Les cristaux de KDP (KH2PO4) et de DKDP (K(H1-xDx)2PO4) sont largement utilisés pour leur propriété optique non linéaire comme convertisseur de fréquence ou cellule de Pockels. Le développement d’un système de croissance rapide par circulation de solution sous conditions stationnaire permet d’obtenir des cristaux de DKDP plus rapidement avec une distribution en deutérium homogène. Cependant, les premiers optiques obtenus par ce système montrent de fortes perturbations optiques en cartographie de surface d’onde ainsi que du crazing (formation de fissure sur le surface résultant d’un échange isotopique entre H/D).pouvant rendre leur utilisation problématique. Des défauts structuraux en topographie des rayons X ainsi qu’un abaissement de surface de 100 nm (mesuré en microtopographie de surface) ont été observés et sont corrélés par leur localisation avec les perturbations optiques. Cette localisation, identifiée comme étant le secteur vicinal shallow, est également la partie du cristal subissant le plus fort échange isotopique H/D. De plus, il a été montré récemment que le crazing pouvait être provoqué par la présence d’impuretés silicate s’incorporant dans une partie spécifique du cristal, le secteur shallow. Afin de déterminer qui, de l’incorporation d’impureté ou de l’échange isotopique, est responsable des défauts observés, des mesures similaires ont été réalisées sur une lame de KDP. Des perturbations optiques et des défauts structuraux ont également été observés, traduisant le fait que le deutérium exacerbe certains défauts, tel que l’abaissement de surface, mais n’en est pas l’origine. L’incorporation d’impureté dans le secteur shallow est donc l’hypothèse retenue quant à l’origine des perturbations optiques. Afin d’améliorer la qualité des optiques, les paramètres de croissance tels que la température, la sursaturation et le pH ont été modifiés pour identifier des conditions optimales de croissance, sans défauts structuraux ni perturbations optiques. Les topographies aux RX des cristaux obtenues dans les différentes conditions testées, montrent qu’une croissance avec un pH acide présente des qualités optiques prometteuses. Parallèlement, des mesures en ICP-MS ont été réalisées afin d’identifier l’impureté s’incorporant dans le secteur shallow, révélant une corrélation possible entre concentration en calcium et contraste en topographie aux RX. / KDP (KH2PO4) and deuterated DKDP (K(H1-xDx)2PO4) crystals are widely used for their nonlinear optical properties as frequency converters or Pockels cells. The development of a system for rapid growth under stationary conditions led to obtain DKDP crystals in shorter time with homogeneous distribution of deuterium. However, the first uncoated optics cut from DKDP crystals grown with such system showed significant perturbations of the laser wave front (optical distortions) as well as crazing (formation of cracks on the surface due to the isotopic H/D exchange), which may render problematic the utilization of these crystals as optics for high energy lasers. Recently, it has been shown that crazing could be promoted by the presence of silicate impurities incorporated into specific parts of the crystal: the vicinal sectors, shallow. To obtain DKDP crystals with optimal optical properties it was thus of major importance to determine the origin of the optical distortions, their eventual correlation with crazing and identify the mechanism responsible: nature of impurity, its gradient between sectors and what part does the isotopic composition play. We have confirmed for KDP the direct correlations observed in DKDP between vicinal sectors, contrasts in X-ray topography and optical distortions. Complications specific to DKDP related to deuterium losses were observed: crazing and surface alteration takes place only in the vicinal sectors previously identified. So even if inhomogeneous deuterium losses in DKDP may cause optical distortion by itself and should thus be avoided in coated optics, other causes exist. Hence, gradients of traces impurities inside the crystal appear to be at the origin of several phenomena leading to optical distortions. To improve optical quality, growth parameters, as temperature, supersaturation and pH, are modified to identify optimal conditions. X-ray topography obtained for each parameters demonstrate that a crystal grown at acid pH havs a very low density of defects. Simultaneously, ICP-MS is used to identify impurity incorporating inside vicinal sector shallow, revealing a correlation between Ca2+ concentration and structural defects in X-ray topography.

No description available.

Carbon nanotubes (CNT) are a new form of carbon with exceptional electrical and mechanical properties. This makes them attractive as inclusions in nanocomposite materials with the potential to provide improvements in electrical and mechanical properties and allows for the creation of a new range of multifunctional materials. In this study single wall carbon nanotubes (SWCNT) were dispersed in polystyrene using a solution mixing method, with the aid of a surfactant. A good dispersion was achieved and the resulting nanocomposites were characterized for electrical conductivity and mechanical properties by 3 point flexural and fracture toughness tests. Results show a significant improvement in electrical properties with electrical percolation occurring between 0.1 and 0.2 wt%. A minor improvement was observed in the flexural modulus but the strength and fracture toughness values in the nanocomposites decreased relative to the neat material. Scanning electron microscopy (SEM) was performed to characterize the morphology and fracture surface of the specimens. The results of testing and microscopy show that the presence of the nanotubes has an adverse effect on the crazing mechanism in Polystyrene (PS) resulting in a deterioration of the mechanical properties that depend on this mechanism.

Carbon nanotubes (CNT) are a new form of carbon with exceptional electrical and mechanical properties. This makes them attractive as inclusions in nanocomposite materials with the potential to provide improvements in electrical and mechanical properties and allows for the creation of a new range of multifunctional materials. In this study single wall carbon nanotubes (SWCNT) were dispersed in polystyrene using a solution mixing method, with the aid of a surfactant. A good dispersion was achieved and the resulting nanocomposites were characterized for electrical conductivity and mechanical properties by 3 point flexural and fracture toughness tests. Results show a significant improvement in electrical properties with electrical percolation occurring between 0.1 and 0.2 wt%. A minor improvement was observed in the flexural modulus but the strength and fracture toughness values in the nanocomposites decreased relative to the neat material. Scanning electron microscopy (SEM) was performed to characterize the morphology and fracture surface of the specimens. The results of testing and microscopy show that the presence of the nanotubes has an adverse effect on the crazing mechanism in Polystyrene (PS) resulting in a deterioration of the mechanical properties that depend on this mechanism.

In polymer matrix composites (PMCs) manufacturing processes can induce de- fects, e.g., voids, fiber misalignment, irregular fiber distribution in the cross-section and broken fibers. The effects of such defects can be beneficial or deleterious de- pending on whether they cause failure suppression or enhancement by localized de- formation processes e.g., crazing, shear yielding and fiber-matrix debonding. In this study, a computational approach is formulated and implemented to develop solu- tions for general boundary-value problems for PMC microstructures that accounts for micromechanics-based constitutive relations including fine scale mechanisms of material failure. The defects considered are voids, and the microstructure is explic- itly represented by a distribution of fibers and voids embedded in a polymer matrix. Fiber is modeled as a linearly elastic material while the polymer matrix is mod- eled as an elastic-viscoplastic material. Two distinct models for the matrix behavior are implemented: (i) Drucker–Prager type Bodner model that accounts for rate and pressure-sensitivity, and (ii) improved macromolecular constitutive model that also accounts for temperature dependence, small-strain softening and large-strain harden- ing. Damage is simulated by the Gearing-Anand craze model as a reference model and by a new micromechanical craze model, developed to account for craze initiation, growth and breakdown. Critical dilatational energy density criterion is utilized to predict fiber-matrix debonding through cavitation induced matrix cracking. An extensive parametric study is conducted in which the roles of void shape, size and distribution relative to fiber in determining damage initiation and evolution are investigated under imposed temperature and strain rate conditions. Results show there are significant effects of voids on microstructural damage as well as on the overall deformational and failure response of composites.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21547号 / 理博第4454号 / 新制||理||1640(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 田中 耕一郎, 教授 前野 悦輝, 教授 山本 潤 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The purpose of this study was to characterize the craze growth behavior of polycarbonate (PC) as a function of stress level, model the residual mechanical properties of PC at various craze levels and strain rates, and determine if the total surface area of crazing is the sole factor in residual properties or if the crazing stress plays a role. To obtain these goals, a new in-situ reflective imaging technique was developed to quantify the craze severity in transparent polymers. To accomplish the goal of craze growth rate characterization, polycarbonate samples were placed under a creep load in a constant temperature, constant humidity environment. Using the new technique, the relative craze density was measured as a function of time under load at stresses of 40, 45, and 50 MPa. The craze growth rates were found to increase exponentially with stress level, and the times to 1% relative craze density were found to decrease exponentially with stress level. One exception to this behavior was found at a crazing stress of 50 MPa at which over half of the samples tested experienced delayed necking, indicating competitive mechanisms of crazing and shear yielding. The draw stress was found to be a lower bound below which delayed necking will not occur in a reasonable time frame. The yield stress, elastic modulus, failure stress, and ductility were correlated to crazing stress, relative craze density, and strain rate using a Design of Experiments (DOE) approach. The yield stress was found to correlate only to the strain rate, appearing to be unaffected by the presence of crazes. No correlation was found between the elastic modulus and the experimental factors. The failure stress was found to decrease with an increase in relative craze density from 0 to 1%, increase with an increase in crazing stress from 40 to 45 MPa, and correlate to the interaction between the crazing stress and the strain rate. The ductility of polycarbonate was found to decrease significantly with an increase in relative craze density, a decrease in crazing stress, and an increase in strain rate. The craze microstructure was correlated to the magnitude of stress during craze formation. The area of a typical craze formed at 40 MPa was measured to be more than 2.5 times larger than the area of a typical craze formed at 45 MPa. The fewer, but larger, crazes formed at the lower stress level were found to decrease the failure strength and ductility of polycarbonate more severely than the large number of smaller crazes formed at the higher stress level. / Ph. D.

The interaction between poly(ether ether ketone) (PEEK) and three solvents (i.e., methylene chloride, tetrahydrofuran, and acetone) was studied by means of several complementary techniques. A series of eleven 0.3 mm thick PEEK films was produced. Each film had a certain crystallinity index and crystal morphology, as revealed by optical microscopy, differential scanning calorimetry (DSC), and wide angle X-ray scattering (WAXS). Dynamic solvent uptake measurements were performed on each film with the three solvents. Methylene chloride swelled both amorphous and semi-crystalline PEEK to high degrees, while tetrahydrofuran and acetone swelled amorphous PEEK only. After desorption, the samples were carefully analyzed to characterize solvent-induced crystallization (SINC), which occurred in amorphous PEEK exposed to all three solvents. Diffusion of methylene chloride and tetrahydrofuran in amorphous PEEK was observed in fractured specimens by scanning electron microscopy, while SINC was followed by DSC. The SINC process was found to be diffusion controlled. Diffusion of both solvents through the polymeric film took place in the first third of the equilibrium time, while swelling occurred in the remaining time. The mechanical properties of all solvent-exposed PEEK films were tested by three types of experiment (i.e., glass cone technique, microtensile tests, and tensile test in the environmental scanning electron microscope (ESEM)), which were first verified with another semi-crystalline thermoplastic polymer, isotactic polypropylene. PEEK specimens were stressed in the inside of glass cones and immersed in a series of solvents. Differences among solvent uptakes of stressed and unstressed specimens were explained in terms of crazing and SINC. Microtensile tests were performed on completely swollen PEEK specimens. Plasticization and delocalized crazing were found in the case of amorphous PEEK exposed to the three solvents and semi-crystalline PEEK exposed to methylene chloride, while classical crazing occurred in the other specimens. Finally, an amorphous PEEK specimen was swollen in acetone and stretched in the ESEM in acetone vapor. A very ductile deformation was observed, which occurred at the necked region between two notches. The results are discussed in terms of T_g depression and plasticization. / Ph. D.

No description available.

Made available in DSpace on 2014-12-17T14:58:15Z (GMT). No. of bitstreams: 1 MayaraSCFL_DISSERT.pdf: 5165682 bytes, checksum: c5b249c3b897f27db4e517452be9b9ce (MD5) Previous issue date: 2012-04-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Composites based on PEEK + PTFE + CARBON FIBER + Graphite (G_CFRP) has increased application in the top industries, as Aerospace, Aeronautical, Petroleum, Biomedical, Mechanical and Electronics Engineering challenges. A commercially available G_CFRP was warmed up to three different levels of thermal energy to identify the main damage mechanisms and some evidences for their intrinsic transitions. An experimental test rig for systematize a heat flux was developed in this dissertation, based on the Joule Effect. It was built using an isothermal container, an internal heat source and a real-time measurement system for test a sample by time. A standard conical-cylindrical tip was inserted into a soldering iron, commercially available and identified by three different levels of nominal electrical power, 40W (manufacturer A), 40W (manufacturer B), 100W and 150W, selected after screening tests: these power levels for the heat source, after one hour of heating and one hour of cooling in situ, carried out three different zones of degradation in the composite surface. The bench was instrumented with twelve thermocouples, a wattmeter and a video camera. The twelve specimens tested suffered different degradation mechanisms, analyzed by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetry) techniques, Scanning Electron Microscopy (SEM) and Energy-Dispersive X-Rays (EDX) Analysis. Before and after each testing, it was measured the hardness of the sample by HRM (Hardness Rockwell M). Excellent correlations (R2=1) were obtained in the plots of the evaporated area after one hour of heating and one hour of cooling in situ versus (1) the respective power of heat source and (2) the central temperature of the sample. However, as resulting of the differential degradation of G_CFRP and their anisotropy, confirmed by their variable thermal properties, viscoelastic and plastic properties, there were both linear and non-linear behaviour between the temperature field and Rockwell M hardness measured in the radial and circumferential directions of the samples. Some morphological features of the damaged zones are presented and discussed, as, for example, the crazing and skeletonization mechanism of G_CFRP / Comp?sitos baseados em matrizes polim?ricas de PEEK e PTFE, refor?adas com fibra de carbono e grafite (G_CFRP) apresentam crescente aplica??o e desafios ? Engenharia nas ind?strias Aeroespacial, Aeron?utica, de Petr?leo, Biom?dica, Mec?nica e Eletr?nica. Um comp?sito G_CFRP foi aquecido em tr?s n?veis de energia t?rmica para identificar os principais mecanismos de dano e algumas evid?ncias em suas transi??es de mecanismos. Uma bancada experimental foi desenvolvida para sistematizar o fluxo t?rmico com base no Efeito Joule. Foi constru?da usando-se um recipiente isot?rmico, uma fonte quente interna e um sistema de medidas em tempo real para ensaiar um corpo-de-prova (CP) de cada vez. Uma ponta c?nica-cil?ndrica foi inserida em um ferro de soldar, comercialmente dispon?vel e identificado por tr?s diferentes n?veis de pot?ncia el?trica, 40W (fabricante A), 40W (fabricante B), 100W e 150W, selecionados ap?s ensaios piloto: estes n?veis de pot?ncia para a fonte quente, ap?s uma hora de aquecimento e uma hora de resfriamento in situ, promoveu tr?s zonas diferentes de degrada??o na superf?cie do comp?sito. A bancada foi instrumentada com doze termopares, um watt?metro e uma c?mera de v?deo. Os doze C.P. ensaiados apresentaram diferentes mecanismos de degrada??o, analisados pelas t?cnicas de Calorimetria Diferencial Explorat?ria (DSC) e Termogravimetria (TG), e pelas an?lises de Microscopia Eletr?nica de Varredura (MEV) e Energia Dispersiva de Raios-X (EDS). Antes e ap?s cada ensaio, foram feitos ensaios de dureza Rockwell M (HRM). Excelentes correla??es (R2=1) foram obtidas nas curvas da ?rea evaporada ap?s uma hora de aquecimento e uma hora de resfriamento in situ versus (1) a respectiva pot?ncia da fonte quente e (2) a temperatura central do C.P. entretanto, como resultado da degrada??o diferencial do G_CFRP e da sua anisotropia, confirmadas por suas propriedades t?rmicas vari?veis, propriedades viscoel?sticas e viscopl?sticas, houve comportamentos linear e n?o-linear entre o campo de temperatura e a HRM medidos nas dire??es radial e circunferencial dos C.P. Algumas peculiaridades morfol?gicas das zonas de dano s?o apresentadas e discutidas, como, por exemplo, os mecanismos de dano por crazing e esqueletiza??o do G_CFRP