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Estudo do mecanismo de ação antirradicalar de betalaínas / Study of the mechanism of antiradical action of betalainsKarina Kinuyo Nakashima 21 December 2015 (has links)
Foi preparada uma série de quatro betalaínas com o objetivo de determinar o efeito da metilação do nitrogênio imínico e da presença de uma hidroxila fenólica na posição 3 do anel aromático sobre a estabilidade e propriedades antirradicalares, fotofísicas e redox desta classe de pigmentos vegetais. O estudo destes compostos, chamados de m-betalainofenol, N-metil-m-betalainofenol, fenilbetalaína e N-metil-fenilbetalaína, revelou que os derivados metilados apresentam um deslocamento hipsocrômico sutil dos máximos de absorção e fluorescência em relação aos compostos não metilados. Os deslocamentos de Stokes são maiores em cerca de 4 kJ mol-1 para os derivados metilados e os rendimentos quânticos de fluorescência cerca de três vezes menores. A hidrólise destas betalaínas foi investigada na faixa de pH entre 3 e 7. Todas as betalaínas são mais persistentes em pH = 6 e a metilação da porção imínica aumenta significativamente a estabilidade da betalaína em meio aquoso. A presença da porção fenólica, em comparação a um grupo fenila, não afeta as propriedades fotofísicas dos compostos e tem um efeito menos pronunciado do que o da metilação sobre a estabilidade destes em meio aquoso. O comportamento eletroquímico dos compostos foi estudado por voltametria cíclica, nas mesmas condições de pH. A N-metilação foi novamente mais significativa do que a hidroxilação, provocando aumento de até 200 mV no potencial de pico anódico. O aumento do pH diminuiu o potencial de pico anódico dos quatro compostos, com uma razão entre prótons e elétrons igual a 1 para a maioria dos picos. A capacidade antirradicalar foi quantificada pelo ensaio colorimétrico TEAC baseado na redução de ABTS•+. Os dois derivados N-metilados apresentaram, em média, o mesmo valor de TEAC, apesar de um ser fenólico e o outro não. Já entre os não metilados, que têm TEAC de 2 a 3 unidades inferior à dos outros, a presença do fenol provoca elevação da capacidade antirradicalar. Os resultados sugerem a participação dos elétrons do anel 1,2,3,4-tetraidropiridínico, acoplados ao próton do nitrogênio imínico na ação antirradicalar de betalaínas. / A series of four artificial betalains was prepared in order to determine the effect of imine nitrogen methylation and phenyl hydroxylation (position 3) over stability and antiradical, photophysical and redox properties of this class of natural pigments. The study of m-betalainophenol, N-methyl-m-betalainophenol, phenylbetalain and N-methylbetalain, revealed that the methylated compounds present a small hypsochromic shift of both absorption and fluorescence maxima when compared to the others. The Stokes shifts are around 4 kJ mol-1 higher for methylated betalains, whereas the quantum yields are approximately three times lower. Their hydrolysis was investigated between pH 3 and 7. All compounds are more persistent in pH = 6, and imine methylation increases the overall stability in aqueous medium. The presence of a phenol group, in comparison with a phenyl substituent, has a minor effect on the photophysical properties of betalains and has a less pronounced effect over stability than that of methylation. The electrochemical behavior was studied by cyclic voltammetry, in the same pH range, and is also more significantly affected by methylation, rather than by hydroxylation. Methylation increases anodic peak potential up to 200 mV, and the potential is also much higher in more acidic media for all compounds. The number of protons involved in the electrochemical oxidation is the same as the number of electrons for most peaks The antiradical capacity was quantified using the TEAC assay, and ABTS•+ as radical. The methylated betalains presented, in average, the same TEAC value, although only one of them is phenolic. Among the non methylated, which are 2 to 3 units more efficient than the others, the phenolic one has a greater TEAC. These results suggest a participation of the 1,2,3,4-tetraidropiridinic ring electrons in the oxidation by ABTS•+, coupled to the imine nitrogen proton.
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The Process-Structure-Property Relationships of a Laser Engineered Net Shaping (LENS) Titanium-Aluminum-Vanadium Alloy that is Functionally Graded with BoronSeely, Denver W 04 May 2018 (has links)
In this study, we quantified the Chemistry-Process-Structure-Property (CPSP) relations of a Ti-6Al-4V/TiB functionally graded material to assess its ability to withstand large deformations in a high throughput manner. The functionally graded Ti-6Al-4V/TiB alloy was created by using a Laser Engineered Net Shaping (LENS) process. A complex thermal history arose during the LENS process and thus induced a multiscale hierarchy of structures that in turn affected the mechanical properties. Here, we quantified the functionally graded chemical composition; functionally graded TiB particle size, number density, nearest neighbor distance, and particle fraction; grain size gradient; porosity gradient. In concert with these multiscale structures, we quantified the associated functionally graded elastic moduli and overall stress-strain behavior of eight materials with differing amounts of titanium, vanadium, aluminum, and boron with just one experiment under compression using digital image correlation techniques. We then corroborated our experimental stress behavior with independent hardening experiments. This paper joins not only the Process-Structure-Property (PSP) relations, but couples the different chemistries in an efficient manner to effectively create the CPSP relationships for analyzing titanium, aluminum, vanadium, and boron together. Since this methodology admits the CPSP coupling, the development of new alloys can be solved by using an inverse method. Finally, this experimental data now lays down the gauntlet for modeling the sequential CPSP relationships.
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Investigation of Phase Morphology and Blend Stability in Ionomeric Perfluorocyclobutane (PFCB)/Poly(vinylidene difluoride) (PVDF) Copolymer Blend MembranesOsborn, Angela Michelle 10 December 2010 (has links)
This research is focused on the investigation of phase morphology and blend stability within ionomeric perfluorocyclobutane (PFCB)/poly(vinylidene difluoride) (PVDF) copolymer blend membranes. The morphologies of these unique materials, designed as proton exchange membranes (PEMs) for proton exchange membrane fuel cells (PEMFCs), have been examined not only in the as-cast/as-received state, but also as a function of exposure to various ex-situ aging environments. The morphological investigations used to probe the response of these ionomer blends have been designed to mimic the environment within a PEMFC and will therefore enhance our understanding of the implications of morphological changes which may occur during fuel cell operation.
Thermal annealing of the membranes has been conducted to determine the materials' morphological response to various temperatures in the absence of hydration. The results of these thermal annealing studies have facilitated the isolation of morphological contributions stemming from thermal exposure. Immersion of the blend membranes in liquid water has allowed for singular identification of the role of hydration in the blend membranes' morphological rearrangement and phase stability. However, as the typical fuel cell environment to which these membranes will be exposed is complicated by the presence of both temperature and humidity, our ex-situ investigations have also included the exposure of PFCB/PVDF copolymer blend membranes to simultaneous thermal annealing and hydration conditions – a treatment we refer to as "hygrothermal aging." This unique procedure serves as a simplified method whereby the complex fuel cell environment may be simulated, and the resultant morphological response researched.
While the work presented herein has enhanced our understanding of the blend stability of the specific membranes investigated, we have also advanced the fundamental knowledge of the role of morphology with respect to the fuel cell performance of blend materials and the corresponding implications of morphological rearrangements. Such an understanding is essential in the development of morphology-property relationships and eventual optimization of membrane materials designed for use in fuel cells. / Ph. D.
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Probing diffusion and molecular dynamics to study self-assembly and intermolecular interactions in macromolecular and colloidal systems using NMR diffusometry and spectroscopyUppala, Veera Venkata Shravan 13 January 2025 (has links)
The growing demand for technological advancements in energy storage and pharmaceuticals, driven by population growth and climate change, has created an urgent need for the development of novel materials with finely tuned and targeted properties. Polymers, with their inherent versatility, have emerged as key players in modulating the functionality of such advanced materials. However, achieving precise control over the performance of the materials requires a deep understanding of the molecular interactions, self-assembly processes, and transport phenomena that govern their behavior at the nanoscale.
This dissertation focuses on the application of advanced nuclear magnetic resonance (NMR) techniques to probe the molecular dynamics and diffusion behavior in complex macromolecular and colloidal systems. Two key NMR techniques – NMR diffusometry and dynamic NMR spectroscopy – are employed to probe the motion and exchange process of molecules within these systems. By providing insights into the dynamics of the constituents, these methods are particularly powerful in unraveling the intermolecular interactions that govern material functionality.
The materials under investigation include block copolymer micelles (BCMs), ligand-capped quantum dots (QDs), and linear polyelectrolyte chains – each with unique structural characteristics and promising applications. Block copolymer micelles are of particular interest for drug delivery applications due to their ability to encapsulate and release therapeutic agents in controlled manner. Colloidal quantum dots, with their size-tunable electronic properties, have great potential in photovoltaics and biosensing. Linear polyelectrolytes, characterized by their charged backbones, are crucial for energy storage and biomedical applications.
Through a detailed analysis of the translational motion of molecules, this work reveals key molecular insights, including intermolecular interactions, the coexistence of molecules in distinct chemical environments, and their exchange mechanism between these environments. These findings establish critical structure-property relationships in each material system, providing a foundation for rational design and optimization of their functional performance.
The results obtained in this research not only contribute to our fundamental understanding of the molecular behavior of these complex systems but also have practical implications for design of next-generation materials. By leveraging the power of NMR-based techniques, this dissertation offers a pathway for enhancing material properties in the desired applications. The findings emphasize the critical role of molecular characterization techniques in advancing the field of material science and facilitating the development of more efficient, high-performance materials tailored to meet the demands for modern technology. / Doctor of Philosophy / Rising global challenges, such as energy storage and healthcare, demand innovations for new technologies. At the core of many of these innovations are advanced materials, which must be meticulously designed to meet specific performance requirements. Polymers, in particular, play a key role in these developments due to their versatile properties. To create materials with precise functionality, a deeper understanding of the chemistry and molecular interactions that govern their behavior is essential.
This dissertation focuses on using nuclear magnetic resonance (NMR), a powerful analytical tool, to probe molecular motions and interactions in advanced materials. Specifically, this research has developed NMR methodologies to investigate polymer-based micelles (surfactants) for drug-delivery applications, semiconductor nanoparticles for solar cells and sensor applications, and molecular weight determination of charged polymer chains.
The research aims to reveal new insights into the behavior of these materials and how such knowledge can be harnessed to design more effective systems for applications in medicine and energy. By studying molecular motions and interactions, this work aspires to contribute to the development of next-generation materials capable of addressing some of the world's most pressing challenges.
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Nouveaux copolymères dérivés d'esters cellulosiques par polymérisation radicalaire contrôlée. Application à la purification du carbonate de diméthyle par un procédé de séparation par membrane / New copolymer derivatives from cellulosic esters by controlled radical polymerization - Application to the dimethyl carbonate purification with a membrane-based separation processHeurtefeu, Magali 09 October 2008 (has links)
Ce travail a consisté en la synthèse de nouveaux copolymères d’acétate de cellulose greffés par du poly(méthyl diéthylène glycol méthacrylate) avec un nombre et une longueur de greffons variables par une méthode de polymérisation radicalaire contrôlée : l’Atom Transfer Radical Polymerization (ATRP). Deux familles de matériaux ont été obtenues ayant mêmes compositions (entre 20 et 50% en masse de greffons) mais des architectures différentes : de nombreux greffons courts ou peu de greffons longs. Ces matériaux ont ensuite été étudiés pour la séparation par pervaporation de mélanges azéotropiques de type aprotique/protique : carbonate de diméthyle/méthanol et éthyl tert-butyl éther/éthanol. Pour la séparation du premier mélange, la réticulation des copolymères s’est avérée nécessaire, conduisant à des matériaux qui restent fragiles sous contrainte et qui présentent des flux élevés au détriment d’une très faible sélectivité. Pour cette séparation, ces matériaux permettent cependant de dépasser la limite thermodynamique imposée par l’azéotrope. Pour le mélange éthyl tert-butyl éther/éthanol, les copolymères montrent d’excellentes performances en extrayant l’éthanol de manière très sélective. L’introduction de greffons permet d’augmenter le flux de pervaporat tout en ne diminuant que faiblement la sélectivité par rapport à l’acétate de cellulose précurseur. L’analyse de la microstructure des copolymères montre que les copolymères avec peu de greffons longs sont beaucoup plus ségrégés que ceux avec de nombreux greffons courts. Les résultats de perméabilité montrent des comportements différents selon l’architecture du copolymère cohérents avec leur microstructure / This work deals with the synthesis of new copolymers of cellulose acetate grafted with poly(methyl diethylene glycol methacrylate) with different numbers and lengths of grafted chains by controlled radical polymerization (Atom Transfer Radical Polymerization ATRP). Two families of materials were obtained with the same compositions (between 20 and 50% in mass of grafted chains) but different architectures : a lot of short chains or a few long chains. These materials were then studied for the pervaporation separation of two aprotic/protic azeotropic mixtures : dimethyl carbonate/methanol and ethyl tert-butyl ether/ethanol. For the separation of the first mixture, copolymers had to be cross-linked but their mechanical withstanding was poor under stress and they showed high fluxes but very low selectivity. Nevertheless, the materials allowed to go over the thermodynamical azeotropic limit. For ethyl tert-butyl ether/ethanol separation, copolymers showed excellent performances with a very selective extraction of ethanol. The presence of grafted chains increased flux along with a slight decrease in selectivity compared with the cellulose acetate precursor. The analysis of the copolymer microstructure showed that copolymers with long grafted chains were more segregated than those with short grafted chains. The results of permeability showed different behaviours according to the copolymer architecture in good agreement with their microstructure
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Processing and characterization of carbon black-filled electrically conductive nylon-12 nanocomposites produced by selective laser sinteringAthreya, Siddharth Ram 24 February 2010 (has links)
Electrically conductive polymer composites are suitable for use in the manufacture of antistatic products and components for electronic interconnects, fuel cells and electromagnetic shielding. The most widely used processing techniques for producing electrically conductive polymer composites place an inherent constraint on the geometry and architecture of the part that can be fabricated. Hence, this thesis investigates selective laser sintering (SLS), a rapid prototyping technique, to fabricate and characterize electrically conductive nanocomposites of Nylon-12 filled with 4% by weight of carbon black. The objective of the dissertation was to study the effects of the SLS process on the microstructure and properties of the nanocomposite. The effect of laser power and the scan speed on the flexural modulus and part density of the nanocomposite was studied. The set of parameters that yielded the maximum flexural modulus and part density were used to fabricate specimens to study the tensile, impact, rheological and viscoelastic properties. The electrical conductivity of the nanocomposite was also investigated. The thermo-mechanical properties and electrical conductivity of the nanocomposites produced by SLS were compared with those produced by extrusion-injection molding.
The structure and morphology of the SLS-processed and extrusion-injection molded nanocomposites were characterized using gas pycnometry, gel permeation chromatography, differential scanning calorimetry, electron microscopy, polarized light microscopy and x-ray diffraction. Physical models were developed to explain the effects of the processing technique on the structure and properties of the nanocomposites. Finally, a one-dimensional heat transfer model of the SLS process that accounted for sintering-induced densification and thermal degradation of the polymer was implemented in order to study the variation in part density with respect to the energy density of the laser beam.
This dissertation demonstrated that SLS can be successfully used to fabricate electrically conductive polymer nanocomposites with a relatively low percolation threshold. This capability combined with the ability of SLS to fabricate complicated three-dimensional objects without part-specific tooling could open up several new opportunities.
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Analyse et modélisation cinétique du vieillissement thermique des matrices PEI et PEEK et ses conséquences sur l’absorption d’eau / Kinetic analysis and modelling of thermal aging of PEI and PEEK matrices and its consequences on water absorptionCourvoisier, Emilie 06 March 2017 (has links)
Le PEI et le PEEK sont des thermoplastiques aromatiques haute performance. Il est envisagé de les utiliser comme matrice de structures composites en environnement de moteur d’avion. En conditions de service, ils seront soumis à des cycles hygrothermiques complexes consistant à des vieillissements thermo-oxydant jusqu’à 180 °C en continu et des vieillissements humide à 70 °C dans 85 % HR. Leur durabilité ayant fait l’objet de peu de travaux de recherche, l'objectif de cette thèse était d’étudier les effets isolés et combinés des vieillissements thermique et humide de ces deux matrices. Tout d’abord, des films minces de PEI et de PEEK ont été oxydés à différentes températures (entre 180 et 320 °C) et pressions partielles d’oxygène (entre 0,21 et 50 bars). Ils ont ensuite été caractérisés aux différentes échelles structurales pertinentes : moléculaire, macromoléculaire, morphologique et macroscopique. Cette caractérisation multi-techniques et multi-échelles a permis de déterminer leurs mécanismes de dégradation thermique. Ensuite, le vieillissement humide du PEI et du PEEK a été étudié entre 30 et 70 °C, entre 10 et 100 % HR, avant et après vieillissement thermique. A partir d’une compilation des données de la littérature pour une large variété de polymères contenant un seul type de groupe polaire dans l’unité monomère, des relations structure - propriété de transport de l'eau ont été établies. Elles confirment que l’hydrophilie et la diffusion d’eau résultent essentiellement d’interactions moléculaires entre les molécules d’eau et les groupes polaires de la matrice polymère. Enfin, un modèle cinétique de thermo-oxydation a été établi pour les matrices PEI et PEEK et a été interfacé avec les relations structure – propriété de transport d’eau. Il permet de simuler l’ensemble des données expérimentales accumulées dans ce travail de thèse. / PEI and PEEK are high performance aromatic thermoplastics. They are planned to be used as matrices of composite materials in aircraft engine environment. In service conditions, they will be subjected to complex hygrothermal cycles consisting in a series of thermo-oxidative agings up to 180 °C and humid agings at 70 °C in 85 % RH. As their durability has been little studied in the literature, the aim of this PhD thesis is to study the separated and combined effects of thermal and humid agings of these two matrices. At first, thin PEI and PEEK films have been oxidised at different temperatures (between 180 and 320 °C) and oxygen partial pressures (between 0.21 and 50 bars). There have been then characterized at different structural scales: molecular, macromolecular, morphological and macroscopic. This multi-technique and multi-scale characterization has enabled the determination of their thermal degradation mechanisms. Then, the humid aging of PEI and PEEK has been studied between 30 and 70 °C and between 10 and 100 % RH, before and after thermal aging. From a literature compilation of data for a large variety of polymers containing a single type of polar group in their monomer unit, structure – water transport property relationships have been established. They confirm that hydrophilicity and water diffusion result essentially from the molecular interactions between water molecules and polar groups in polymer matrices. Finally, a thermos-oxidation kinetic model has been established for PEI and PEEK matrices and has been juxtaposed with the structure – water transport property relationships. It enables to simulate all the experimental data obtained in this PhD work.
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Exploring Multiple Hydrogen Bonding and Ionic Bonding in the Design of Supramolecular PolymersChen, Xi 03 June 2020 (has links)
Supramolecular polymers represent a family of polymeric materials that are held together with dynamic, noncovalent interactions. In contrast to conventional functional polymers that usually have high melt-viscosity due to their covalent nature and chain entanglement, supramolecular polymers combine excellent physical properties with low melt-viscosity, allowing for less energy-intensive processability and recyclability. Dynamic bonding with multiple binding sites, such as multiple hydrogen bonding or multiple ionic bonding, exhibits much stronger binding strength compared to the counterparts containing only a single binding site, thereby allowing for enhanced mechanical integrity to the polymers and facilitate self-assembly. This dissertation focuses on the design of novel supramolecular polymers building from the doubly-charged or quadruple hydrogen bonding (QHB) scaffolds utilizing chain-growth polymerization or step-growth polymerization, as well as elucidate the structure-property-morphology relationships of the polymers.
A 2-step nucleophilic substitution reaction afforded a series of 1,4-diazabicyclo[2.2.2]octane (DABCO)-based styrenic monomers with two pairs of charged groups. An optimized 2-step reversible-addition-fragmentation chain-transfer (RAFT) polymerization synthesized ABA triblock thermoplastic elastomers (TPEs) with a low Tg poly (n-butyl acrylate) central block and a high Tg external charged blocks. Strong ionic interactions between doubly-charged units drove molecular self-assembly to form densely packed, hierarchical microstructures, which contributed to a robust, crosslinked physical network that allows the polymer to retain thermomechanical integrity until degradation. High-resolution single-crystal X-ray diffraction (SCXRD) coupled with powder X-ray diffraction (PXRD) further disclosed a detailed 3-D structural information of molecular arrangement and ion distribution within the charged phase through comparing DABCO-salt monomer single-crystal structure and the corresponding homopolymer XRD pattern. It was found that the physical properties of the DABCO-salt copolymers not only relied on their charge content and architectures but also dependent on their electrostatically-bonded counterions. The size and structure of the counterion determined the strength of dipole-dipole interaction, which significantly impact on thermal property, (thermo)mechanical performance, water affinity, and microstructure.
A cytosine-functionalized monomer, cytosine acrylate (CyA), allowed the synthesis of acrylic ABA triblock TPEs with pendant nucleobase moieties in the external blocks and a low Tg central polymer matrix through RAFT polymerization. Post-functionalization of cytosine (Cyt) bidentate hydrogen bonding sites with alkyl isocyanate, allowed the formation of ureido-cytosine (UCyt) groups in the external block that were readily dimerized through QHB interactions. The UCyt units in the external block enhanced mechanical strength and induced stronger phase-separation of the block copolymers compared to the corresponding Cyt-containing TPE analogs. Facile conventional free-radical polymerization using CyA and subsequent post-functionalization enabled accessibility to random copolymers containing pendant UCyt QHB moieties in the soft polymer matrix. The synergy of the flexible polymer matrix and the dynamic character of QHB groups contributed to the ultra-high elasticity of the polymer and rapid self-healing properties. QHB interactions enabled efficient mechanical recovery upon deformation by facilitating elastic chain retraction to regenerate the original physical network. Finally, one-pot step-growth polymerization through chain extending a novel bis-Cyt monomer and a commercially available polyether diamine using a di-isocyanate extender afforded segmented polyurea series for extrusion additive manufacturing. The molecular design of the polyureas featured soft segments containing flexible polyether chain and a relatively weak urea hydrogen bonding sites in the soft segment and rigid UCyt hydrogen bonding groups in the hard segment. The reversible characteristics of QHB enabled low viscosity at the processing temperature while providing mechanical integrity after processing and reinforced bonding between the interlayers, which contributed to the remarkable strength, elasticity, toughness, and interlayer adhesion of the printed parts. / Doctor of Philosophy / This dissertation focuses on designing supramolecular thermoplastic elastomers containing strong noncovalent interactions, i.e., quadruple hydrogen bonds or double ionic bonds. Inspired from noncovalent interactions in our mother nature, a series of bio-inspired monomers functionalized with nucleobase or ionic units were synthesized through scalable reactions with minimal purification steps. Polymerization of the functional monomers through step-growth or chain-growth polymerization techniques affords a variety of supramolecular thermoplastic elastomers with well-defined structures and architectures. These thermoplastic elastomers comprise soft and hard constituents; the former contains low glass transition polymer chains that provide elasticity while the latter contains strong noncovalent units to impart mechanical strength. Varying the soft/hard component ratios enables polymers with tunable physical properties to address different needs.
Systematic characterizations of these supramolecular polymers revealed their distinct properties from the polymers containing the covalent or weak noncovalent interactions and facilitate molecular-level understanding of the polymers. Generally, incorporating strong noncovalent interactions increases the temperature for polymer segmental motion and extends thermomechanical plateau windows. Additionally, the strong association strength of those non-covalent interactions promotes microphase separation and self-assembly, contributing to a high degree of structural ordering of the polymers. Moreover, the dynamic characteristics of the noncovalent interactions offer the polymers with reversible properties, which not only enables melt-processability and recyclability of the polymer but also contributes to a series of smart properties, including self-healing, shape-memory, and recoverability. Thus, the molecular design using supramolecular chemistry provides promising avenues to developing functional materials with enhanced mechanical properties, processability, and stimuli-responsiveness for emerging applications.
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Quantification of Structural Topology in Branched PolymersRamachandran, Ramnath 20 April 2012 (has links)
No description available.
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Die Holzmodifikation als Chance für einheimische Holzarten im MusikinstrumentenbauZauer, Mario 07 May 2024 (has links)
Ein Teil der Arbeit beschäftigt sich mit der Aufarbeitung zur anatomischen und chemischen strukturellen Zusammensetzung von vorrangig einheimischen Hölzern, um schließlich die physikalischen Eigenschaften bzw. deren Differenzen, auch im Unterschied zwischen Laub- und Nadelholz phänomenologisch im Sinne der Struktur-Eigenschafts-Beziehungen zu verstehen.
Die Verbesserung von holzphysikalischen Defiziten wird im Rahmen der Arbeit hauptsächlich mithilfe von physikalischen Verfahren erläutert. Dazu erfolgen ausführliche Beschreibungen zum mechanischen Verdichten quer zur Faserrichtung des Holzes, der thermischen Modifikation sowie der Kombination aus beiden Verfahren. Dazu werden sowohl jeweils die verfahrenstechnischen Parameter und Vorgehensweisen als auch die resultierenden anatomischen, chemischen und den damit verbundenen physikalischen Eigenschaftsänderungen erläutert, insbesondere in Abhängigkeit der Parameteranwendung sowie im Unterschied zwischen Laub- und Nadelholz.
Darüber hinaus werden bereits durchgeführte Studien zur physikalischen, chemischen und biologischen Holzmodifikation zur Verbesserung der akustischen Eigenschaften von Hölzern und deren möglicher Eignung für den Musikinstrumentenbau vorgestellt, zusammengefasst und jeweils bewertet.
Schließlich werden zwei ausgewählte Fallbeispiele beschrieben, welche die Zielsetzung verfolgten, einheimische Holzarten mithilfe der physikalischen Holzmodifikation als Tropenholzersatz in Konzertgitarren und Elektro-Bassgitarren bauteilspezifisch zu verwenden. Der jeweilige Lösungsansatz wurde einerseits durch Einsatz der thermischen Modifikation und andererseits mithilfe einer Kombination aus dem Plastifizieren, mechanischen Verdichten quer zur Faserrichtung und der anschließenden thermischen Modifikation verfolgt. Zur Material- und Instrumentencharakterisierung wurden hierbei verschiedene Testmethoden verwendet und bewertet.:1 Einleitung 1
1.1 Hintergrund und Motivation 1
1.2 Aufbau und Vorgehensweise 5
2 Struktureller Aufbau und relevante Eigenschaften von Holz 6
2.1 Anatomie des Holzes 6
2.2 Chemie des Holzes 18
2.3 Physik des Holzes 39
3 Holzmodifikation 91
3.1 Allgemeines 91
3.2 Verdichten quer zur Faserrichtung 95
3.3 Thermische Modifikation 119
3.4 Kombination: Querverdichten und thermische Behandlung 167
4 Holzmodifikation im Musikinstrumentenbau 185
5 Thermische Modifikation am Beispiel von Klassikgitarren 221
5.1 Grundlagen und Erwartungen 221
5.2 Technologische Umsetzung 230
5.3 Prüfmethoden und Bewertungskriterien 233
5.4 Ergebnisse und Diskussion 247
5.4.1 Allgemeines 247
5.4.2 Optik, Rohdichte und Sorption 248
5.4.3 Mechanische Kennwerte 254
5.4.4 Akustische Kennwerte 262
5.4.5 Objektives Klangverhalten (Anzupftests) 271
5.4.6 Subjektives Klangverhalten (Spieltests) 276
6 Kombination von Querverdichten und thermische Behandlung am Beispiel des Griffbrettbaus für Elektro-Bassgitarren 285
6.1 Grundlagen und Erwartungen 285
6.2 Technologische Umsetzung 291
6.3 Prüfmethoden und Bewertungskriterien 294
6.4 Ergebnisse und Diskussion 296
6.4.1 Allgemeines 296
6.4.2 Optik, Rohdichte, Sorption 298
6.4.3 Mechanische Kennwerte 312
6.4.4 Akustische Kennwerte 315
6.4.5 Objektives Klangverhalten (Anzupftests) 323
6.4.6 Subjektives Klangverhalten (Spieltests) 327
7 Zusammenfassung 330
8 Ausblick 338
Literaturverzeichnis 340
Abbildungsverzeichnis 379
Tabellenverzeichnis 394 / One part of the thesis deals with the processing of the anatomical and chemical structural composition of primarily native woods in order to finally understand the physical properties and their differences, also in the difference between hardwood and softwood phenomenologically in the sense of structure-property relationships.
The improvement of wood-physical deficits is mainly explained within the scope of the work with the help of physical methods. Detailed descriptions are given of mechanical densification across the grain direction of the wood, thermal modification and the combination of both methods. The process parameters and procedures as well as the resulting anatomical, chemical and associated physical property changes are explained, in particular depending on the parameter application and the difference between hardwood and softwood.
Furthermore, the work is dedicated to studies that have already taken place on physical, chemical and biological wood modification to improve the acoustic properties of woods and their possible suitability in musical instrument making, summarized and evaluated in each case.
Finally, two selected case studies are described which pursued the objective of using native wood species as a component-specific substitute for tropical wood in concert guitars and electric bass guitars with the aid of physical wood modification. The respective solution approach was pursued on the one hand by using thermal modification and on the other hand by using a combination of plasticizing, mechanical densification across the grain direction and subsequent thermal modification. Various test methods were used and evaluated for both material and instrument characterization.:1 Einleitung 1
1.1 Hintergrund und Motivation 1
1.2 Aufbau und Vorgehensweise 5
2 Struktureller Aufbau und relevante Eigenschaften von Holz 6
2.1 Anatomie des Holzes 6
2.2 Chemie des Holzes 18
2.3 Physik des Holzes 39
3 Holzmodifikation 91
3.1 Allgemeines 91
3.2 Verdichten quer zur Faserrichtung 95
3.3 Thermische Modifikation 119
3.4 Kombination: Querverdichten und thermische Behandlung 167
4 Holzmodifikation im Musikinstrumentenbau 185
5 Thermische Modifikation am Beispiel von Klassikgitarren 221
5.1 Grundlagen und Erwartungen 221
5.2 Technologische Umsetzung 230
5.3 Prüfmethoden und Bewertungskriterien 233
5.4 Ergebnisse und Diskussion 247
5.4.1 Allgemeines 247
5.4.2 Optik, Rohdichte und Sorption 248
5.4.3 Mechanische Kennwerte 254
5.4.4 Akustische Kennwerte 262
5.4.5 Objektives Klangverhalten (Anzupftests) 271
5.4.6 Subjektives Klangverhalten (Spieltests) 276
6 Kombination von Querverdichten und thermische Behandlung am Beispiel des Griffbrettbaus für Elektro-Bassgitarren 285
6.1 Grundlagen und Erwartungen 285
6.2 Technologische Umsetzung 291
6.3 Prüfmethoden und Bewertungskriterien 294
6.4 Ergebnisse und Diskussion 296
6.4.1 Allgemeines 296
6.4.2 Optik, Rohdichte, Sorption 298
6.4.3 Mechanische Kennwerte 312
6.4.4 Akustische Kennwerte 315
6.4.5 Objektives Klangverhalten (Anzupftests) 323
6.4.6 Subjektives Klangverhalten (Spieltests) 327
7 Zusammenfassung 330
8 Ausblick 338
Literaturverzeichnis 340
Abbildungsverzeichnis 379
Tabellenverzeichnis 394
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