a DS of 1.5-1.7 showed the highest values concerning tensile strength (up to 42 MPa) and Youngs modulus (up to 1390 MPa). Especially starch hexanoate with DS <2 and starch butanoate with a DS >2 revealed mechanical properties which are comparable to usually applied polymers for food packaging, e. g. polyethylene (tensile strength: 15-20 MPa, E-Mod: 300-1300 MPa). Tensile strength and Youngs modulus were reduced with increasing length of the esterified fatty acid. Wide-angle X-Ray scattering (WAXS) and infrared spectroscopy (ATR-FTIR) explained this tendency by an increasing intermolecular distance of the starch in the material. Glassy transitions of the materials were detected and showed a dependency on the type of esterified fatty acid and the DS. The crystalline structures of the esterified long-chain fatty acids revealed a melting peak. All films came out to be hydrophobic with contact angles against water >95°. The tensile strength and the Youngs modulus of the highly substituted products could be further improved by blending them with biobased polyterpenes as well as the acylated Zein. A thermoplastic processing without the use of any plasticizer additives was possible for products with a medium and high DS. Homogeneous, transparent testing specimens were obtained. The specific mechanical values were comparable with the casted films, although the highest values for the tensile strength and the elongation were lower. Investigations of the hardness showed comparable values to polyethylene. Selected samples were further processed to fibers by melt spinning. Especially starch esters with high DS revealed homogeneous fibers with a significant increase in the tensile strength compared to the film or testing specimen. Even fatty acid starch esters with a medium DS were processed by the melt-spinning, but their higher glassy transition lead to a reduced softening behavior. To transfer this concept to the class of proteins, different methods of synthesis were studied in the first step, which differed in their amount of acylation. The acylation using fatty acid chlorides lead to highest values. With regard to a well-marked organic solvent solubility, in the case of WPI the acylation with carbonyldiimidazol (CDI)-activated fatty acid was established. For Zein, the acid chloride acylation in pyridine gave the desired results. It came out the fatty acid acylated soluble WPI could not be thermoplastic processed without additional plasticizers. By using biobased oleic acid as additive, the potential of acylated WPI as a thermoplastic filler in blends with e. g. fatty acid esters of starch was shown. In contrast, fatty acid acyl derivatives of Zein revealed well marked glassy transitions <100 °C with an adequate thermal stability. While Zeinoleate could be formed into transparent films via solvent casting without any plasticizer additives, low amounts of tall oil enabled film-forming in the case of acyl derivatives with shorter fatty acids as well. All derivatives revealed a well-marked hydrophobicity. Finally, Zeinoleate was thermoplastically processed into fibers by melt-spinning without any further additives.

This thesis focuses on the different degradation mechanisms of the stainless steel in a travelling grate in a Grate-Kiln iron ore pellet indurator. The travelling grate is a conveyor belt that transports green-body pellets to a rotary kiln while the pellets are being dried and pre-heated to a temperature of 900-1100 °C by recycled hot air. After unloading of the pellets to the rotary-kiln for further sintering, the travelling grate is cooled in room temperature while returning to the loading zone of the wet pellets. The steel was tested during thermal cycling in a test-rig, in order to simulate the influence of thermo mechanical fatigue and oxide spallation. The influence of erosion-deposition was investigated in a modified horizontal industrial combustion kiln at 800 °C, with slag and coal from production used as erosive media and combustion fuel, respectively. The influence of minor alloying additions of Mn, Si and Ti on the microstructure was explored by eight different casted alloy compositions. Isothermal heat treatments were performed at 800 °C during 200 hours on steel immersed in deposits recovered from a travelling grate in production. The three main degradation mechanisms found in this work are thermal spallation, erosion-deposition and deposit induced accelerated corrosion (DIAC). Thermal spallation of the oxide layer is caused by the thermal expansion difference between the oxide and the metal during heating and cooling. It has been found that Ti improves the spallation resistance while Si reduces it. Spallation of deposits is another cause believed to increase the degradation. Erosion-deposition appears due to simultaneous erosion and deposition of particles on the travelling grate that causes erosion or deposition depending on the amount of alkali metals in the environment. The velocity of the particles also influences erosion and deposition in the way that higher velocities increase erosion. DIAC is proposed to form on the travelling grate due to the concentration of chloride- and sulphate containing alkali metals in the deposits.  Other than these major degrading mechanisms, minor degradation mechanisms such as internal oxidation, sigma formation, carburization and sensitization towards inter-granular attack have been found inside the steel during heating. Thermo mechanical fatigue (TMF) causes intergranular cracks in the material of the travelling grate. Casting issues such as micro-segregation have also been addressed in this thesis. A few different ways to improve degradation resistance have been proposed, such as homogenization heat treatments, optimization of process parameters and inhibitor solutions.

Bread waste represents a significant portion of global food waste, necessitating innovative approaches for its valorization. This research project explores the utilization of bread waste through fermentation with Aspergillus oryzae to produce fungal film which could be used for textile applications. While previous studies have examined various applications of food waste, this project specifically targets the textile industry, aiming to mitigate pollution associated with conventional textile manufacturing. The objective of this project was to investigate the feasibility of creating fungal films derived from bread waste. Additionally, to analyze the material's properties through assessments of tensile strength, microscopic analysis, and the identification of an appropriate methodology for this investigation. The biomass suspension was prepared using an ultrafine grinder, and a kitchen blender was subsequently employed to minimize the presence of remaining solids from the grinding process. Additionally, a range of strategies for film casting and wet laying were implemented and evaluated. Wet laying involved combining fungal biomass with tannin to mimic the characteristics of leather. On the other hand, casting utilized pre-treated biomass suspension to assess the formation and quality of the films. As the research progressed and different tannins were used to treat the biomass, a methodology was developed, and glycerol was introduced as a plasticizer. Furthermore, nanocellulose was later incorporated exclusively for the casting of the films to serve as a binder. The films that were produced gave interesting results are observed in casted sheets containing nanocellulose and glycerol-infused biomass (3% BM + 2% Cellulose + 0.13 g Glycerol), exhibiting exceptional tensile strength (35.1 ± 3.42 MPa) and elongation (16.7 ± 5.98%). Wet laid biomass sheets treated with Tara and glycerol display tensile strength (19.9 ± 3.55 MPa) and elongation (6.66 ± 3.02%). These findings signify the potential for developing fungal films from bread waste, necessitating further research to refine methodologies. Overall, this research project paves the way for future advancements in fungal films derived from bread waste. By investigating the use of Aspergillus oryzae and employing wet laying and casting techniques, the project establishes a foundation for sustainable textile production. The successful utilization of bread waste not only addresses the issue of food waste but also contributes to reducing pollution in the textile industry.

The design and analysis of large casted parts present significant challenges due to their complex geometry. Finite Element (FE) modeling is a vital tool for understanding the performance of casted components. However, the computational requirements associated with these parts often lead to excessive processing times and resource utilization. This thesis aims to enhance the efficiency of the mid-surface model creation by developing an FE modeling approach suited explicitly for large casted components. The study begins by exploring the background of casted parts and their applications. A comprehensive analysis of modeling and meshing techniques is conducted, emphasizing their application to large casted components. Building upon this knowledge, different ideas are examined, leading to the proposal of a methodology combining CAD strategies for design features, hybrid meshing techniques, and approaches aimed at reducing FE modeling time to streamline the overall process.To validate the proposed approach, a series of case studies involving casted parts with varying levels of complexity are undertaken. Real-world casting process parameters are considered, highlighting the advantages and limitations in each ideation phase. The proposed methodology is tested and show cased to expert engineers to evaluate its efficiency and feasibility. Furthermore, the efficiency of the new approach is quantitatively evaluated in terms of processing time. The developed methodology offers engineers and researchers a powerful tool to accelerate the design process and optimize FE modeling time while managing computational costs. As industries continue to push the boundaries of size and complexity in casted part design, the insights and techniques presented in this thesis offer a valuable resource for addressing the various engineering challenges inherent in future endeavors. / Utformningen och analysen av stora gjutna delar innebär betydande utmaningar på grund av deras komplexa geometri. Finita Element (FE)-modellering är ett viktigt verktyg för att förstå prestandan hos gjutna komponenter. De beräkningskrav som är förknippade med dessa delar leder dock ofta till alltför långa handläggningstider och resursutnyttjande. Detta examensarbete syftar till att förbättra effektiviteten av skapandet av mittyteta modeller genom att utveckla en FE-modelleringsmetod som är specifikt lämpad för stora gjutna komponenter. Studien börjar med att utforska bakgrunden till gjutna delar och deras tillämpningar. En omfattande analys av modellerings-och diskret iseringstekniker genomförs, med tonvikt på deras tillämpning på stora gjutna komponenter. Med utgångspunkt i denna kunskap undersöks olika idéer, vilket leder till förslaget om en metod som kombinerar CAD-strategier för designfunktioner, hybridmodelleringstekniker och tillvägagångssätt som syftar till att minska FE-modelleringstiden för att effektivisera den övergripande processen. För att validera det föreslagna tillvägagångssättet genomförs en serie fallstudier som involverar gjutna delar med varierande nivåer av komplexitet. Verkliga gjutprocessparametrar beaktas, vilket belyser fördelarna och begränsningarna i varje idéfas. Den föreslagna metoden testas och visas upp för expertingenjörer för att utvärdera dess effektivitet och genomförbarhet. Dessutom utvärderas effektiviteten av det nya tillvägagångssättet kvantitativt i termer av handläggningstid. Den utvecklade metoden erbjuder ingenjörer och forskare ett kraftfullt verktyg för att påskynda designprocessen och optimera FE-modelleringstiden samtidigt som de hanterar beräkningskostnader. När industrier fortsätter att tänja på gränserna för storlek och komplexitet idesign av gjutna delar, erbjuder de insikter och tekniker som presenteras i denna avhandling en värdefull resurs för att ta itu med de olika tekniska utmaningarna som är inneboende i framtida strävanden.