Le bouchon en liège aggloméré joue un rôle clé dans la conservation des vins effervescents car c’est de lui que dépendent les échanges de gaz (CO2 et O2) entre le vin et le milieu extérieur. L’objectif de cette thèse est de déterminer les propriétés mécaniques et barrières des bouchons en liège aggloméré afin d’identifier les paramètres de formulation pouvant impacter ces propriétés et mettre en avant des points critiques, qu’il est nécessaire de contrôler au cours de la fabrication.La caractérisation de la structure du liège aggloméré a permis de mettre en évidence une porosité intergranulaire importante, qui est fortement réduite lorsque l’on utilise des granulés de liège de plus petite taille et lorsque le bouchon est comprimé dans le goulot.L’étude des propriétés mécaniques du liège aggloméré montre que l’élasticité du matériau augmente avec le taux d’hydratation du matériau, l’utilisation de granulés de liège de petites tailles et l’emploi d’un polymère adhésif dont la proportion de phase cristalline est faible. En revanche, la teneur en adhésif au sein du liège aggloméré semble ne pas avoir d’impact sur les propriétés mécaniques.Concernant les propriétés de transfert des bouchons pour vins effervescent de type A2R, les coefficients de diffusion du CO2 ont été mesurés, pour la première fois, dans les différents composants du bouchon (manche, film de colle, rondelle de liège). Le transfert est essentiellement régit par un mécanisme de diffusion de surface au travers du réseau d’adhésif. Plus le réseau d’adhésif est homogène au sein du corps aggloméré et entre les deux rondelles, plus les propriétés barrières seront élevées. La compression du bouchon dans le goulot augmente fortement les propriétés barrières.Enfin, il semblerait que les propriétés mécaniques et de transfert du liège aggloméré soient peu impactés par le vieillissement à condition toutefois que le réseau de colle polyuréthane ne soit pas en contact direct avec un milieu très concentré en éthanol car dans ce cas des phénomènes de solvolyse entrainent une forte dégradation des propriétés barrières et mécaniques du matériau.Mots clés : Liège naturel, liège aggloméré, structure, propriétés mécaniques, transfert de gaz, diffusion de surface, vieillissement. / The agglomerated cork stopper plays a key role in the preservation of sparkling wines because the gas exchanges (CO2 and O2) between the wine and the external environment depend on the stopper. The objective of this work is to determine the mechanical and barrier properties of agglomerated cork stoppers in order to identify the formulation parameters that can impact these properties, and highlight several critical points, which must be controlled during the process.The characterization of the agglomerated cork structure has revealed a large intergranular porosity, which is greatly reduced when smaller cork granules are used and when the cork is compressed in the bottleneck.The study of the mechanical properties of agglomerated cork shows that the elasticity of the material increases with the hydration of the material, the use of small cork granules and adhesive polymer with a low proportion of crystalline phase. On the other hand, the adhesive content within the agglomerated cork does not seem to have an impact on the mechanical properties.Concerning the transfer properties of agglomerated cork stoppers for sparkling wines, the CO2 diffusion coefficients were measured, for the first time, in the various parts of the stopper (agglomerated body, adhesive film, cork disc). The diffusion is essentially governed by a surface diffusion mechanism through the adhesive network. The more the adhesive network is homogeneous within the agglomerated body and between the two washers, the higher the barrier properties will be. Compression of the cork in the bottleneck greatly increases the barrier properties.Finally, it seems that the mechanical and transfer properties of agglomerated cork are slightly impacted by the aging provided that the network of polyurethane glue is not in contact with a highly concentrated ethanol medium, due to solvolysis phenomena that can occur and thus cause a strong degradation of the barrier and mechanical properties of the material.Keyword: Natural cork, agglomerated cork, structure, mechanical properties, gas transfer, surface diffusion, aging

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25298号 / 工博第5257号 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 村田 靖次郎, 教授 近藤 輝幸, 教授 中村 正治 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

abstract: Although many of the effects of the flute’s design and mechanisms have been previously studied, the flute’s stopper remains relatively unexplored. Stoppers are traditionally made of cork, are used to seal the upper end of the headjoint tubing, and determine the overall intonation of the flute. However, new stoppers made of different types of materials have been created to serve an additional purpose: to improve various aspects of player performance. These new non-cork stoppers vary in design and material, and claim to improve players’ projection, resonance, response, and other qualities. This research project discusses the history of the flute’s stopper and its functions, usage, and effects to improve general stopper knowledge and assist flutists interested in trying or purchasing non-cork stoppers available today. Because only three small studies have been published on the stopper’s acoustic and perceived effects to date, two single-blind experiments were conducted to determine the stoppers’ potential acoustic and perceived effects on listener and player perception. Five of the most popular stoppers available today were tested: the Bigio Stopper, Celestine Rexonator, Seidman Flute Stopper Plug, Swap-Stopper, and the traditional cork stopper. To determine the stopper’s acoustic effects, which can be quantified, an acoustic experiment was conducted to investigate the stoppers’ effect on intensity in decibels (which correlates with perceived loudness) and spectral centroid in hertz (which correlates with perceived tonal brightness). Perception tests were conducted to examine how both players and listeners perceive the stoppers’ effects on projection, response, tone quality, and timbre. The results of these experiments will help flutists better understand the effects of the stopper and navigate the stopper-makers’ claims about non-cork stoppers available for purchase today. / Dissertation/Thesis / Doctoral Dissertation Music 2020

Les silicones auto-cicatrisants de façon autonome (sans stimulus externe) présentent de faibles propriétés mécaniques, limitant leur utilisation industrielle. L’objectif de cette étude était de dépasser cette limitation. Nos travaux se sont intéressés aux copolymères segmentés PDMS-urée constitués de blocs souples (SS) et rigides (HS). Tout d’abord, nous avons étudié la relation entre la structure des bis-urées et les propriétés macroscopiques. Nous avons ainsi montré que la symétrie des HS gouverne la rigidité de ces matériaux. Toutefois, la présence de HS symétriques inhibe la cicatrisation du matériau. Puis, nous avons développé un nouveau concept permettant d’accélérer leur cinétique de cicatrisation. Un stoppeur de chaine macromoléculaire a été ajouté à la formulation de ces silicones thermoplastiques, créant un défaut dans l’assemblage supramoléculaire, conduisant à des clusters organiques plus petits et plus dynamiques. Néanmoins, contrairement aux plastifiants, la chute du module de Young observée par rapport à la matrice est limitée. D’ailleurs, nous reportons la synthèse d’un copolymère PDMS-urée avec un module de traction de 1MPa dont 90% de la contrainte à rupture peut être récupérée après cicatrisation pendant 24h à 25°C. Ce concept a aussi été adapté à un thermoplastique commercial (GENIOMER80). Enfin, notre défi a été d’optimiser la balance entre rigidité et autocicatrisation. Dans ce contexte, nous avons synthétisé de nouvelles matrices plus rigides, ainsi que des additifs avec des groupements associatifs de plus grande énergie cohésive. Nous avons alors pu repousser la limite de rigidité accessible aux silicones auto-cicatrisants de façon autonome (3MPa). / Autonomous self-healable (without external stimulus) silicones exhibit too low mechanical properties restricting their use in industry. The aim of this study was to overcome this limitation. We focused our work on segmented PDMS-urea copolymers made of soft (SS) and hard segments (HS). First the investigation of the relationship between the bis-urea chemical structure and the macroscopic properties was made. Results shown that, the symmetry of HS governs materials rigidity. Moreover, with a too symmetrical HS, the material does not exhibit self-healing abilities. We have developed a new concept improving the healing efficiency of these materials. The idea was to add to the formulation of these silicone thermoplastics a macromolecular chain stopper. The new additive creates a defect in the supramolecular assembly which leads to smaller and more dynamic H-bonding clusters and hence a faster healing kinetic. Unlike plasticizers, this additive deteriorates the tensile modulus only marginally. We therefore report a stress at break recovery of 90% after 24 hours at room temperature for a PDMS-urea copolymer with a tensile modulus of 1MPa. The concept was also extented to a commercial thermoplastic (GENIOMER80). Finally, our last challenge was to manage the balance between rigidity and chains dynamics allowing self-healable materials with good mechanical properties. In this context we have synthesized new matrixes with higher HS percentage and additives with stickers with higher cohesive energy. These new syntheses have led to an improvement of the rigidity limit reachable by the autonomous self-healable silicones (3MPa).

Brass musicians are known to experience a performance problem that is sometimes called valsalva maneuver or musical stuttering. This problem is known to cause difficulty starting a first note, tension in the throat, and tightness in the chest. Unfortunately, the research literature lacks sufficient details for evidence-based interventions. Therefore, the purpose of this study is to characterize and define this performance problem as experienced by brass musicians. An online epidemiologic survey was developed and deployed to collect data from brass musicians who have experienced this problem in their own playing. The survey was designed to acquire data in order to characterize and define the phenomenon through a biopsychosocial framework. The survey was also designed to assess whether this problem aligns with Altenmuller's heuristic model of motor control disruptions. A diverse group of brass musicians (n = 252) participated and offered relevant details for characterizing and defining this problem. Analysis of characteristic data suggests this problem is not a form of musical stuttering. Considering these data through Altenmuller's model suggests that this problem is experienced as a spectrum of motor disruptions that can develop into a unique type of musician's dystonia. While additional research is warranted, the results of this study are applicable to brass musicians, brass pedagogues, music educators, and performing arts health clinicians.