京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19377号 / 農博第2147号 / 新制||農||1037(附属図書館) / 学位論文||H28||N4957(農学部図書室) / 32391 / 新制||農||1037 / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 吉村 剛, 教授 藤井 義久, 准教授 森 直樹 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

The objective of this study was to develop a model to predict the viscoelastic material functions of a vinyl ester (VE) polymer (Derakane 441-400, Ashland Co.,) with variations in its material properties. Short-term tensile creep/creep recovery experiments were conducted at two stress levels and at four temperatures below the glass transition temperature of the VE polymer, with 10 replicates for each test configuration. Experimental strains in both the longitudinal and transverse directions were measured using a digital image correlation technique. The measured creep strain versus time responses were subsequently used to determine the creep compliances using the generalized viscoelastic constitutive equation with a Prony series representation. The variation in the creep compliances of Derakane 441-400 was described by formulating the probability density functions (PDFs) and the corresponding cumulative distribution functions (CDFs) of the creep compliances using the two-parameter Weibull and log-normal distributions. The maximum likelihood estimation technique was used to obtain the Weibull shape and its scale parameters and the log-normal location and its scale parameters. The goodness-ofit of the distributions was determined by performing Kolmogorov-Smirnov (K-S) hypothesis tests. Based on the K-S test results, the Weibull distribution is a better representation of the creep compliances of Derakane 441-400 when compared to the log-normal distribution. Additionally, the Weibull scale and shape parameters of the creep compliance distributions were shown to be time and temperature dependent. Therefore, two-dimensional quadratic Lagrange interpolation functions were used to characterize the Weibull parameters to obtain the PDFs and subsequently the CDFs of the creep compliances for the complete design temperature range during steady state creep. At each test temperature, creep compliance curves were obtained for CDF values of 0.05, 0.50 and 0.95 and compared with the experimentally obtained lowest, mean and highest creep compliances, respectively. The predicted creep compliances of Derakane 441-400 in the design space are in good agreement with the experimental data.

A data analytic materials informatics methodology is proposed after applying different data mining techniques on some datasets of particular domain in order to discover and model certain patterns, trends and behavior related to that domain. In essence, it is proposed to develop an information mining tool for vapor-grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites as a case study. Formulation and processing factors (VGCNF type, use of a dispersing agent, mixing method, and VGCNF weight fraction) and testing temperature were utilized as inputs and the storage modulus, loss modulus, and tan delta were selected as outputs or responses. The data mining and knowledge discovery algorithms and techniques included self-organizing maps (SOMs) and clustering techniques. SOMs demonstrated that temperature had the most significant effect on the output responses followed by VGCNF weight fraction. A clustering technique, i.e., fuzzy C-means (FCM) algorithm, was also applied to discover certain patterns in nanocomposite behavior after using principal component analysis (PCA) as a dimensionality reduction technique. Particularly, these techniques were able to separate the nanocomposite specimens into different clusters based on temperature and tan delta features as well as to place the neat VE specimens in separate clusters. In addition, an artificial neural network (ANN) model was used to explore the VGCNF/VE dataset. The ANN was able to predict/model the VGCNF/VE responses with minimal mean square error (MSE) using the resubstitution and 3olds cross validation (CV) techniques. Furthermore, the proposed methodology was employed to acquire new information and mechanical and physical patterns and trends about not only viscoelastic VGCNF/VE nanocomposites, but also about flexural and impact strengths properties for VGCNF/ VE nanocomposites. Formulation and processing factors (curing environment, use or absence of dispersing agent, mixing method, VGCNF fiber loading, VGCNF type, high shear mixing time, sonication time) and testing temperature were utilized as inputs and the true ultimate strength, true yield strength, engineering elastic modulus, engineering ultimate strength, flexural modulus, flexural strength, storage modulus, loss modulus, and tan delta were selected as outputs. This work highlights the significance and utility of data mining and knowledge discovery techniques in the context of materials informatics.

The use of nanoreinforcements in automotive structural composites has provided promising improvements in their mechanical properties. For the first time, a robust statistical design of experiments approach was undertaken to demonstrate how key formulation and processing factors (nanofiber type, use of dispersing agent, mixing method, nanofiber weight fraction, and temperature) affected the dynamic mechanical properties of vapor-grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites. Statistical response surface models were developed to predict nanocomposite storage and loss moduli as functions of significant factors. Only ~0.50 parts of nanofiber per hundred parts resin produced a roughly 20% increase in the storage modulus versus that of the neat VE at room temperature. Optimized nanocomposite properties were predicted as a function of design factors employing this methodology. For example, the use of highshear mixing (one of the mixing methods in the design) with the oxidized VGCNFs in the absence of dispersing agent or arbitrarily with pristine VGCNFs in the presence of dispersing agent was found to maximize the predicted storage modulus over the entire temperature range (30-120 °C). To study the key concept of interphase in thermoset nanocomposites, molecular dynamics simulations were performed to investigate liquid VE resin monomer interactions with the surface of a pristine VGCNF. A liquid resin having a mole ratio of styrene to bisphenol A-diglycidyl dimethacrylate monomers consistent with a 33 wt% styrene VE resin was placed in contact with both sides of pristine graphene sheets, overlapped like shingles, to represent the outer surface of a pristine VGCNF. The relative monomer concentrations were calculated in a direction progressively away from the surface of the graphene sheets. At equilibrium, the styrene/VE monomer ratio was higher in a 5 Å thick region adjacent to the nanofiber surface than in the remaining liquid volume. The elevated styrene concentration near the nanofiber surface suggests that a styrene-rich interphase region, with a lower crosslink density than the bulk matrix, could be formed upon curing. Furthermore, styrene accumulation in the immediate vicinity of the nanofiber surface might, after curing, improve the nanofiber-matrix interfacial adhesion compared to the case where the monomers were uniformly distributed throughout the matrix.

Molecular dynamics (MD) simulations have been performed to investigate the system equilibrium through the atomic/molecular interactions of a liquid vinyl ester (VE) thermoset resin with the idealized surfaces of both pristine vapor-grown carbon nanofibers (VGCNFs) and oxidized VGCNFs. The VE resin has a mole ratio of styrene to bisphenol-A-diglycidyl dimethacrylate VE monomers consistent with a commercially available 33 wt% styrene VE resin (Derakane 441-400). The VGCNF-VE resin interactions may influence the distribution of the liquid VE monomers in the system and the formation of an interphase region. Such an interphase may possess a different mole ratio of VE resin monomers at the vicinity of the VGCNF surfaces compared to the rest of the system after resin curing. Bulk nano-reinforced material properties are highly dependent on the interphase features because of the high surface area to volume ratio of nano-reinforcements. For example, higher length scale micromechanical calculations suggest that the volume fraction and properties of the interphase can have a profound effect on bulk material properties. Interphase formation, microstructure, geometries, and properties in VGCNF-reinforced polymeric composites have not been well characterized experimentally, largely due to the small size of typical nano-reinforcements and interphases. Therefore, MD simulations offer an alternative means to probe the nano-sized formation of the interphase and to determine its properties, without having to perform fine-scale experiments. A robust crosslinking algorithm for VE resin was then developed as a key element of this research. VE resins are crosslinked via free radical copolymerization account for regioselectivity and monomer reactivity ratios. After the VE crosslinked network was created, the constitutive properties of the resin were calculated. This algorithm will be used to crosslink equilibrated VE resin systems containing both pristine and oxidized VGCNFs. An understanding of formation and kinematics of a crosslinked network obtained via MD simulations can facilitate nanomaterials design and can reduce the amount of nanocomposite experiments required. VGCNF pull-out simulations will then be performed to determine the interfacial shear strength between VGCNFs and the matrix. Interphase formation, thickness and interfacial shear strength can directly feed into higher length scale micromechanical models within a global multiscale analysis framework.

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Ester Almqvist lived between 1868 and 1934. She was one of the most eminent Swedish landscape painters in the early 20th century. This essay analyses Esters portraying of the landscape, the people and the relation between each other. The analysis is made with Erwin Panofsky's iconographic method viewed from a feminist point of view. Ester Almqvist displayed the landscape as spirited, where the human is part of the landscape. The human is a working human which is part in a bigger context where the human has a value only by existing regardless of gender, age, looks and attributes.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第24795号 / 医博第4987号 / 新制||医||1066(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 小林 恭, 教授 波多野 悦朗, 教授 羽賀 博典 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

This research investigated effect of submicron glass fiber modification on mechanical performance of short carbon fiber reinforced vinyl ester resin. Firstly, the mixture of resin and glass fiber was made by mixing submicron fiber into resin in a homogenizer at the speed of 5000 rpm in 30 minutes. Then, this modified resin was reinforced by short carbon fiber at the length of 1 mm, 3mm and 25 mm. The modifying effects were accessed by evaluating mechanical properties such as: bending, tensile, impact test as well as dynamic mechanical analysis. To explain some manners of material caused by adding glass fiber into resin, some techniques were also used (IFSS, SEM, laser microscope scanner, ultrasonic S-scan, X-ray ...). / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24636号 / 工博第5142号 / 新制||工||1982(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大内 誠, 教授 秋吉 一成, 教授 大北 英生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM