Vocal fold scarring, caused by injury and inflammation, presents significant treatment challenges. Tissue engineering might be a promising treatment for vocal fold restoration or regeneration. It is important to investigate how scaffold properties alter cell behavior instead of screening thousand of materials, which is fundamental knowledge for rational scaffold design. This work studies how tuning only one parameter, mechanical strength of the hydrogel scaffold, influences the extracellular matrix production of encapsulated porcine vocal fold fibroblast (PVFF). PVFF cells were encapsulated by photopolymerization in 10 wt%, 20 wt%, and 30 wt% poly(ethylene glycol) diacrylate (PEGDA) hydrogels (MW 10,000), with the similar biochemical environment and network structure but different mechanical properties. Cell adhesive peptide, RGDS, was grafted into each hydrogel network to mimic a cell adhesive environment. The glycosaminoglycans (GAGs) production per cell increased from 10 wt% to 20 wt%, 30 wt% gels, with an increase in hydrogel stiffness. The collagen production per cell increased from 10 wt% to 20 wt% gels but no further increase occurred with the increasing modulus from 20 wt% to 30 wt% gels. Interestingly, in hydrogels of intermediate modulus (20% PEGDA hydrogels), the highest elastin per cell was observed compared with gels with higher and lower storage modulus after day 30. Histological analysis showed GAGs, collagen and elastin were distributed pericellularly. However, the organization of collagen type I appeared to be influenced by gel mechanical properties, which was confirmed by immunohistological analysis. Furthermore, the immunohistological analysis showed that the phenotype of PVFF is regulated by the stiffness of the PEG hydrogel. This study demonstrates that different levels of VFF ECM formation may be achieved by varying the mechanical properties of PEG hydrogels and validates a systematic and controlled platform for further research of cell-biomaterials interaction.

L'intérêt industriel des composites alumine-zircone ZTA (Zirconia Toughened Alumina) a déjà été largement démontré dans la littérature, notamment pour les applications biomédicales telles que les prothèses orthopédiques. La combinaison du renforcement par transformation de phase de la zircone et de la stabilité de la matrice d'alumine permet de dépasser les propriétés mécaniques des composés monolithiques. La dépendance des propriétés mécaniques vis-à-vis des conditions d'élaboration rend toutefois la production industrielle de tels composites très complexe. Le premier objectif de cette thèse CIFRE, en collaboration avec la société Nanoe et le laboratoire SPMS, est la production de composites alumine-zircone contenant de 2.5 à 50%m de zircone pour ensuite pouvoir les caractériser systématiquement en termes de propriétés microstructurales, structurales et mécaniques, notamment en se concentrant sur les aspects de stabilité de la phase tétragonale de la zircone. La méthode de production industrielle mise au point permet d'obtenir des composites denses à plus de 99% et présentant des microstructures fines et homogènes. Les tailles de grains des deux matériaux dans le composite sont dépendantes de sa composition en zircone mais indépendantes du taux de stabilisant dans la zircone. La comparaison des propriétés microstructurales aux résultats structuraux et mécaniques nous a permis de mettre en évidence plusieurs phénomènes. Hormis la variation de taille de grain et de macro-contraintes due à la différence de coefficients de dilatation thermique, l'alumine est relativement insensible à l'effet du composite. Le contrôle de la stabilité de la phase tétragonale dans les composites nécessite la prise en compte de multiples phénomènes à différentes échelles. À l'échelle de la maille, le premier effet bien connu est celui du dopage par l'oxyde d'yttrium qui stabilise la phase tétragonale. Nous avons mis un autre effet en évidence : les macro-tensions appliquées par la matrice d'alumine déstabilisent la maille tétragonale. Pourtant la rétention de la phase tétragonale de la zircone pure dans la matrice d'alumine est rendue possible par l'effet d'inhibiteur de croissance et la rigidité de l'alumine. La matrice d'alumine stabilise donc la phase tétragonale à l'échelle du grain. Cette observation nous a notamment permis de déterminer la taille critique de transformation spontanée de la zircone pure dans les composites alumine-zircone qui est comprise entre 250 et 310nm. De la même manière, l'absence de vieillissement pour les composites contenant moins de 40%m de zircone nous indique que la taille critique de vieillissement de la zircone dopée à 3%mol d'oxyde d'yttrium est comprise entre 310 et 360nm dans le composite. Il faut donc maîtriser chacun de ses effets pour obtenir à la fois le renforcement par transformation le plus efficace et la meilleure résistance au vieillissement. D'après notre étude, cet optimum se situe entre 1 et 2%mol d'oxyde d'yttrium pour des ZTA présentant une taille de grain de zircone inférieure à 300nm. / Industrial interest of alumina-zirconia composites (ZTA Zirconia Toughened Alumina) is very well-known, especially for biomedical applications as orthopedics prosthesis. Combining the toughening by phase transformation of zirconia and the stability of the alumina matrix allows to reach better mechanical properties than the monolithic compounds. The dependence between mechanical properties and elaboration process makes the industrial production pretty complex. The first aim of this work in collaboration between Nanoe Company and the SPMS laboratory is the achievement of the production of ZTA with 2.5 to 50wt%. The second aim is the systematical study of microstructural, structural and mechanical properties of ZTA by focusing on the key parameters for the stability of the tetragonal phase. The developed industrial process leads to ZTA with densities above 99% and with very fine and well-dispersed microstructures. Both grain size materials depend on the composition in zirconia but did not depend on the yttria content in zirconia. Thanks to the comparison between microstructural, structural and mechanical properties, we identified several phenomenons. Excepting the variation of grain size and macrostrains due to the difference between coefficient of thermal expansion of alumina and zirconia, the alumina is more or less unaffected by the composite effect. Several phenomenons at different scale have an influence on the stability of tetragonal zirconia. At the lattice scale, the stabilizing effect of yttria is well-known. We identified another effect, the tensile stress applied by the alumina matrix destabilize the tetragonal zirconia. Even though, the retention of the tetragonal phase of unstabilized zirconia is achieved thanks to the inhibition of grain growth and the rigidity of the alumina matrix. The alumina matrix stabilizes the tetragonal zirconia at the grain scale. This observation allows us to determine that the critical grain size for spontaneous transformation for unstabilized zirconia ranges between 250 and 310nm. In the same way, the resistance of ZTA until 40wt% to the ageing indicates that the critical grain size for ageing for 3mol% yttria doped zirconia ranges between 310 and 360nm. In order to obtain the more efficient toughening by phase transformation and the better ageing resistance, we need to have an entire control of all these effects. This study concluded that the best compromise between toughening and ageing is achieved for ZTA with zirconia grain size below 300nm and doping between 1 and 2mol% of yttria.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22497号 / 農博第2401号 / 新制||農||1077(附属図書館) / 学位論文||R2||N5277(農学部図書室) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 矢野 浩之, 教授 和田 昌久, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Yes / This paper evaluates the influence of mineral admixtures partially replacing cement, sea sand replacing quartz, sea water replacing fresh water on ultra-high performance concrete (UHPC). The fluidity and mechanical properties were studied. Besides, the impermeability, chloride resistance and freeze-thaw resistance were investigated. Failure modes, scanning electron microscope (SEM) analysis, mass loss, relative dynamic modulus of elasticity and mechanical properties of UHPCs after freeze-thaw cycles were conducted. The results showed the fluidity of UHPC paste gradually increases with the improvement of water-binder ratio. It is recommended that the water-binder ratio of UHPC be set at 0.19. The fluidity also increases with the improvement of the content of slag, fly ash and water reducer, but decreases with the improvement of silica fume content. The flexural and compressive strengths of UHPC enhance with the improvement of the content of silica fume, but reduce with the improvement of the content of fly ash and slag. The UHPCs made of quartz sand, river sand and sea sand, all, achieve a high strength. UHPCs prepared at standard curing conditions, with or without steel fibers, mixed by artificial seawater and made of sea sand, exhibited excellent impermeability and chloride resistance. The frost resistant grade of all UHPC specimens prepared by standard curing are greater than F500 exhibiting excellent freeze-thaw resistance and sustainability.

No description available.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23945号 / 農博第2494号 / 新制||農||1090(附属図書館) / 学位論文||R4||N5380(農学部図書室) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 北島 薫, 准教授 岡田 直紀, 教授 小杉 緑子 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Yes / Designing and manufacturing functional parts with enhanced mechanical property is a major goal of fused filament fabrication (FFF) for polymeric elastomers, which exhibits major advantages in producing such parts with a range of structures. But the unsatisfactory mechanical performance constrains greatly its real application and there is yet no consensus in the mechanical characterization of printed samples. This work takes the nozzle height as the considered factor and tests the tensile property of FFF-printed thermoplastic polyurethane (TPU). Rheological property of the TPU melt, represented here by die swell behavior and shear viscosity, were measured initially to obtain a preliminary assessment of the material suitability and an optimization of melt extrusion conditions for FFF processing. Then correlation between the cross-section profile of deposited bead and the tensile performance of printed sample were evaluated. Both the shape of deposited bead and the bonding strength of two adjacent beads are emphasized when explaining the measured tensile strength. The significance of molecular permeation efficiency at bead-bead interfaces, and bonding-releasing patterns between adjacent beads to the tensile failure of printed objects is discussed. / The support provided by China Scholarship Council (CSC, 201806465028) for Xiang Lin during his academic visit in University of Bradford is acknowledged.

Traditionally, lead-based bearing overlays dominate the commercial automotive market and it has been proven that an excellent combination of properties can be attained through their use. However, lead is a toxic metal and a cumulative poison in humans. According to the European Union End-of-Life Vehicle (ELV) Directive proposed in 1997, vehicles that registered in'all the member states after 1st July 2003 should contain no lead, mercury, cadmium and hexavalent chromium. In this study, a new sulphate-gluconate electrolyte was used to produce multilayer SnCo coatings, aimed at a lead-free overlay for future market use. Tin-cobalt compositionally modulated alloy (CMA) coatings produced from sulphategluconate electrolytes have been previously examined as a potential replacement for lead-free bearing overlays [1]. However, some obstacles may exist which limit their potential use on an industrial scale. For example, long electroplating times are required to produce a thick coating which is very undesirable from an industrial viewpoint, and also the possible elemental interdiffusion occurring in the coating system under engine operating temperatures could rapidly deteriorate the coating properties. In addition, there is an increasing demand from automotive industry to further improve bearing overlay properties, for example for high performance and high compression ratio engines.

Nanocomposites with expandable smectites such as montmorillonite layered silicates (MLS) in polymer matrices have attracted extensive application interest. Numerous MLS concentrations have been used with no particular justification. Here, we investigate the effects of MLS dispersion within the matrix and on mechanical performance. The latter is resolved through a three-prong investigation on rate dependent tensile results, time dependent creep results and the influence of a sharp notch in polypropylene (PP) nanocomposites. A fixed concentration of maleated polypropylene (mPP) was utilized as a compatibilizer between the MLS and non-polar PP. Analysis of transmission electron micrographs and X-ray diffraction patterns on the surface and below the surface of our samples revealed a unique skin-core effect induced by the presence of clay. Differential scanning calorimetric and polarized optical microscopic examination of spherulites sizes showed changes in nucleation and growth resulting from both the maleated PP compatibilizer and the MLS. These structural changes resulted in a tough nanocomposite, a concept not reported before in the PP literature. Nonlinear creep analysis of the materials showed two concentrations 3 and 5 % wt of PP, which reduced the compliance in the base PP. The use of thermal wave imaging allowed the identification of ductile failure among materials, but more important, aided the mapping of the elastic and plastic contributions. These are essential concepts in fracture analysis.

Le moussage du polypropylène (PP) et du polystyrène (PS) par le scCO2 est étudié de manière systématique avec l’accent sur la relation entre le procédé, la microstructure et les propriétés mécaniques. La première partie de cette thèse porte sur l’amélioration de la résistance au choc du PP par cristallisation induite par le scCO2. Dans un deuxième temps, le PP fortement orienté avec des structures shish-kebab et sphérolite est utilisé pour étudier l’influence de la structure cristalline sur la nucléation et la croissance des cellules pendant le procédé de moussage sous le scCO2. Ensuite, les influences des conditions de moussage ainsi que celles des paramètres structuraux de la mousse de PS ont été étudiées. Les mousses de PS à cellules isotropes ont été comparées avec celles de PS à cellules orientées. Enfin, un procédé de moussage discontinu en deux étapes est développé afin de produire des mousses de PS à cellules bi-modales en utilisant le scCO2 en tant qu’agent de moussage. Cette structure unique de petites et grandes cellules réparties de manière homogène au travers de l’ensemble du volume de la mousse confère à cette dernière des propriétés particulières. / In this work, scCO2 induced foaming of PP or PS is systematically studied with emphasis on the relationship between process, microstructure and mechanical properties. The first part of the thesis deals with the toughening of iPP by scCO2 induced crystallization for the fine separation of rigid crystalline domains and soft amorphous ones in the polymer matrix. The highly oriented iPP with “shish-kebab” and “spherulite” are then used for CO2 foaming to investigate the effect of crystalline structure on the formation of cell nucleation and growth. In addition, the effect of the foaming conditions and the cell structural parameters of PS foams on the mechanical properties are studied systematically. PS foams with isotropic cell morphology and oriented cell one are prepared. Finally, a two-step depressurization batch process is developed to produce bi-modal cell structure PS foams by using scCO2 as the blowing agent. This unique cell structure with both small and large cells homogenously distributed throughout the entire volume of the foam sample might have particular properties.