京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21591号 / 理博第4498号 / 新制||理||1646(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 依光 英樹, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

North Atlantic short-finned squid (Illex illececbrosus) is an underutilized species and calico scallops (Argopecten gibbys) do not achieved the same market value as Sea scallops due to their small size. North Atlantic short-finned squid have limited consumer acceptability due to their smaller, thinner, and more leathery texture than Atlantic long-finned squid (Loligo pealei). The market limitation of calico scallops is derived from their small size compared to other species of scallops available in the marketplace. Thus, restructuring or engineering food technology applied to these species to produce new products will result in more profit to the industry. Restructured squids were fabricated with heat-set binders according to the following combinations: starch, egg white albumin, fish sarcoplasmic protein, starch and egg white albumin, and starch and fish sarcoplasmic protein at various levels. Increasing the level of starch from 2 to 10% decrease the hardness, cohesiveness, and springiness of restructured squid. Two percent egg white albumin improved the hardness and cohesiveness, while 2% fish sarcoplasmic protein improved cohesiveness and springiness of the squid gel. The hardness, cohesiveness, and springiness of starch-based combinations decreased as a function of starch. Restructured scallops were prepared from cold-set binders: alginate and microbial transglutaminase at the 1% level with different setting times to yield the highest binding strength. At the setting temperature of 5° C, restructured scallops bound with alginate presented the greatest binding strength at 2 hr setting, while those bound with microbial transglutaminase required 24 hr to reach the maximum binding strength. Although alginate benefits the manufacturer with respect to the shorter setting time, the lower binding strength values may result in a decrease in consumer acceptability. / Master of Science

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<p>Ni-Fe alloys have been used in industrial applications over the past century due to their unique mechanical and magnetic properties. Currently, researchers are interested in enhancing the performance of Ni-Fe alloys by modifying their microstructure. An example of this would be the use of ultra-fine nanocrystalline Ni-Fe alloys for magnetic shielding products that are uniquely shaped and cost effective. These nanocrystalline materials usually exhibit good soft magnetic properties, such as high saturation magnetization, low coercivity and good magnetic permeability. The following study has been devoted to the magnetic properties of electrodeposited nanocrystalline Ni-Fe alloys.</p> <p>The structure and texture of electrodeposited Ni-Fe alloys was studied by two-dimensional XRD. The Ni-Fe alloys with Fe content from 24.9at. % to 54.2at. % were comprised exclusively of the FCC phase. For 60.2at. % Fe sample, a mixed phase of BCC and FCC structure was found. The lattice parameter increased with increasing Fe content until 54.2at. %, and then decreased due to the presence of BCC structure. The increase in lattice parameter was attributed to the iron replacement of nickel in the Ni crystalline lattice. Texture analysis shows that all Ni-Fe alloys with different Fe content exhibit the fiber texture with a major component of theaxis aligned perpendicular to the sample plane. A second component iswith a significantly lower volume fraction. It also shows that the Ni-Fe alloy with 44.2at. % Fe exhibits the highest volume fraction of random orientation.</p> <p>Magnetic measurements showed that all Ni-Fe nanocrystalline alloys exhibit soft magnetic properties with narrow hysteresis loops. The saturation magnetization increased linearly with increasing Fe content. The magnetization at T = 2K were slightly higher than that at T = 298K. The lowest coercivity~6Oe was obtained at 44.2 at. % Fe content.</p> <p>Good agreement between Random Anisotropy Model (RAM) theory and experimental data for all the Ni-Fe alloys has been obtained. By fitting the high field magnetization curve with the Law of Approach to Saturation (LATS), the magnetocrystalline anisotropy constant (K_eff) were obtained. K_eff decreased with increasing temperature. Also, the ferromagnetic exchange lengths for each Ni-Fe alloy were calculated. They are 26nm, 21nm, 19nm, 18nm, 17nm for Ni-24.9at.%Fe, Ni-33.1at.%Fe, Ni-44.2at.%Fe, Ni-54.2at.%Fe, Ni-60.2at.%Fe at room temperature, respectively. The exchange lengths are larger than the average grain size (D) for all of the samples. The results confirmed the feasibility of Random Anisotropy Model for the prediction of the magnetic properties of the nanocrystalline Ni-Fe alloys fabricated by electrodeposition.</p> / Master of Applied Science (MASc)

Magnetic nanoparticles coated with polymers hold great promise as materials for applications in biotechnology. In this body of work, magnetic fluids for the treatment of retinal detachment are examined closely in three regimes; motion of ferrofluid droplets in aqueous media, size analysis of the polymer-iron oxide nanoparticles, and calculation of interparticle potentials as a means for predicting fluid stability. The macromolecular ferrofluids investigated herein are comprised of magnetite nanoparticles coated with tricarboxylate-functional polydimethylsiloxane (PDMS) oligomers. The nanoparticles were formed by reacting stoichiometric concentrations of iron chloride salts with base. After the magnetite particles were prepared, the functional PDMS oligomers were adsorbed onto the nanoparticle surfaces. The motion of ferrofluid droplets in aqueous media was studied using both theoretical modeling and experimental verification. Droplets (~1-2 mm in diameter) of ferrofluid were moved through a viscous aqueous medium by an external magnet of measured field and field gradient. Theoretical calculations were made to approximate the forces on the droplet. Using the force calculations, the times required for the droplet to travel across particular distances were estimated. These estimated times were within close approximation of experimental values. Characterization of the sizes of the nanoparticles was particularly important, since the size of the magnetite core affects the magnetic properties of the system, as well as the long-term stability of the nanoparticles against flocculation. Transmission electron microscopy (TEM) was used to measure the sizes and size distributions of the magnetite cores. Image analyses were conducted on the TEM micrographs to measure the sizes of approximately 6000 particles per sample. Distributions of the diameters of the magnetite cores were determined from this data. A method for calculating the total particle size, including the magnetite core and the adsorbed polymer, in organic dispersions was established. These estimated values were compared to measurements of the entire complex utilizing dynamic light scattering (DLS). Better agreement was found for narrow particle size distributions as opposed to broader distributions. The stability against flocculation of the complexes over time in organic media were examined via modified Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations. DLVO theory allows for predicting the total particle-particle interaction potentials, which include steric and electrostatic repulsions as well as van der Waals and magnetic attractions. The interparticle potentials can be determined as a function of separation of the particle surfaces. At a constant molecular weight of the polymer dispersion stabilizer, these calculations indicated that dispersions of smaller PDMS-magnetite particles should be more stable than those containing larger particles. The rheological characteristics of neat magnetite-PDMS complexes (i.e, no solvent or carrier fluid were present) were measured over time in the absence of an applied magnetic field to probe the expected properties upon storage. The viscosity of a neat ferrofluid increased over the course of a month, indicating that some aggregation occurred. However, this effect could be removed by shearing the fluids at a high rate. This suggests that the particles do not irreversibly flocculate under these conditions. / Ph. D.

Magnetic nanoparticles are of considerable interest owing to their potential applications in biotechnology and the magnetic recording industry. Iron oxides have received much attention owing to their oxidative stability and biocompatibility; however, other transition metals and their alloys are also under investigation. Cobalt has one of the largest magnetic susceptibilities of these materials, but it readily oxidizes upon exposure to air resulting in antiferromagnetic oxide. Hence, coating cobalt nanoparticles with an oxygen-impermeable sheath would confer numerous benefits. Cobalt nanoparticles were prepared by the thermolysis of dicobalt octacarbonyl in two block copolymer micellar systems, wherein the copolymers were precursors to graphite or silica. Subsequent heat treatment of the samples at 600-700oC was conducted to condense the polymer coating around the cobalt nanoparticles and form oxygen impervious graphite or silica sheaths. Magnetic and structural characterization of these novel materials afforded pertinent information about their physical properties. Magnetic susceptometry indicated that the graphite coated cobalt nanoparticles resisted oxidation for over one year. The silica coated cobalt nanoparticles had high saturated specific magnetic moments, but the coatings were brittle and grinding the particles resulted in oxidation over time. Transmission electron microscopy (TEM), high-resolution TEM (HRTEM) and energy-filtered TEM (EFTEM) were employed to study particle size and structural differences of the cobalt nanoparticles before and after heat treatment. The mean particle size and size distribution increased for the graphite coated cobalt particles, due to particle sintering at 700oC. In the silica coated cobalt nanoparticle system, the mean particle size increased when the sample was heat-treated at 600oC leading to a bimodal distribution. This bimodal distribution was explained by a fraction of the particles sintering, while others remained discrete. When the silica system was heat treated at 700oC, the particle size and size distribution remained similar to those of the pre-heat-treated sample, indicating that no sintering had taken place. The rapid pyrolysis of the polymer at 700oC may serve to lock the cobalt nanoparticles into a silica matrix, thus preventing them from coming into contact with one another and sintering. Several diffraction techniques (selected area electron diffraction (SAD), nano-beam electron diffraction (NBD) and x-ray diffraction (XRD)) were used to probe the crystal structure of graphite and silica coated cobalt nanoparticles, which was determined to be predominantly face-centered cubic. Anisotropic magnetic nanoparticles (nanorods) have an increased magnetophoretic mobility over spherical magnetic nanoparticles with the same equatorial radius. This property makes them attractive candidates for in vivo biological applications. Anisotropic mixed ferrite nanoparticles were coated with a biocompatible hydrophilic block copolymer to render them dispersible in aqueous media. Polymer coated mixed ferrite particles exhibited magnetic properties similar to that of pure magnetite, as the total level of other transition metals in the nanoparticulate system was less than 5%. Electron energy loss spectroscopy (EELS) and (EFTEM) confirmed that the dominant elements in the mixed ferrite nanoparticles were iron and oxygen. Furthermore, HRTEM, SAD and XRD analyses indicated that the crystal structure for the mixed ferrite nanoparticles was inverse spinel. X-ray diffraction peaks at low angles for the coated mixed ferrite rods corresponded to poly(ethylene oxide) peaks, suggesting that the block copolymer employed as a dispersant was associated with the particles. / Ph. D.

Le couplage des propriétés ferromagnétiques et semiconductrices représente une perspective prometteuse, afin de réaliser des technologies qui exploitent le spin des électrons. Ceci permettra de stocker et traiter des bits informatiques de façon instantanée dans le même dispositif, plutôt que dans des dispositifs séparés (mémoire et processeur). La Spintronique pourrait alors révolutionner la technologie de l'information. Un candidat potentiel pour la fabrication d'hétérostructures métal ferromagnétique/semiconducteur pour des applications en Spintronique, est le système Mn-Ge. Ce système qui est compatible avec la technologie CMOS, présente une phase intéressante pour la Spintronique qui est Mn5Ge3, avec une possibilité d'épitaxie sur le Ge(111). Afin d'intégrer cette phase dans des procédés de fabrication, nous étudions la diffusion réactive à l'état solide entre un film de Mn et un substrat de Ge (comme dans le cas de la formation des siliciures dans la technologie CMOS). L'accent a été mis sur la séquence de formation de phases lors de la réaction entre un film nanométrique de Mn et le Ge, l'influence de l'interface sur cette réaction, et sur la diffusion du Mn dans le Ge. L'incorporation du carbone dans des films minces de Mn5Ge3 a montré une augmentation notable de la température de Curie : nous présentons alors l'effet du carbone sur la réaction Mn-Ge, et sa redistribution dans les couches minces MnxGey. / Coupling ferromagnetic and semi-conducting properties represents a pathway toward producing technologies that exploit the spin of electrons. That would allow store and process computer bits instantly in a same device, rather than separate devices (memory and CPU). The Spintronics could then revolutionize the information technology. A potential candidate for the fabrication of heterostructures ferromagnetic metal / semiconductor for Spintronics applications is the Mn-Ge system. This system is compatible with CMOS technology, and presents an interesting phase for Spintronics which is Mn5Ge3 phase, which is able to be grown epitaxially on Ge(111). To integrate this phase in the manufacturing process, we study the solid state reactive diffusion between a thin Mn film and Ge substrate, to form a germanide upon the Ge substrate (as in the case of the formation of silicides in CMOS technology). Emphasis was placed on the sequence of phase formation during the reaction between a 50 nm thick Mn film and Ge, the influence of the interface on the reaction, and the diffusion of Mn in Ge. Incorporation of carbon in thin Mn5Ge3 films showed a significant increase in the Curie temperature, we then present the effect of carbon on the reaction Mn-Ge and its redistribution in thin MnxGey films.

Plus de vingt ans après la découverte de la supraconductivité à haute température critique, le mécanisme physique sous-jacente n'est pas encore bien cerné. En 2008, la découverte d'une nouvelle famille de supraconducteurs à haute température critique, les supraconducteurs à base de fer, a donné l'espoir de trouver une compréhension plus profonde des mécanismes de ce type de supraconductivité. Synthétiser des l'échantillons de grande qualité, la caractérisation des propriétés supraconductrices, l'étude des symétrices du gap et du paramètre d'ordre sont des étapes essentielles pour révéler le mécanisme. La connaissance précise du mécanisme permettra de profiter pleinement des propriétés remarquables de ces matériaux dans leurs applications industrielles si prometteuses. La thèse décrit d'abord la croissance de monocristaux de Ba$_{1-x}$K$_x$Fe$_2$As$_2$ et l'étude de leurs propriétés supraconductrices, menant vers la proposition d'une structure de gap du supraconducteur et d'un paramètre d'ordre pour les supraconducteurs à base de fer Ba-122 à partir de mesures de résistivité, de sondes à effect Hall, de spectroscopie d'Andreev en mode point-contact et de l'imagerie magnétique par la microscopie à nano-squid.Dans le chapitre 1, les événements historiques les plus marquants de la supraconductivité sont rappelés, les propriétés essentielles des supraconducteurs et le dévelopment des théories de la supraconductivité sont esquissés avant de présenter brièvement la découverte des supraconducteurs à base de fer et de donner un aperçu des questions actuelles de recherche dans ce domaine.Dans le chapitre 2, la procédure de croissance de monocristaux de Ba$_{1-x}$K$_x$Fe$_2$As$_2$ par la méthode de "self-flux", leur caractérisation par diffraction et par l'analyse de dispersion d'énergie des rayons X et la sensibilité des mesures de résistivité et de susceptibilité AC sont décrites. Puis nous présentons quelques résultats des mesures de la résistivité dépendante de la température de monocristaux du composé Ba$_{1-x}$K$_x$Fe$_2$As$_2$ (0,23 $\leq x \leq$ 0,4) sous champs magnétiques allant jusqu'à 9 T et dépendante de l'angle.Dans le chapitre 3, nous exposons quelques points essentiels du système de mesure à base de sonde de Hall que nous avons construit. Ensuite, nous présentons des mesures d'aimantation locale et globale sur des polycristaux de SmFeAsO$_{0.9}$F$_{0.1}$ synthétisés à haute pression, et de monocristaux de Ba$_{0.6}$K$_{0.4}$Fe$_2$As$_2$ effectuées par sonde de Hall et VSM.Dans le chapitre 4, nous donnons une brève introduction à la spectroscopie d'Andreev en mode point-contact, puis nous appliquons cette technique à des monocristaux de Ba$_{0.6}$K$_{0.4}$Fe$_2$As$_2$ et à une série de monocristaux de BaFe$_{2-x}$Ni$_x$As$_2$ couvrant une large gamme de dopage.Dans le chapitre 5, le développement d'un microscope de force à nano-SQUID et les mesures effectuées sur un film Rhénium d'épaisseur de 80 nm sont présentés. Le microscope peut acquérir des images topographiques et magnétiques simultanément. La plage de balayage maximale à 0.8 K est de \unit{70} {\micro\meter} $\times$ \unit{85}{\micro\meter} et sa résolution magnétique est d'environ $1,5 \times10^{-4}\Phi_0/\sqrt{\textrm{Hz}}$. Dans le chapitre 6, nous présentons quelques résultats des mesures de $\lambda$ par imagerie par microscopie de force à nano-squid sur des monocristaux de Ba(Fe$_{1-x}$Ni$_x$)$_2$As$_2$, couvrant tout le diagramme de phase. Sur les m\^{e}mes cristaux ont été effectuées des mesures du premier champ critique, de la variation de fréquence d'un oscillateur à diode tunnel et de la capacité calorifique.Enfin, au chapitre 7, un résumé détaillé et critique est présenté. / More than twenty years after the discovery of high temperature superconductors, the underlying physical mechanism is still not well understood. In 2008, the discovery of a new family of high temperature superconductors, the iron-based superconductors, provided us a new chance to understand the high temperature superconductivity. Synthesizing high quality sample, detecting the basic superconducting properties, the gap structure and order parameter symmetry are essential steps in revealing the mechanism and application of new superconductors. This dissertation describes the growth of Ba$_{1-x}$K$_x$Fe$_2$As$_2$ single crystals and the study of superconducting properties, gap structure and order parameter on Ba-122 iron-based superconductors with resistivity, Hall probe, point contact Andreev reflection spectroscopy and scanning nano-squid microscopy measurements. Some historical events concerning superconductivity are recalled, and some key properties and theories of superconductivity are presented in Chapter 1. Then we will briefly introduce the discovery and current research situation of the iron-based superconductors. In Chapter 2, the growth procedure of Ba$_{1-x}$K$_x$Fe$_2$As$_2$ single crystals with self-flux method, and the characterization of the crystals with diffraction and energy dispersive analysis of x-ray, AC susceptibility and resistivity measurements are described. Then we report some results from temperature dependent resistivity measurements on Ba$_{1-x}$K$_x$Fe$_2$As$_2$ (0.23 $\leq x \leq$ 0.4) single crystals in magnetic fields up to 9 T and angle dependent resistivity measurements on Ba$_{0.6}$K$_{0.4}$Fe$_2$As$_2$ single crystals. In Chapter 3, we introduce some details about a Hall probe measurement system we built. Then we present local and global magnetization measurements on high pressure SmFeAsO$_{0.9}$F$_{0.1}$ polycrystals and Ba$_{0.6}$K$_{0.4}$Fe$_2$As$_2$ single crystals with Hall probe and VSM.In Chapter 4, we give a brief introduction about point contact Andreev reflection spectroscopy, then we report the measurements on Ba$_{0.6}$K$_{0.4}$Fe$_2$As$_2$ single crystal and a series of electron-doped BaFe$_{2-x}$Ni$_x$As$_2$ single crystals over a wide doping range.In Chapter 5, the development of a scanning nano-SQUID force microscope and measurements performed on a 80 nm Rhenium film are presented. The microscope can take topographic and magnetic images simultaneously. The maximal scanning range is \unit{70}{\micro\meter} $\times$ \unit{85}{\micro\meter} and the magnetic resolution is about $1.5 \times10^{-4}\Phi_0/\sqrt{\textrm{Hz}}$. In Chapter 6, we present some results from lower critical field, tunnel diode oscillator, heat capacity and scanning nano-squid microscopy measurements on systematic doped Ba(Fe$_{1-x}$Ni$_x$)$_2$As$_2$ single crystals..Finally, in Chapter 7, a detailed summary is presented.

Ce travail de thèse porte sur l’étude du carbure de silicium, dopé avec du fer dans le but de réaliser un semi-conducteur magnétique dilué à température ambiante pour des applications à la spintronique. Le dopage en fer a été réalisé par implantation ionique de type multi-énergie (30 - 160 keV) à différentes fluences, conduisant à une concentration atomique constante de 2 % de 20 à 100 nm. Il a été suivi d’un recuit à haute température dans le but d’homogénéiser la concentration en dopants. Les implantations se sont déroulées à une température de 550 °C. L’optimisation des propriétés magnétiques et électroniques du SiC–Fe, de même que la compréhension des mécanismes physiques à l’origine du magnétisme induit, ont nécessité une caractérisation poussée de la microstructure des matériaux implantés. Les objectifs de ce travail ont été d’une part, de réaliser une étude à l’échelle atomique de la nanostructure en fonction des conditions d’implantations (température, fluence) et des traitements thermiques post-implantation, et d’autre part, de déterminer les propriétés magnétiques des matériaux implantés. Dans ce travail, nous avons montré par Sonde Atomique Tomographique, la présence de nanoparticules dont la taille moyenne augmente avec la température de recuit. La cartographie chimique des nanoparticules a permis de révéler l’existence de phases riches en Fe pour les échantillons recuits. L’étude magnétique (spectrométrie Mössbauer et Squid) a montré que la contribution ferromagnétique est due principalement aux nanoparticules magnétiques et/ ou aux atomes de fer magnétiques dilués dans la matrice. La corrélation entre les propriétés structurale et magnétique a permis de montrer que les atomes de fer dilués dans la matrice et substitués sur sites de silicium contribuent au signal ferromagnétique en dessous de 300 K. Nous avons donc montré dans ce travail, que la taille et la nature des phases présentes dans les nanoparticules dépendent des conditions d’implantation et des températures de recuit et qu’il est nécessaire de recuire les échantillons à haute température pour faire apparaître un ordre ferromagnétique. / This PhD thesis focuses on the study of SiC, doped with Fe in order to elaborate a diluted magnetic semiconductor at room temperature for spintronic applications. The iron doping was carried out by ion implantation of multi-energy type (30-160 keV) at different fluences, leading to a 2% constant atomic concentration between 20 to 100 nm, followed by a high temperature annealing in the goal of homogenizing the dopant concentration. The implantation temperature during this process is 550 °C, in order to avoid amorphization. The optimization of the magnetic and electronic properties of SiC-Fe, as well as the understanding of the physical mechanisms at the origin of induced magnetism, require a thorough characterization of the microstructure of the implanted materials. The objectives of this work are, on the one hand, to carry out an atomic scale study of the nanostructure according to the implantation conditions (temperature, fluence) and the post-implantation annealing and the other hand, to characterize the magnetic properties of implanted materials. In this work, we have shown by atom probe tomographic, the existence of nanoparticles whose the average size increases with the annealing temperature. The chemical mapping of the nanoparticles shows the presence of the Fe-rich phases for the annealed samples. Magnetic study (Mössbauer spectrometry and Squid) shows the ferromagnetic contribution is due to the magnetic nanoparticles and/or the diluted Fe atoms in the matrix. The correlation between structural and magnetic properties allowed showing that diluted Fe atoms and substitute to Si sites contribute to the ferromagnetic contribution below 300 K. In coupling many characterization techniques in order to give a detailed description of the different studied samples, we have shown that the size and nature of the phase present in the nanoparticles depend on the implantation conditions and the annealing temperatures and consequently it is necessary to anneal our samples at high temperature to reveal ferromagnetic order.