L'objectif de cette thèse a été de démontrer la pertinence du procédé sol-gel photoinduit pour la synthèse de films nanocomposites originaux à partir de précurseurs hybrides mono- et bis-silylés. Bien que mentionné dans la littérature, ce procédé basé sur une catalyse via des super-acides de Bronsted créés par la photolyse d'un photogénérateur d'acides reste à ce jour très marginal. Selon la nature des précurseurs mis en oeuvre, la photopolymérisation sol-gel a parfois été combinée à une photopolymérisation organique pour mener à l'obtention en une seule étape de réseaux hybrides organique-inorganique. Au cours de ces travaux, l'accent a tout d'abord été mis sur la caractérisation structurale des matériaux synthétisés. Pour cela, des mesures par spectroscopie infrarouge à transformée de Fourier, résonance magnétique nucléaire du 29Si et du 13C en phase solide et diffraction des rayons X ont été réalisées. Ces études ont permis de révéler les nombreux avantages liés à la voie photochimique tels que la forte réactivité, le caractère vivant de la réaction, l'absence d'eau ou de solvant et l'obtention de matériaux organisés à l'échelle locale. Enfin, l'originalité de cette étude a également résidé dans la mise en œuvre de nombreuses techniques de caractérisation thermo-mécanique des films : analyse mécanique dynamique, calorimétrie différentielle à balayage, nanoindentation, tribologie et tests de résistance à la rayure. L'influence de la nature chimique de la fonctionnalité organique du précurseur employé a ainsi pu être soulignée et des corrélations entre microstructure et propriétés finales des matériaux photopolymérisés ont été établies. / The present work questioned the interest of sol-gel photopolymerization as a novel route to synthesize nanocomposite films from hybrid mono- and bis-silylated precursors. The potentialities of this process that is based on a catalysis promoted by photogenerated Bronsted superacids have been poorly investigated so far. Depending on the precursor nature, the sol-gel photopolymerization was possibly combined with an organic photopolymerization in a view to generate the dual crosslinking of the organic and inorganic networks in a single step. A first aspect of this work concemed the structural properties of the hybrid films: Fourier transformed IR spectroscopy, 29Si and 13C solid state Nuclear Magnetic Resonance spectroscopy and X-rays analysis were thus implemented. These experiments highlighted the numerous advantages of the photoinduced sol-gel process: its high reactivity, its living character, the absence of water or solvent and the local organization in the resulting films. Finally, the thermo-mechanical properties of the UV­ cured materials were assessed by using a wide range of characterization techniques: dynamic mechanical analysis, differentia!scanning calorimetry, nanoindentation, tribological and scratch tests. The effect of the organic moiety functionality of the precursors was thus evidenced and relationships between microstructure and properties ofthe hybrid films were established.

In an engine component the repeated start-stop cycles cause temporal and local inhomogeneous temperatures, which in turn lead to a type of low-frequency loading, plastic deformation and eventually failure due to thermo-mechanical fatigue. Simultaneously, high-frequency mechanical loading arises from the cyclic combustion pressure and from road induced vibrations. These types of loadings that mainly are in the elastic region are usually denoted high cycle fatigue (HCF). In order to improve efficiency, power density and to reduce emissions, future truck engines will be subjected to higher temperatures and higher combustion pressures which will affect the service life of the different engine components. As a consequence, there is a need to determine the limitations of the used alloys under these service conditions as exactly as possible. In this master thesis work the fatigue properties of one grey iron (EN-GJL 250) and one compacted graphite iron (EN-GJV 400) has been investigated under realistic loading conditions. The results show that a change from the grey iron to the compacted graphite iron will result in a significant increase of the fatigue life. The investigation also reveal that the life will increase significantly if the maximum temperature can be decreased tens of degrees. Further, the results indicate that addition of a relatively small HCF load may give a large decrease of the fatigue life. / Motorkomponenter utsätts för upprepade start och stopp, vilka skapar tillfälliga och lokala temperaturvariationer. Dessa resulterar i lågfrekventa lastväxlingar, plastiska deformationer och eventuella brott i form av termodynamisk utmattning (TMF). Det sker dessutom en högfrekvent mekanisk last, genererad av förbränningen och från vägvibrationer. Dessa laster är mestadels elastiska och benämns högcykelutmattning (HCF). För att kunna förbättra verkningsgrad och minska emissioner kommer framtida lastbilsmotorer att utsättas för högre förbränningstryck och högre temperaturer, vilket kommer påverka motorernas livslängd. För detta krävs det att materialens begränsningar utreds under ett verklighetstroget förhållande. I detta exjobb kommer utmattningsegenskaperna för ett gråjärn (EN-GJL 250) och ett kompaktgrafikjärn (EN-GJV 400) utredas under realistiska lastförhållanden. Resultatet påvisar att ett byte från gråjärn till kompaktgrafitjärn ger en signifikant ökad livslängd. Det framkommer också att livslängden kan ökas genom att sänka den maximala temperaturen ett tiotal grader. Analysen påvisar även att en relativt liten HCF last kan ge kraftigt förkortad livslängd.

In an engine component the repeated start-stop cycles cause temporal and local inhomogeneous temperatures, which in turn lead to a type of low-frequency loading, plastic deformation and eventually failure due to thermo-mechanical fatigue. Simultaneously, high-frequency mechanical loading arises from the cyclic combustion pressure and from road induced vibrations. These types of loadings that mainly are in the elastic region are usually denoted high cycle fatigue (HCF). In order to improve efficiency, power density and to reduce emissions, future truck engines will be subjected to higher temperatures and higher combustion pressures which will affect the service life of the different engine components. As a consequence, there is a need to determine the limitations of the used alloys under these service conditions as exactly as possible. In this master thesis work the fatigue properties of one grey iron (EN-GJL 250) and one compacted graphite iron (EN-GJV 400) has been investigated under realistic loading conditions. The results show that a change from the grey iron to the compacted graphite iron will result in a significant increase of the fatigue life. The investigation also reveal that the life will increase significantly if the maximum temperature can be decreased tens of degrees. Further, the results indicate that addition of a relatively small HCF load may give a large decrease of the fatigue life. Keywords:Thermo-mechanical fatigue, TMF, CGI, LGI, fatigue, thermal strain. / Motorkomponenter utsätts för upprepade start och stopp, vilka skapar tillfälliga och lokala temperaturvariationer. Dessa resulterar i lågfrekventa lastväxlingar, plastiska deformationer och eventuella brott i form av termomekanisk utmattning (TMF). Det sker dessutom en högfrekvent mekanisk last, genererad av förbränningen och från vägvibrationer. Dessa laster är mestadels elastiska och benämns högcykelutmattning (HCF). För att kunna förbättra verkningsgrad och minska emissioner kommer framtida lastbilsmotorer att utsättas för högre förbränningstryck och högre temperaturer, vilket kommer påverka motorernas livslängd. För detta krävs det att materialens begränsningar utreds under ett verklighetstroget förhållande. I detta exjobb kommer utmattningsegenskaperna för ett gråjärn (EN-GJL 250) och ett kompaktgrafikjärn (EN-GJV 400) utredas under realistiska lastförhållanden. Resultatet påvisar att ett byte från gråjärn till kompaktgrafitjärn ger en signifikant ökad livslängd. Det framkommer också att livslängden kan ökas genom att sänka den maximala temperaturen ett tiotal grader. Analysen påvisar även att en relativt liten HCF last kan ge kraftigt förkortad livslängd. Nyckelord: Termomekanisk utmattning, TMF, CGI, LGI, termisk töjning.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21767号 / 工博第4584号 / 新制||工||1714(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 乾 晴行, 教授 安田 秀幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

A vast array of high value parts in land- and air-based turbomachinery are subjected to non-isothermal cycling in the presence of mechanical loading. Crack initiation, growth and eventual failure more significantly reduce life in these components compared to isothermal conditions. More accurate simulation of the stress and strain evolution at critical locations of components, as well as test specimens, can lead to a more accurate prediction of remaining life to a structural integrity specialists. The focus of this thesis is to characterize the effects of thermomechanical fatigue (TMF) on generic turbomachinery alloy. An expression that can be used to estimate the maximum and minimum stress under a variety of loading conditions is formulated. Analytical expressions developed here are modifications of classic mechanics of materials methods (e.g. Neuber's Rule and Ramberg-Osgood). The novel models are developed from a collection of data based on parametric finite element analysis to encompass the complex load history present in turbine service conditions. Relevance of the observations and formulated solutions are also explored for the case of a tensile specimen containing a v-shaped notch. Accurate estimations of non-isothermal fatigue presented here endeavor to improve component lifing and decrease maintenance costs.

Shape memory alloys when deformed can produce strains as high as 8%. Heating results in a phase transformation and associated recovery of all the accumulated strain, a phenomenon known as shape memory. This strain recovery can occur against large forces, resulting in their use as actuators. The goal of this project is to lower the operating temperature range of shape memory alloys in order for them to be used in cryogenic switches, seals, valves, fluid-line repair and self-healing gaskets for space related technologies. The Ni-Ti-Fe alloy system, previously used in Grumman F-14 aircrafts and activated at 120 K, is further developed through arc-melting a range of compositions and subsequent thermo-mechanical processing. A controlled atmosphere arc-melting facility and vertical vacuum quench furnace facility was commissioned to fabricate these alloys. The facility can create a vacuum of 10-7 Torr and heat treat samples up to 977 °C. High purity powders of Ni, Ti and Fe in varying ratios were mixed and arc-melted into small buttons weighing 0.010 kg to 0.025 kg. The alloys were subjected to solutionizing and aging treatments. A combination of rolling, electro-discharge machining and low-speed cutting techniques were used to produce strips. Successful rolling experiments highlighted the workability of these alloys. The shape memory effect was successfully demonstrated at liquid nitrogen temperatures through a constrained recovery experiment that generated stresses of over 40 MPa. Differential scanning calorimetry (DSC) and a dilatometry setup was used to characterize the fabricated materials and determine relationships between composition, thermo-mechanical processing parameters and transformation temperatures.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24220号 / 工博第5048号 / 新制||工||1788(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 五十嵐 晃, 教授 杉浦 邦征, 教授 KIM Chul-Woo / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The work reported in this dissertation is intended to propose, analyze and demonstrate a technology for a high temperature integrated power electronics module, for high temperature (e.g those over 200oC) applications involving high density and low stress. To achieve this goal, this study has examined some existing packaging approaches, such as wire-bond interconnects and solder die-attach, flip-chip and pressure contacts. Based on the survey, a high temperature, multilayer 3-D packaging technology in the form of an Embedded Chip Module (ECM) is proposed to realize a lower stress distribution in a mechanically balanced structure with double-sided metallization layers and material CTE match in the structure. Thermal and thermo-mechanical analysis on an ECM is then used to demonstrate the benefits on the cooling system, and to study the material and structure for reducing the thermally induced mechanical stress. In the thermal analysis, the high temperature ECM shows the ability to handle a power density up to 284 W/in3 with a heat spreader only 2.1x2.1x0.2cm under forced convection. The study proves that the cooling system can be reduced by 76% by using a high temperature module in a room temperature environment. Furthermore, six proposed structures are compared using thermo-mechanical analysis, in order to obtain an optimal structure with a uniform low stress distribution. Since pure Mo cannot be electroplated, the low CTE metal Cr is proposed as the stress buffering material to be used in the flat metallization layers for a fully symmetrical ECM structure. Therefore, a chip area stress as low as 126MPa is attained. In the fabrication process, the high temperature material glass and a ceramic adhesive are applied as the insulating and sealing layers. Particularly, the Cr stress buffering layer is successfully electroplated in the high temperature ECM by means of the hard chrome plating process. The flat metallization layer is accomplished by using a combined structure with Cr and Cu metallization layers. The experimental evaluations, including the electrical and thermal characteristics of the ECM, have been part of in the study. The forward and reverse characteristics of the ECM are presented up to 250oC, indicating proper device functionality. The study on the reverse characteristics of the ECM indicates that the large leakage current at high temperature is not due to the package surrounding the chip, but chiefly caused by the Schottky junction and the chip passivation layer. Finally, steady-state and transient measurements are conducted in terms of the thermal measurements. The steady-state thermal measurement is used to demonstrate the cooling system reduction. To obtain the thermal parameters of the different layers in the high temperature ECM, the transient thermal measurement is applied to a single chip ECM based on the temperature cooling-down curve measurement. / Ph. D.

Energy piles are deep foundation elements designed to utilize near-surface geothermal energy, while at the same time serve as foundations for buildings. The use of energy piles for geothermal heat exchange has been steadily increasing during the last decade, yet there are still pending questions on their thermo-mechanical behavior. The change in temperature along energy piles, resulting from their employment in heat exchange operations, causes axial displacements, thermally induced axial stresses and changes in mobilized shaft resistance which may have possible effects on their behavior. In order to investigate these effects, an extensive field test program, including conventional pile load tests and application of heating-cooling cycles was conducted on three energy piles during a period of six weeks. Temperature changes were applied to the test piles with and without maintained mechanical loads to investigate the effects of structural loads on energy piles. Moreover, the lengths of the test piles were determined to represent different end-restraining conditions at the toe. Various sensors were installed to monitor the strain and temperature changes along the test piles. Axial stress and shaft resistance profiles inferred from the field test data along with the driven conclusions are presented herein for all three test piles. It is inferred from the field test results that changes in temperature results in thermally induced compressive or tensile axial stresses along energy piles, the magnitude of which increases with higher restrictions such as structural load on top or higher toe resistance. Moreover, lower change in shaft resistance is observed with increasing restrictions along the energy piles. In addition to the design, deployment, and execution of the field test, a thermo-mechanical cyclic numerical model was developed as a part of this research. In this numerical model, load-transfer approach was coupled with the Masing's Rule in order to simulate the two-way cyclic axial displacement of energy piles during temperature changes. The numerical model was validated using the field test results for cyclic thermal load and thermo-mechanical load applications. It is concluded that the use of load-transfer approach coupled with the Masing's Rule is capable of simulating the cyclic thermo-mechanical behavior of energy piles. / Ph. D.

PTMO-urethane and urea diacrylates (UtDA, UrDA) were synthesized from a two-step reactions of bis (4-isocyanatocyclohexyl) methane (HMDI) with either α,Ï -hydroxy-terminated poly (tetramethylene oxide) (PTMO Mn 250, 1000, 2000 and 2900 g/mol) or α,Ï -aminopropyl-terminated PTMO and 2-hydroxyethyl acrylate (HEA). PTMO-based ester precursors (EtDA) were also synthesized from α,Ï -hydroxy-terminated PTMO (Mn 1000 and 2000 g/mol). Two bis acetoacetates were synthesized from acetoacetylation of 1,4-butanediol and 250 g/mol hydroxy-terminated PTMO with tert-butyl acetoacetate. ¹H NMR spectroscopy confirmed the structure and average molecular weights (Mn)of diacrylates. Mn of these precursors were in the range of 950 to 3670 g/mol by ¹H NMR. The rheological properties of diacrylates were studied and activation energies for flow were calculated. Activation energies increased with increasing Mn and hydrogen-bond segment content. Michael carbon addition was employed to covalently crosslink the precursors resulting in networks with gel fractions better than 90%. DSC and DMA experiments revealed that networks had a broad distribution of glass transition temperatures depending on Mn and degree of hydrogen bonding present in the diacrylates. Their Tg's varied from -61 ºC to 63 ºC depending on the crosslinking density and hydrogen-bonding segment content. TGA revealed that UtDA and UrDA networks had an improved thermal stability compared to their EtDA counterparts. Tensile properties showed a variation depending on the structure and Mn of diacrylate and BisAcAc precursors. The storage moduli of networks precursor change from 25.3 MPa to 2.0 MPa with increasing Mn of the urethane diacrylate Elongation at break increased from 255% to 755 % for the same networks. The Young's moduli increased from 3.27 MPa for EtDA 2000 to 311.1 MPa for UrDA 2000 which was attributed to increasing degree of hydrogen-bonding. Acid functionalization of C70 P Baytubes multiwalled carbon nanotubes (MWCNT) generated acid-functionalized nanotubes (MWCNT-COOH). Suspension of MWCNT-COOH in organic solvents (chloroform, toluene, THF, DMF and 2-propanol) were prepared. DLS indicated average particle diameters of MWCNT-COOH in DMF and in 2-propanol were 139 nm and 162 nm respectively. FESEM of suspensions revealed aggregate free dispersion of MWCNT-COOH in DMF and 2-propanol. MWCNT-COOH containing composite networks were prepared. FESEM images of fracture surfaces of UtDA showed MWCNT-COOH were well-dispersed in the composites. DMA showed an increase in the rubbery plateau modulus which correlated with the MWCNT-COOH content in the networks. Tensile testing also revealed a relationship between MWCNT-COOH content and young's moduli and strain at break of networks. Storage moduli of networks increased from 25 MPa to 211 MPa with increasing MWCNT-COOH content whereas elongation at break decreased from 255 % to 146 %. UtDAs and pentaerythritol tetraacrylate (PETA) were crosslinked under UV radiation (6 passes, 1.42 ± 0.05 W.cm2 for each pass) in the presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA) (1 wt. % of the mixture) UV initiator. DMA demonstrated the presence of broad glass transition regions with a range of Tg's which varied from -60 °C to -30°C. Tensile testing also revealed the relationship between Young's moduli, strain at break and the molecular weight of the diacrylates. The increasing molecular weight of urethane diacrylate precursors caused a drop in the storage moduli of networks from 15.8 MPa to 1.4 MPa and an increase in elongation at break from 76 % to 132 %. / Master of Science