{"created":"2023-06-20T13:20:14.881018+00:00","id":259,"links":{},"metadata":{"_buckets":{"deposit":"9ae6b23a-c018-4ce1-a513-e569c7bb4fe5"},"_deposit":{"created_by":1,"id":"259","owners":[1],"pid":{"revision_id":0,"type":"depid","value":"259"},"status":"published"},"_oai":{"id":"oai:ir.soken.ac.jp:00000259","sets":["2:427:10"]},"author_link":["7922","7924","7923"],"item_1_creator_2":{"attribute_name":"著者名","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"林, 久史"}],"nameIdentifiers":[{}]}]},"item_1_creator_3":{"attribute_name":"フリガナ","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"ハヤシ, ヒサシ"}],"nameIdentifiers":[{}]}]},"item_1_date_granted_11":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"1992-03-16"}]},"item_1_degree_grantor_5":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_name":"総合研究大学院大学"}]}]},"item_1_degree_name_6":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士（理学）"}]},"item_1_description_12":{"attribute_name":"要旨","attribute_value_mlt":[{"subitem_description":"　　　Aqueous solutions of small organic molecules often show anoma-\nlous behavior in various transport and thermal properties. The formation of\n some kind of molecular aggregates or microinhomogeneity has generally\n been invoked for explaining these peculiarities. However, details of the\n microinhomogeneity are not clear as yet.\n　　　The small angle X-ray scattering (SAXS) method is one of the most\n direct ones to study microinhomogeneity. In the analysis, SAXS intensity\n curve (I(s)) is expanded as follows: \n　　　　I(s)=r<small>0</small>-r<small>2</small>s<sup>2</sup>+r<small>4</small>s<sup>4</sup>-r<small>6</small>s<sup>6</sup>+ ... ...(1)\nwhere \n　　　　r<small>2i</small>=(1/(2i+1)i)<Δρ<small>e</small>(O)Δρ<small>e</small>(r)>r<sup>2i</sup> 4πr<sup>2</sup>dr.     . . . (2) \n  Here s is the scattering parameter(s=4πsinθ/λ,where 2θ is the scattering\n angle and λ is the wavelength of X-rays), Δρ<small>e</small>(r) is the difference in the\n electron density from the average at position r, and < > denotes the\n ensemble average. The 'moment' determined through a SAXS measure-\nment (r<small>2i</small>) reflects various properties of the solution. The zero-angle scat-\ntering intensity (I(O)), which relates to the square of the number of mole\ncules concerning the microinhomogeneity, is equal to r<small>0</small> . The mean square\n fluctuation is concentration (<N>(ΔC<small>1</small>)<sup>2</sup>>) is derived from I(O). The correla-\ntion length (ξ), which indicates the average size of the microinhomogenei-\n ty, is calculated as (r<small>2</small>/r<small>0</small>)<sup>0.5</sup>. These two (r<small>0</small> and r<small>2</small> ) have been chief concern\n in the previous SAXS studies.\n　　　Higher order coefficients in eq. (1), which have not been employed\n in previous SAXS studies, have a possibility to give additional information\n about microinhomogeneity as long as accurate enough SAXS data can be\n accumulated. To understand the complicated mixing state of the molecular\n aqueous solutions, it is required to use as many kinds of indicators of\n microinhomogeneity as possible. Thus, in this thesis, the author has\n attempted to apply the higher order coefficients to studying the mixing\n state.\n　　　A point-focusing diffractometer with a double-bent LiF crystal\n monochromator as well as a position-sensitive proportional counter has\n been constructed to obtain accurate SAXS data. With this diffractometer,\n small-angle resolution of better than 0.42 is achieved. To evaluate the\n performance of the diffractometer, SAXS data on several pure liquids and\n aqueous solutions were measured. The results showed that this diffrac-\n tometer produced incident beams intense enough to measure SAXS on\n solutions, making a collimation effect negligible simultaneously.\n　　　With the diffractometer mentioned above, it is possible to accurately\n determine the higher order coefficients. Accordingly, the following new\n parameter (χ) is proposed:\n　　　　χ=r<small>0</small> r<small>4</small>/r<small>2</small><sup>2</sup>                         . . (3) \nBeing related with r<small>4</small> , this dimensionless parameter reflects the shape of\n I(s). Several theoretical SAXS functions were examined in order to under-\nstand the physical meaning of χ further, and χ has been interpreted to\n represent the size dispersion of fluctuating clusters formed in solution: a\n large/small χ corresponds to a large/small size dispersion.\n　　　To examine whether or not an analysis in terms of χ is meaningful\n in understanding the mixing state, the SAXS curve shape of 2-butoxyeth-\n anol (BE) and 1-propanol (abbreviated to NPA) aqueous solution has\n been extensively studies. The behavior of χ for the two aqueous solutions\n shows marked contrast.\n　　　BE aqueous solution has a lower critical solution temperature near\n room temperature, and its correlation length (ξ) and concentration fluctua-\ntion (<N><(ΔC<small>1</small>)<sup>2</sup>>) showed very large variations with temperature and\n concentration. In accordance with <N><(ΔC<small>1</small>)<sup>2</sup>> and ξ,χ markedly\n changed with both concentration and temperature.\n　　　On the other hand, NPA mixes with water at any concentration and\n at any temperature. ξ changed gradually with concentration but showed\n almost no change with temperature. The χ of NPA aqueous solution\n changed smoothly with concentration but varied only slightly with tempera-\nture; modest/immodest local structure change with temperature and\n concentration of NPA/BE aqueous solution is reflected on χ. Thus, it has\n been experimentally proved that χ is very sensitive to the mixing state and\n is accordingly available as a useful parameter.\n  　　　In terms of the obtained χ's, a new piece of information about clus-\nters formed in the two aqueous solutions can be discussed. In BE aque-\nous solution, χ is the smallest and is about 0.8 near the critical composi-\ntion (around BE 5 mole%) at all the temperature studied and near the<\n miscibility curve in phase diagram. In NPA aqueous solution, χ takes a\n minimum value and is about 1.1 around NPA 15 mole% at all the tempera-\nture studied. Because χ is small, it is predicted that clusters having a fairly\n well-defined size are dominant in these regions. This interesting sugges-\ntion should be ascertained in future work.\n　　　A use of the diffractometer constructed in this work has also made\n it possible to obtain SAXS data within a short time. Hence, the growth of\n nickel and iron silicates in the mixed solution of metal ethylene glycolates,\n water, and tetraethoxysilane has been monitored with SAXS. At an early\n stage of polymerization, the fractal dimension (D) increases, reaching a\n constant value while the reaction is still in progress. The D value suggests\n that the structure of the gels containing metals is different from that made\n without metals. Useful catalysts are prepared by the calcination of the\n gels. A relationship between the structures of the gel and of the catalyst is\n discussed.","subitem_description_type":"Other"}]},"item_1_description_18":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_1_description_7":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_description":"総研大甲第14号","subitem_description_type":"Other"}]},"item_1_select_14":{"attribute_name":"所蔵","attribute_value_mlt":[{"subitem_select_item":"有"}]},"item_1_select_8":{"attribute_name":"研究科","attribute_value_mlt":[{"subitem_select_item":"数物科学研究科"}]},"item_1_select_9":{"attribute_name":"専攻","attribute_value_mlt":[{"subitem_select_item":"08 機能分子科学専攻"}]},"item_1_text_10":{"attribute_name":"学位授与年度","attribute_value_mlt":[{"subitem_text_value":"1991"}]},"item_1_version_type_23":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"HAYASHI, Hisashi","creatorNameLang":"en"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2016-02-17"}],"displaytype":"simple","filename":"甲14_要旨.pdf","filesize":[{"value":"346.4 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"要旨・審査要旨 / Abstract, Screening Result","url":"https://ir.soken.ac.jp/record/259/files/甲14_要旨.pdf"},"version_id":"44b35451-a5c3-4b6e-9915-edbe3fd4b9e1"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2016-02-17"}],"displaytype":"simple","filename":"甲14_本文.pdf","filesize":[{"value":"6.4 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"本文 / Thesis","url":"https://ir.soken.ac.jp/record/259/files/甲14_本文.pdf"},"version_id":"03b33ed9-36e5-487d-9f54-16013278ab67"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"thesis","resourceuri":"http://purl.org/coar/resource_type/c_46ec"}]},"item_title":"Ｘ線小角散乱法による水溶液の不均一性の研究","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Ｘ線小角散乱法による水溶液の不均一性の研究"},{"subitem_title":"Small-Angle X-Ray Scattering Studies onInhomogeneity In Aqueous Mixtures","subitem_title_language":"en"}]},"item_type_id":"1","owner":"1","path":["10"],"pubdate":{"attribute_name":"公開日","attribute_value":"2010-02-22"},"publish_date":"2010-02-22","publish_status":"0","recid":"259","relation_version_is_last":true,"title":["Ｘ線小角散乱法による水溶液の不均一性の研究"],"weko_creator_id":"1","weko_shared_id":1},"updated":"2023-06-20T14:58:13.947375+00:00"}