This dissertation includes two research topics. This first topic focuses on fundamental studies of monolignols and lignin, including polymerization and degradation. The second part reports a polymeric material that was crosslinked but can be reprocessed. In order to understand lignin from a molecular level and promote biopolymer conversion, we investigated the dehydrogenative copolymerization and degradation of two monolignols: caffeyl (C) alcohol and p-coumaryl (H) alcohol. The copolymerization and degradation were monitored by a quartz crystal microbalance with dissipation (QCM-D). Atomic force microscopy (AFM) was applied to investigate the topologies of the copolymer and degraded films. Horseradish peroxidase (HRP) was used as the enzyme for the dehydrogenative polymerization of monolignols and chelator-mediated Fenton chemistry was used to degrade the lignin. With constant monolignol concentration, we found that as the fraction of H in the polymerization feed increased, the amount of lignin formed increased, and the films became more rigid. For the degradation process of the resultant lignins, the presence of more C-monolignol during polymerization facilitated greater degradation. This work demonstrated the chemical factors that influenced the physical properties of lignin and lignin degradation, which could impact biofuel production. We further investigated the surface-initiated dehydrogenative polymerization of a new monolignol 5-hydroxyconiferyl (5H) alcohol using a QCM-D. HRP was immobilized on gold sensors. Various experimental conditions were studied. The dehydrogenative polymerization of 5H-monolignol was influenced by the concentration of monolignols and temperature, but was not affected by the hydrogen peroxide concentration, which was different from other monolignols. We also compared the polymerization kinetics of 5H-monolignol and the topology of the resulting lignin thin films with other monolignols. Furthermore, we utilized enzymatic and chemical degradation methods to treat the 5H-lignin. The 5H-lignin film was degraded thoroughly via a chelator-mediated Fenton reaction. This study provided a comprehensive understanding of 5H-monolignol polymerization and degradation and could be used as a reference for the exploration of the applications of the 5H-monolignol. In this dissertation, a separate study involved a vitrimer. It was a crosslinked polymer, but could be reprocessed and reshaped. The new vitrimer was based on poly (methyl methacrylate-co-hydroxymethyl methacrylate). Aromatic disulfides that underwent a dynamic exchange reaction were incorporated as crosslinkers. The structure of the material was identified by proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy (FTIR). Thermal properties and mechanical properties were studied through thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and Instron tests. Furthermore, the chemical resistance was explored. Notably, that new material exhibited comparable mechanical performance for three cycles when reprocessed via a hot press to reprocess. / Doctor of Philosophy / Lignin is a complex phenylpropanoid polymer and is one of the most abundant biopolymers in nature. Conversion of lignin into biofuels or other fine chemicals has drawn significant attention in recent years. Understanding molecular details of lignin formation and degradation is of fundamental importance for the biorefinery. Although a number of studies have improved our knowledge about lignin, many important aspects remain unknown. Lignin arises from dehydrogenative polymerization of three types of monolignols, named p-coumaryl (H), coniferyl (G), and sinapyl (S) alcohols. Recently, a new monolignol, caffeyl (C) alcohol, has been found. In this work, the surface-initiated copolymerization of C-monolignol and H-monolignol was conducted through an in vitro synthesis. Furthermore, chelator-mediated Fenton reactions were applied to degrade the resulting lignin. The effect of C-lignin incorporation on degradation was studied. It was found that, when more C-lignin was incorporated, the percentage of degradation was larger. These findings are likely to guide the conversion of lignocellulosic biomass into value-added products. A new monolignol, 5-hydroxyconiferyl (5H) alcohol, was investigated in this dissertation. The surface-initiated dehydrogenative polymerization of 5H was conducted under various experimental conditions, including different temperature, monomer concentration, and hydrogen peroxide concentration. Furthermore, degradation by enzymatic and non-enzymatic methods were studied. It was found that the 5H-lignin was recalcitrant to enzyme, but can be degraded by a non-enzymatic procedure. The synthesis and degradation were monitored by a quartz crystal microbalance with dissipation (QCM-D), which is a label-free method and can provide real-time data. Thermosets are the materials that are chosen for many applications due to their structural stability and mechanical properties. However, due to their permanent crosslinkages, they cannot be reprocessed or recycled. In this dissertation, a new crosslinked polymer material called a vitrimer was reported. The material was developed based upon poly (methyl methacrylate) (PMMA) and aromatic disulfide linkages, which are exchangeable chemical bonds. The exchange reaction occurs very quickly at elevated temperature. As a result, the material can be easily reprocessed and also exhibited chemical stability and mechanical properties similar to conventional thermosets.

Assuming that its deformation is both static and homogeneous, a method was devised within the framework of finite strain theory to calculate the elastic constants of a crystal at zero pressure as well as functions of pressure. As this method can be used for a crystal of any symmetry with a variety of potentials, elastic constant calculations were completed for both quartz and cristobalite using the potentials derived by Lasaga and Gibbs (1987, 1988), Tsuneyuki et al. (1988), van Beest et al. (1990) and Boisen and Gibbs (1993). Among the four theoretical potentials derived from force fields calculated for molecule H₆Si₂Q₇, two potentials associated with the SiO bond stretching as well as the OSiO and the SiOSi bond angle bending terms yield reasonable agreements with the experimental data, supporting the assumption that the binding forces in crystals are similar to those in small molecules (Gibbs 1982). Using the semi-empirical potentials, including the SQLOO potential derived with the covalent model (Boisen and Gibbs 1993) and two derived with the ionic model (Tsuneyuki et al. 1988; van Beest et al. 1990), calculations of the elastic constants reproduce the experimental results for both quartz and cristobalite. The pressure derivatives of the elastic constants calculated with these potentials also agree with the experimental results measured for quartz at low pressures and yield pressure derivatives of the bulk modulus that are in close agreement with that observed for quartz. Using the SQLOO potential, although the results of the calculations do not agree with the experimental data as well as those calculated using the two ionic potentials, the agreement of the calculations made with the theoretical potentials was improved significantly. Finally, using the three semi-empirical potentials, the elastic constants were calculated as functions of pressure for quartz and cristobalite up to their transitional pressures. Calculated for both quartz and cristobalite, different behaviors of the elastic constants were found using different potentials. For cristobalite, the variations of its elastic constants and bulk modulus are better modeled by the SQLOO potential as its structural behaviors calculated with the SQLOO potential are consistent with the X-ray diffraction studies. / Master of Science

No description available.

No description available.

Hydrogen is a component of spacecraft fuel that is explosive at atmospheric concentrations of four percent or higher. A study was undertaken to determine potential systems for use in tow types of hydrogen sensors that will be useful for real time hydrogen detection, both in ground storage and utilization facilities and in spacecraft. Quantitative detection demands a small, highly sensitive, and highly selective sensor. These detectors will be useful in areas such as the vicinity of joints, couplings, and stress points in the hydrogen storage and plumbing system of the space shuttle. Qualitative detection requires the other sensor to cover large areas, use no power, and be easily monitored visually or with a camera. Such a sensor will serve two purposes: it will allow general detection of hydrogen in a large space where poorly positioned point sensors would fail; it will also aid in locating and repairing any hydrogen leaks that might occur. A manganese (IV) oxide film was produced on the surface of a quartz crystal microbalance and this system was investigated for use as a small, quantitative hydrogen sensor. A reproducible response to hydrogen in the form of an increase in the frequency of vibration of the quartz crystal under an applied voltage was demonstrated. Other coatings were also investigated. A number of indicator compounds were screened for response to hydrogen to serve as large area sesnors. The metallochromic indicator, calmagite, produced a noticeable darkening upon exposure to hydrogen, demonstrating its potential for use as a qualitative, large area hydrogen sensor.

Dans la recherche de nouveaux matériaux piézoélectriques pour capteurs haute température (T > 600°C), nous nous sommes intéressés au matériau α-GeO2 dont le domaine de stabilité structurale en température et l'activité piézoélectrique seraient les plus importants parmi les composés isotypes du quartz-α. La littérature rapporte quelques limitations de ces deux propriétés dans le cas de monocristaux de α-GeO2 provenant de synthèses sous pression en milieu aqueux dues notamment à la présence de groupements hydroxyles au sein de la structure. Afin de remédier à cette contamination, une autre voie de croissance a été appliquée à GeO2 ; la méthode du flux par nucléation spontanée et à partir d'un germe monocristallin. Pour faciliter la croissance de la phase quartz-α de GeO2, métastable dans les conditions ambiantes, nous avons envisagé de substituer une faible partie des cations Ge4+ par des cations Si4+ (environ 10 % atomique). Après optimisation des différents paramètres expérimentaux, les cristaux synthétisés lors de ce travail ont été analysés par plusieurs techniques de caractérisation complémentaires (spectroscopies infrarouge et Raman, analyse E.D.X., D.R.X sur monocristal et sur poudre et D.S.C.) qui ont démontré leur excellente qualité cristalline, l'absence de contamination chimique (dans la limite de détection des techniques de caractérisation) et l'absence de transition de phase de la structure quartz-α, de la température ambiante à la fusion de ces matériaux (proche de 1100°C). L'approche de l'activité piézoélectrique de α-GeO2 en fonction de la température a été réalisée via l'étude de ses propriétés électromécaniques par spectroscopie d'impédance et spectroscopie Brillouin. Nous avons ainsi démontré que le matériau de structure quartz-α de GeO2 résonnait à très haute température (≈ 900°C) avec cependant une intensité diminuée par rapport à celle enregistrée à température ambiante. / In the research of new piezoelectric materials for high temperature sensors (T > 600°C), we have been interested in α-GeO2 material which would exhibit the most important piezoelectric activity and structural stability domain with temperature among the α-quartz isotype compounds. Some limitations are described in the literature concerning those two properties in the case of hydrothermally-grown α-GeO2 single crystals mainly due to the presence of hydroxyl groups in their structure. To prevent this contamination, another growth approach was applied to GeO2: flux-growth method by spontaneous nucleation and from a crystalline seed. To facilitate the growth of the α-quartz phase of GeO2, metastable in ambient conditions, we have thought to substitute a part of Ge4+ cations by Si4+ cations (around 10 atomic per cent). After optimization of the different experimental parameters, flux-grown single-crystals were analyzed by several complementary characterization techniques (infrared and Raman spectroscopies, E.D.X. analyses, single-crystal and powder X-R.D. and D.S.C.) which have demonstrated their excellent crystalline quality, the absence of chemical contamination (inside the detection limit of characterization techniques) and the absence of phase transition of the α-quartz structure, from ambient temperature to the fusion of those materials (around 1100°C). The observation of piezoelectric activity of α-GeO2 as a function of temperature was realized from the study of its electromechanical properties by impedance spectroscopy and Brillouin spectroscopy. By these means, we have demonstrated that the α-quartz structure of GeO2 still resonate at very high temperature (≈ 900°C) with a weaker intensity compared to that recorded at ambient temperature.

Atualmente, podemos perceber que uma grande dependência dos sistemas desenvolvidos sob a seara da criptografia foi instaurada em todos nós. Principalmente no tocante dos sistemas criptográficos de chave pública, que são vastamente utilizados na Internet. No entanto, a criptografia de chave pública viu-se ameaçada e começou a investigar novas fontes de problemas para seus sistemas quando Shor em 1997 desenvolveu um algoritmo de tempo polinomial para fatorar inteiros e para calcular o logaritmo discreto em um computador quântico. Neste contexto, Patarin propõe a função alçapão HFE (Hidden Field Equations), uma trapdoor baseada nos Problemas MQ (Multivariate Quadratic) e IP (Isomorfismo de Polinômios). Tais problemas não são afetados pelo algoritmo de Shor, além disto o Problema MQ foi demonstrado por Patarin e Goubin como sendo NP-completo. Apesar do HFE ter sua versão básica quebrada, ele apresenta variações -- obtidas através de modificadores genéricos -- resistentes aos principais ataques da atualidade. O Quartz -- esquema de assinatura digital baseado no HFEv-, com escolha especial de parâmetros -- é um bom exemplo desta resistência a ataques algébricos que visem a recuperação da chave privada, pois até hoje permanece seguro. Além de também se destacar por gerar assinaturas curtas. Todavia, Joux e Martinet -- baseados em axiomas do Ataque pelo Paradoxo de Aniversário -- provaram que o Quartz é maleável, demonstrando que caso o adversário possua um par (mensagem, assinatura) válido, ele conseguirá obter uma segunda assinatura com 2^(50) computações e 2^(50) chamadas ao oráculo de assinatura, logo muito abaixo dos padrões de segurança atuais que são de, no mínimo, 2^(112). Desta forma, baseado no Quartz, apresentamos um novo esquema de assinatura digital resistente a ataques adaptativos de mensagem escolhida que realizem chamadas ao oráculo aleatório, com um nível de segurança estimado em 2^(112). Nosso criptossistema proporciona, ainda, um ganho de eficiência no algoritmo de verificação de assinatura e na inicialização dos vetores que serão utilizados pelos algoritmos de assinatura e verificação. Além de, também, disponibilizarmos uma implementação do Quartz Original e do Quartz Aprimorado, na linguagem de programação Java. / Today, we can see that a large dependence of the systems developed under the cryptography was introduced in all of us. Especially in terms of public key cryptosystems, which are widely used on the Internet. However, public key cryptography was threatened and began to investigate new sources of problems for their systems when Shor in 1997 developed a polynomial time algorithm for factoring integers and to compute the discrete logarithm in a quantum computer. In this context, Patarin proposed Hidden Field Equations (HFE), a trapdoor based on MQ (Multivariate Quadratic) and IP (Isomorphism of Polynomials) problems. Such problems are not affected by the Shor algorithm, moreover MQ Problem was demonstrate by Patarin and Goubin as NP-complete. Despite the basic HFE has broken, it varies secure, obtained by generic modification. The Quartz -- digital signature scheme based on HFEv-, with special choice of parameters -- is a good example of this resistance to algebraic attacks aimed at the recovery of the private key, because even today remains secure. Furthermore, it also generates short signatures. However, Joux and Martinet -- based on axioms of Birthday Paradox Attack -- proved that Quartz is malleable, showing that if the adversary has a pair (message, signature) valid, he can get a second signature with 2^(50) computations and 2^(50) calls to the signing oracle, so far the current security standards that are at least 2^(112). Thus, based on Quartz, we present a new digital signature scheme, achieving the adaptive chosen message attacks that make calls to the random oracle, with a secure level estimated at 2^(112). Our cryptosystem also provides an efficiency gain in signature verification algorithm and initialization vectors that will be used for signing and verification algorithms. Further we provide an implementation of Original Quartz and Enhanced Quartz in the Java programming language.

Dans le domaine des cristaux piézoélectriques, le quartz est l'un des plus employés dans l'industrie électroniques pour des applications comme oscillateurs ou dans le domaine temps-fréquence. Le quartz-alpha SiO2 montre une décroissance de ses propriétés au-delà de 250°C, une transition de phase alpha-beta à 573°C et un faible coefficient de couplage électromécanique k autour de 8%. Bien que ses propriétés d'optique non-linéaire soient bien connues, son faible coefficient chi2 ne lui permet pas d'être utilisé dans des dispositifs doubleurs de fréquence. L'objectif de cette étude est d'augmenter la distorsion structurale et la polarisabilité de ce matériau en substituant une partie des atomes de silicium par des atomes plus volumineux tels que le germanium ou d'autres éléments. Afin de faire croitre des cristaux de taille centimétrique, la technique hydrothermale a été employée dans des autoclaves hautes pressions. Des cristaux de quartz-alpha de type Si(1-x)GexO2 ont été réalisés sur des germes de quartz-alpha SiO2 (001). Des cristaux volumineux avec différentes teneurs en germanium ont été obtenus puis analysés par spectroscopie infrarouge et par EPMA. Les propriétés piézoélectriques et d'optique non-linéaire ont été mesurées sur ces cristaux montrant une augmentation des propriétés physiques. Puis des croissances cristallines avec des atomes plus volumineux que le germanium ont été réalisées afin d'en augmenter davantage les propriétés physiques. Des substitutions par les éléments suivants ont été entreprises : Mn, V, Ti, et Sn / In the field of piezoelectric crystals, quartz is one of the widely used materials in industry for electronic device application as oscillators for the time-frequency domain. alpha-Quartz SiO2 shows a decrease of its piezoelectric properties above 250°C, an alpha-quartz to beta-quartz phase transition at 573°C and a low electromechanical coupling factor of about 8%. Although its nonlinear optics properties are well known, its low chi2 coefficient prevent it to be used in frequency doubling devices. The goal of this study is to increase the structural distortion and the polarizability of this material by substituting part of the silicon atoms with larger atoms such as germanium or other elements. In order to grow centimeter-size single crystals we use hydrothermal methods in high-pressure autoclaves. Crystal growth of mixed alpha-quartz Si(1-x)GexO2 crystals was successfully performed on pure alpha-quartz SiO2 (001) seeds. Large crystals with different germanium content were obtained and analyzed by infrared spectroscopy and EPMA. Piezoelectric and nonlinear optical properties were measured on these crystals, which exhibit a improved physical properties. Then crystal growths with larger elements than germanium were performed in order to further improve their physical properties. Substitution by the following elements: Mn, V, Ti and Sn were investigated.

In this study, we have investigated the effect of substrate temperature, use of adhesive layer, deposition rate, annealing and substrate prebaking on the morphology of gold films deposited onto quartz surfaces. For the film growth, physical vapor deposition methods namely electron beam and thermal depositions have been used. Surface morphology of the films have been characterized with atomic force microscopy. Our aim was to confirm the general trends observed for these parameters in our evaporator system for a limited working range in order to produce gold films which are suitable to be used simultaneously for quartz crystal microbalance and helium atom diffraction measurements. At the end of this study, we confirmed the general trends regarding the effect of these parameters stated in literature except annealing process. We obtained a minimum 170 nm2 atomically flat surface with a roughness value smaller than 0.200 nm by thermal deposition method.

In 1880, French brothers Jacques and Pierre Curie discovered the phenomenon of piezoelectricity in naturally occurring quartz crystal, sometimes referred to as 'nature's timekeeper.' By 1959, tens of millions of devices that exploited quartz crystal's piezoelectric character were being used in the technologies of radio, telephony, and electronic timekeeping. This dissertation analyzes the rapid rise of quartz crystal technology in the United States by looking at the growth of its knowledge base as reflected primarily in patents and journal articles. The major finding of this analysis is that the rise of quartz crystal technology cannot be fully understood by looking only at individuals, institutions, and technological factors. Rather, this work posits that the concept of technological community is indispensible in explaining rapid technological growth and diffusion that would otherwise seem inexplicable. In the late 1920s, and again in the early 1940s, the knowledge base of quartz crystal technology experienced exponential growth, partly due to U.S. government patronage and enlightened regulation. However, as this study shows, quartz crystal engineers, scientists, and entrepreneurs could not have mobilized as quickly and effectively as they did unless a vibrant technological community already existed. Furthermore, the United States' ability to support such a thriving community depended in part on an early 20th century American culture that displayed an unmatched enthusiasm for democratic communications media, most especially broadcast radio and universal telephone service. Archival records, professional journal articles, government reports, manufacturer catalogs, and U.S. patents have been used to document this history of the quartz crystal technological community. This dissertation contributes to the literature on technological communities and their role in facilitating technological and ecomonic growth by showing that though such communities often form spontaneously, their growth may be nurtured and stimulated through enlightened government regulation. As such, this dissertation should be of interest to scholars in the fields of history of technology, business history, management studies, and public policy.