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O/HO vapor generator for contrast-variation neutron scattering有馬 寛*; 高田 慎一; 笠井 聡*; 大内 啓一*; 森川 利明*; 宮田 登*; 宮崎 司*; 青木 裕之; 岩瀬 裕希*; 廣井 孝介; et al.
Journal of Applied Crystallography, 56(6), p.1802 - 1812, 2023/12
被引用回数：0 パーセンタイル：0.02(Chemistry, Multidisciplinary)The contrast-variation technique in neutron scattering experiments plays a pivotal role in distinguishing partial structures within multi-component complexes, facilitating the elucidation of distinct sample constituents. This differentiation is achieved using different isotopes, namely hydrogen and deuterium, which possess varying neutron scattering characteristics. This study presents a novel vapor generator designed for neutron scattering experiments, enabling continuous control of the DO/HO ratio of the vapor. This feature is especially useful for contrast-variation studies. The generator features two saturators and four mass flow controllers, allowing for the rapid and independent generation of DO/HO vapors. Additionally, the incorporation of the two-temperature method ensures accurate dew point control within a margin of 
0.2
Cdp. This setup proves useful for conducting time-resolved experiments and can accelerate research on functional polymers, such as polymer electrolyte membranes for fuel cells, where water potential assumes critical importance.
柴田 基樹*; 中西 洋平*; 阿部 淳*; 有馬 寛*; 岩瀬 裕希*; 柴山 充弘*; 元川 竜平; 熊田 高之; 高田 慎一; 山本 勝宏*; et al.
Polymer Journal, 55(11), p.1165 - 1170, 2023/11
被引用回数：1 パーセンタイル：51.7(Polymer Science)Marine ecosystem degradation due to micro plastics is a significant environmental problem, as acknowledged by Sustainable Development Goal 14. Decomposition of plastics using near critical or supercritical water is one of the promising methods to reduce micro plastics. To attain the optimization of the method for improving environmental friendliness, it is necessary to clarify the structural change of materials during the process. We, thus, investigated the decomposition processes of polystyrene particles dispersed in deuterated water (D
O) during heating under near critical or supercritical conditions by using in situ small-angle neutron scattering. Under subcritical conditions, the PS particles were swollen by DO due to increased compatibility with temperature. Near the critical point in subcritical conditions, the cleavage of PS chains in the particles occurred, so that the swollen ratio was much enhanced though the PS particles kept their shapes. In a supercritical condition, the PS particles were degraded into oil including oligomers or monomers and the phase-separated structures with styrene-rich and DO-rich regions.
Liu, Y.*; 宮田 登*; 宮崎 司*; 春藤 淳臣*; 川口 大輔*; 田中 敬二*; 青木 裕之
Langmuir, 39(29), p.10154 - 10162, 2023/06
被引用回数：1 パーセンタイル：52.07(Chemistry, Multidisciplinary)Water absorbed by epoxy resins from a humid atmosphere considerably influences their structure and properties. Examining the effects of absorbed water on epoxy resins at their interfaces with solid substrates is crucial because of their adhesive applications in various fields. The spatial distribution of absorbed water in epoxy resin thin films under high humidity was investigated in this study by neutron reflectometry. Water molecules were found to accumulate at the SiO/epoxy resin interface after exposure at a relative humidity of 85% for 8 h. The formation of an ca.1 nm-thick condensed water layer was observed, and the thickness of this layer varied with curing conditions of epoxy systems. Furthermore, the water accumulation at the interface was noted to be affected by high-temperature and high-humidity environments. The formation of the condensed water layer is presumed to be related to the features of the polymer layer near the interface. The construction of the interface layer of epoxy resin would be affected by the interface constraint effect on the cross-linked polymer chain during the curing reaction. This study provides essential information for understanding the factors influencing the accumulation of water at the interface in epoxy resins. In the practical application, the process of improving the construction of epoxy resin near the interface would be a reasonable solution to resist the water accumulation in the interface.
Zn
Y
alloy using X-ray photoelectron spectroscopy宮崎 秀俊*; 赤塚 達吉*; 木村 耕治*; 江草 大佑*; 佐藤 庸平*; 板倉 充洋; 高木 康多*; 保井 晃*; 小澤 健一*; 間瀬 一彦*; et al.
Materials Transactions, 64(6), p.1194 - 1198, 2023/06
被引用回数：1 パーセンタイル：54.26(Materials Science, Multidisciplinary)硬X線およびソフトX線光電子分光法、およびバンド構造計算を用いて、MgZnY合金の電子構造を調査し、この材料の相安定性のメカニズムを調べた。MgZnY合金の電子構造は、フェルミエネルギー近傍に疑ギャップを持つ半金属的な電子構造を示した。MgZnY合金の観察された電子構造は、疑ギャップ構造が相安定性に寄与していることを示唆する。
佐藤 庸平*; 江草 大佑*; 宮崎 秀俊*; 木村 耕治*; 板倉 充洋; 寺内 正己*; 阿部 英司*
Materials Transactions, 64(5), p.950 - 954, 2023/05
被引用回数：1 パーセンタイル：54.26(Materials Science, Multidisciplinary)ミルフィーユ構造(MFS)を持つ希釈Mg-Zn-Y合金は、キンク変形を介して長周期積層順序(LPSO)構造を持つMg-Zn-Y合金と同等の機械強度を示す。MFSタイプのMg合金の熱安定性をより深く理解するためには、溶質濃化積層欠陥(SESFs)中のZnおよびYからなる溶質クラスター構造を明確にする必要がある。走査透過型電子顕微鏡(STEM-EELS/EDS)に基づく電子エネルギー損失およびエネルギー分散X線分光法で、MFS-Mg合金のSESFs中のZnおよびYの電子構造と組成を調べた。Zn-L2,3スペクトルは、希釈Mg合金中のZnの価電子電荷がLPSO型Mg-Zn-Y合金と異なることを示した。さらに、希釈MFS-Mg合金のY-L2,3スペクトルのL3/L2の強度比は、LPSO-Mg合金よりも大きく、これはY原子の4d3/2および4d5/2軌道の電子占有がLPSO-Mg合金と異なることを反映している。希釈MFS-Mg合金のSESF組成のSTEM-EELS解析は、Zn/Y比がLPSO-Mg合金よりも低いはずであることを示し、これはSTEM-EDS測定によっても確認された。これらの結果は、希釈MFS-Mg合金のSESFs中のクラスター構造が、LPSO型Mg-Zn-Y合金の理想的なZn6Y8クラスターとは異なるはずであることを示している。
下北 啓輔*; 山本 勝宏*; 宮田 登*; 中西 洋平*; 柴田 基樹*; 竹中 幹人*; 山田 悟史*; 瀬戸 秀樹*; 青木 裕之; 宮崎 司*
Soft Matter, 19(11), p.2082 - 2089, 2023/03
被引用回数：0 パーセンタイル：0(Chemistry, Physical)In the case of poly(methyl methacrylate) (PMMA) thin films on a Si substrate, thermal annealing induces the formation of a layer of PMMA chains tightly adsorbed near the substrate interface, and the strongly adsorbed PMMA remains on the substrate, even after washing with toluene (hereinafter called adsorbed sample). Neutron reflectometry revealed that the concerned structure consists of three layers: an inner layer (tightly bound on the substrate), a middle layer (bulk-like), and an outer layer (surface) in the adsorbed sample. When an adsorbed sample was exposed to toluene vapor, it became clear that, between the solid adsorption layer (which does not swell) and bulk-like swollen layer, there was a "buffer layer" that could sorb more toluene molecules than the bulk-like layer. This buffer layer was found not only in the adsorbed sample but also in the standard spin-cast PMMA thin films on the substrate. When the polymer chains were firmly adsorbed and immobilized on the Si substrate, the freedom of the possible structure right next to the tightly bound layer was reduced, which restricted the relaxation of the conformation of the polymer chain strongly. The "buffer layer" was manifested by the sorption of toluene with different scattering length density contrasts.
眞田 幸尚; 阿部 智久; 佐々木 美雪; 菅野 麻里奈*; 山田 勉*; 中曽根 孝政*; 宮崎 信之*; 押切 圭介*; 渡部 浩司*
Journal of Nuclear Science and Technology, 10 Pages, 2023/00
被引用回数：0 パーセンタイル：0.01(Nuclear Science & Technology)主な放射性物質を除去した「処理水」にはトリチウムが含まれており、日本のステークホルダーからはどのように処理するかが議論されている。施設内の処理水の量は限界に達しており、日本政府は、2023年度(年度:年度)までに海に放流することを決定した。本研究では、福島第一原子力発電所(FDNPS)のトリチウム水放出用のシンプルで実用的なトリチウムモニターを開発した。シンプルで実用的なトリチウムモニターは、薄いプラスチックシンチレーターシートに基づくFDNPSトリチウム水放出用に開発された。開発されたデバイスは、標準的なトリチウム溶液と最小検出可能活性を計算する方法を使用して較正された。厚さ0.25mmのシンチレータ15個を0.26Lのフローセルに配置して、サンプル水を供給し、3,200mm
の有効表面積を得ることができる。完全な水でのトリチウム水の効率は0.000035cpsBq
である。単純なシールド条件下で検出可能な最小活性は7,800BqLであった(測定時間は3,600秒であった)。
下北 啓輔*; 山本 勝宏*; 宮田 登*; 有馬 寛*; 中西 洋平*; 竹中 幹人*; 柴田 基樹*; 山田 悟史*; 瀬戸 秀樹*; 青木 裕之; et al.
Langmuir, 38(41), p.12457 - 12465, 2022/10
被引用回数：0 パーセンタイル：0(Chemistry, Multidisciplinary)We measured the neutron reflectivity (NR) of isotactic polypropylene (PP) thin films deposited on Si substrates modified by hexamethyldisilazane (HMDS) at the saturated vapor pressure of deuterated water at 25C and 60C/85% RH to investigate the effect of HMDS on the interfacial water accumulation in PP-based polymer/inorganic filler nanocomposites and metal/resin bonding materials. We found that the amount of water accumulated at the PP/Si interface decreased with increasing immersion time of the Si substrate in a solution of HMDS in hexane prior to PP film deposition. During the immersion of the Si substrate, the HMDS molecules were deposited on the Si substrate as a monolayer without aggregation. Furthermore, the coverage of the HMDS monolayer on the Si substrate increased with increasing immersion time. At 60C and 85% RH, only a slight amount of interfacial water was detected after HMDS treatment for 1200 min. As a result, the maximum concentration of interfacial water was reduced to 0.1 from 0.3, where the latter corresponds to the PP film deposited on the untreated substrate.
Yamaguchi, Ko*; 川口 大輔*; 宮田 登*; 宮崎 司*; 青木 裕之; Yamamoto, Satoru*; 田中 敬二*
Physical Chemistry Chemical Physics, 24(36), p.21578 - 21582, 2022/09
被引用回数：5 パーセンタイル：70.33(Chemistry, Physical)A better understanding of the chemical reaction between epoxy and amine compounds at a solid interface is crucial for the design and fabrication of materials with appropriate adhesive strength. Here, we examined the curing reaction kinetics of epoxy phenol novolac and 4,4'-diaminodiphenyl sulfone at the outermost interface using sum-frequency generation spectroscopy, and X-ray and neutron reflectivity in conjunction with a full atomistic molecular dynamics simulation. The reaction rate constant was much larger at the quartz interface than in the bulk. While the apparent activation energy at the quartz interface obtained from an Arrhenius plot was almost identical to the bulk value, the frequency factor at the quartz interface was greater than that in the bulk. These results could be explained in terms of the densification and orientation of reactants at the interface, facilitating the encounter of the reactants present.
和泉 篤士*; 首藤 靖幸*; 柴山 充弘*; 宮田 登*; 宮崎 司*; 青木 裕之
Langmuir, 37(47), p.13867 - 13872, 2021/11
被引用回数：2 パーセンタイル：14.88(Chemistry, Multidisciplinary)The structural formation mechanism of phenolic resin-silica interfaces was investigated in situ by neutron reflectometry during curing. There was a 4 nm thick novolac resin adsorption layer on the silica surface before curing. The curing reaction of the novolac resin with hexamethylenetetramine (HMTA) increased the coherent neutron scattering length density of the resin due to the cure shrinkage accompanied by the volatilization of ammonia, which is a byproduct of HMTA decomposition. As curing proceeded at 180C, the thickness of the bulk layer increased despite the cure shrinkage, and the thickness of the interfacial layer decreased from 4 to 1 nm. This is attributed to the diffusion of decomposed HMTA fragments generated in the bulk layer into the interfacial novolac adsorption layer during diffusion throughout the bulk layer, incorporating the upper part of the interfacial layer reacting with the fragment into the bulk layer. On the other hand, the fragments could not diffuse into the tightly bound immobile segments of novolac resin in direct contact with the silica surface, retaining the 1-2 nm thick interfacial layer in the cured resin. This structural formation mechanism caused interfacial cross-link inhomogeneity in the cured resin on the silica surface.
宮崎 司*; 宮田 登*; 有馬 寛*; 吉良 弘*; 大内 啓一*; 笠井 聡*; 津村 佳弘*; 青木 裕之
Langmuir, 37(32), p.9873 - 9882, 2021/08
被引用回数：5 パーセンタイル：38.19(Chemistry, Multidisciplinary)We investigated the structure of the crystalline adsorption layer of poly(vinyl alcohol) (PVA) in hot water by neutron reflectivity in two cases: when the adsorption layer is exposed on the substrate by leaching the upper bulk layer and when it is deeply embedded between a relatively thick PVA film and substrate. In both cases, the PVA adsorption layer consists of three layers on the Si substrate. The bottom layer, consisting of amorphous chains that are strongly constrained on the substrate, is not swollen even in hot water at 90C. The middle layer, consisting of amorphous chains that are much more mobile compared with those in the bottom layer, has no freedom to assume a crystalline form. Only the molecular chains in the top layer are crystallizable in the adsorption layer, leading to a heterogeneous layered structure in the film thickness direction. This layered structure is attributed to the crystallizable chains of PVA during the formation of the adsorption layer driven by hydrogen bonding. However, the structure and dynamics in the adsorption layer may differ in both cases because the molecular chains in the vicinity of the surface seem to be affected by surface effects even in the adsorption layer.
深沢 剛司*; 宮川 高行*; 内田 昌人*; 山本 智彦; 宮崎 真之; 岡村 茂樹*; 藤田 聡*
日本機械学会論文集(インターネット), 87(898), p.21-00007_1 - 21-00007_17, 2021/06
本論文では、積層ゴムを用いた免震構造物の耐震安全マージンに関する基礎研究について述べた。免震構造物で想定される地震応答の変動は、「入力地動による地震応答の変動」と「免震装置の製造に伴う設計値の誤差」の重ね合わせの下で発生する。それらの状態を考慮した地震応答解析は、孤立した構造物の耐震安全マージンを評価するために重要である。本論文は、ナトリウム冷却高速炉(SFR)用のゴム製ベアリングからなる隔離構造物の耐震安全マージンが、地震応答の変動要因を考慮した地震応答解析を通じて日本電気協会ガイド4601(JEAG4601)およびSFRの基礎地動に対して確保されることを明らかにする。さらに、地震応答解析の結果を使用して、耐震安全マージンと線形限界の超過確率との関係について説明する。
Sn and MgSi single crystals齋藤 亘*; 林 慶*; Huang, Z.*; 杉本 和哉*; 大山 研司*; 八方 直久*; 原田 正英; 及川 健一; 稲村 泰弘; 林 好一*; et al.
ACS Applied Energy Materials (Internet), 4(5), p.5123 - 5131, 2021/05
被引用回数：12 パーセンタイル：64.95(Chemistry, Physical)The development of thermoelectric (TE) materials, which can directly convert waste heat into electricity, is vital to reduce the use of fossil fuels. MgSn and MgSi are promising TE materials because of their superior TE performance. In this study, for future improvement of the TE performance, point defect engineering was applied to the MgSn and MgSi single crystals (SCs) via boron (B) doping. Their crystal structures were analyzed via white neutron holography and SC X-ray diffraction. Moreover, nanostructures and TE properties of the B-doped MgSn and MgSi SCs were investigated. The B-doping increased the chemical pressure on the MgSn and MgSi SCs, leading to induce vacancy defects as a point defect. No apparent change was observed in electronic transport, but thermal transport was significantly prevented. This study demonstrates that the vacancy defects can be controlled by the chemical pressure, and can aid in achieving a high TE performance for the MgSn and MgSi SCs.
宮崎 司*; 下北 啓輔*; 山本 勝宏*; 青木 裕之; 山田 悟史*; 宮田 登*
Langmuir, 36(49), p.15181 - 15188, 2020/12
被引用回数：6 パーセンタイル：31.74(Chemistry, Multidisciplinary)We investigated the polymer chain dynamics in a 2-3 nm thick poly(vinyl acetate) (PVAc) adsorption layer on a Si substrate with a native oxide layer via neutron reflectometry combined with toluene vapor-induced swelling. We can investigate the polymer chain dynamics difference in the film thickness direction by the difference in the degree of swelling of the polymer layers detected by neutron reflectometry. The mobility of the polymer chains depends on the distance from the substrate. The results elucidated that the interfacial layer with a thickness of approximately 1 nm did not swell at all with toluene vapor, which is a solvent for PVAc. Meanwhile, the surface layer excessively swells with toluene vapor compared to the bulk. This indicates that the polymer chain within the interfacial region is immobilized by the substrate through hydrogen-bonding interaction, but in the surface region, the surface effect overcomes this interfacial interaction. We concluded that the polymer chains in the adsorption layer are either strongly constrained to the substrate, owing to hydrogen bonding, or more mobile than the bulk, owing to the surface effect.
阿久津 和宏*; 吉良 弘*; 宮田 登*; 花島 隆泰*; 宮崎 司*; 笠井 聡*; 山崎 大; 曽山 和彦; 青木 裕之
Polymers (Internet), 12(10), p.2180_1 - 2180_10, 2020/10
被引用回数：2 パーセンタイル：7.04(Polymer Science)A large background scattering originating from the sample matrix is a major obstacle for fine-structure analysis of a nanometric layer buried in a bulk material. As polarization analysis can decrease undesired scattering in a neutron reflectivity (NR) profile, we performed NR experiments with polarization analysis on a polypropylene (PP)/perhydropolysilazane-derived SiO (PDS)/Si substrate sample, having a deep-buried layer of SiO to elucidate the fine structure of the nano-PDS layer. This method offers unique possibilities for increasing the amplitude of the Kiessig fringes in the higher scattering vector (Qz) region of the NR profiles in the sample by decreasing the undesired background scattering. Fitting and Fourier transform analysis results of the NR data indicated that the synthesized PDS layer remained between the PP plate and Si substrate with a thickness of approximately 109 
;. Furthermore, the scattering length density of the PDS layer, obtained from the background subtracted data appeared to be more accurate than that obtained from the raw data. Although the density of the PDS layer was lower than that of natural SiO, the PDS thin layer had adequate mechanical strength to maintain a uniform PDS layer in the depth-direction under the deep-buried condition.
有馬 寛*; 宮田 登*; 吉田 鉄生*; 笠井 聡*; 大内 啓一*; Zhang, S.*; 宮崎 司*; 青木 裕之
Review of Scientific Instruments, 91(10), p.104103_1 - 104103_7, 2020/10
被引用回数：9 パーセンタイル：56.16(Instruments & Instrumentation)We developed a novel humidity control system for neutron reflectivity measurements based on the two-way gas-flow method that can generate up to 85% relative humidity (RH) within a temperature range of 5-85C. The system consists of a gas-flow-type humidity generator and a thermostatic sample chamber, each of which can independently control the temperature. The key features include rapid humidity response and long stable operation time. The humidity reaches equilibrium within 2 to 5 min during the humidity change, and the system exhibited acceptable stability over a three-day, nonstop experimental measurement duration, with a precision of 1% RH at 85C and 85% RH. The sample chamber is capable of measuring substrate samples with dimensions of up to 2-in. in diameter and 5-mm in thickness. We demonstrate the reflectivity data measured at a pulsed neutron facility, MLF BL17, in the Japan Proton Accelerator Research Complex. The combined use of this system with neutrons permits in situ, time-resolved studies of the swelling process of polyvinyl alcohol and adhesive materials.
和泉 篤士*; 首藤 靖幸*; 柴山 充弘*; 吉田 鉄生*; 宮田 登*; 宮崎 司*; 青木 裕之
Macromolecules, 53(10), p.4082 - 4089, 2020/05
被引用回数：7 パーセンタイル：32.71(Polymer Science)The interfacial structure of a hexamethylenetetramine-cured phenolic resin on a silica surface was investigated by the complementary use of X-ray and neutron reflectivity (XRR and NR, respectively). The contrast-variation technique was applied using DO for the NR analysis in which the coherent neutron scattering length density (SLD) largely changed owing to the DO absorption of the dry phenolic resin and the hydrogen-to-deuterium exchange of phenolic hydroxyl groups. The XRR profile indicated no clear interfacial structure in terms of the mass density, whereas the NR profile indicated the presence of an interfacial nanolayer on the native silica surface according to the SLD. The thickness of the interfacial layer was 1-2 nm, which was independent of the thickness of the bulk resin layer. The formation of the interfacial layer on the silica surface could be caused by preferential adsorption of the novolac resin on the silica surface via strong hydrogen bonding between phenolic units in the novolac resin and silica surface comprising silanol and silyl ether groups resulting in interfacial cross-link inhomogeneity of the phenolic resin on the silica surface in the thickness direction. To the best of our knowledge, this is the first report of an experimental elucidation of the buried interfacial structure between the phenolic resins on the silica surface at a nanometer level.
宮崎 司*; 宮田 登*; 吉田 鉄生*; 有馬 寛*; 津村 佳弘*; 鳥飼 直也*; 青木 裕之; 山本 勝宏*; 金谷 利治*; 川口 大輔*; et al.
Langmuir, 36(13), p.3415 - 3424, 2020/04
被引用回数：14 パーセンタイル：58.64(Chemistry, Multidisciplinary)We investigated in detail the structures in the poly(vinyl alcohol) (PVA) adsorption layers on a Si substrate, which remained on the substrate after immersing the relatively thick 30 - 50 nm films in hot water, by neutron reflectometry under humid conditions. For the PVA with a degree of saponification exceeding 98 mol %, the adsorption layer exhibits a three-layered structure in the thickness direction. The bottom layer is considered to be the so-called inner adsorption layer that is not fully swollen with water vapor. This may be because the polymer chains in the inner adsorption layer are strongly constrained onto the substrate, which inhibits water vapor penetration. The polymer chains in this layer have many contact points to the substrate via the hydrogen bonding between the hydroxyl groups in the polymer chain and the silanol groups on the surface of the Si substrate and consequently exhibit extremely slow dynamics. Therefore, it is inferred that the bottom layer is fully amorphous. Furthermore, we consider the middle layer to be somewhat amorphous because parts of the molecular chains are pinned below the interface between the middle and bottom layers. The molecular chains in the top layer become more mobile and ordered, owing to the large distance from the strongly constrained bottom layer; therefore, they exhibit a much lower degree of swelling compared to the middle amorphous layer. Meanwhile, for the PVA with a much lower degree of saponification, the adsorption layer structure consists of the two-layers. The bottom layer forms the inner adsorption layer that moderately swells with water vapor because the polymer chains have few contact points to the substrate. The molecular chains in the middle layer, therefore, are somewhat crystallizable because of this weak constraint.
Si single crystals林 慶*; 齋藤 亘*; 杉本 和哉*; 大山 研司*; 林 好一*; 八方 直久*; 原田 正英; 及川 健一; 稲村 泰弘; 宮崎 譲*
AIP Advances (Internet), 10(3), p.035115_1 - 035115_7, 2020/03
被引用回数：16 パーセンタイル：73.04(Nanoscience & Nanotechnology)MgSi is a potential thermoelectric (TE) material that can directly convert waste energy into electricity. In expectation of improving its TE performance by increasing electron carrier concentration, the element boron (B) is doped in MgSi single crystals (SCs). Their detailed crystal structures are definitely determined by using white neutron holography and single-crystal X-ray diffraction (SC-XRD) measurements. The white neutron holography measurement proves that the doped B atom successfully substitutes for the Mg site. The SC-XRD measurement confirms the B-doping site and also reveals the presence of the defect of Si vacancy (VSi) in the B-doped MgSi SCs. Regarding TE properties, the electrical conductivity, 
, and the Seebeck coefficient, S, decreases and increases, respectively, due to the decrease in the electron carrier concentration, contrary to the expectation. The power factor of the B-doped MgSi SCs evaluated from and S does not increase but rather decreases by the B-doping.
宮崎 司*; 宮田 登*; 浅田 光則*; 津村 佳弘*; 鳥飼 直也*; 青木 裕之; 山本 勝宏*; 金谷 利治*; 川口 大輔*; 田中 敬二*
Langmuir, 35(34), p.11099 - 11107, 2019/08
被引用回数：22 パーセンタイル：67.64(Chemistry, Multidisciplinary)We investigated the swelling behaviors of poly(vinyl alcohol) (PVA) films deposited on Si wafers with water vapor, which is a good solvent for PVA for elucidating structural and dynamical heterogeneities in the film thickness direction. Using deuterated water vapor, structural and dynamical differences in the thickness direction can be detected easily as different degrees of swelling in the thickness direction by neutron reflectivity. Consequently, the PVA film with a degree of saponification exceeding 98 mol % exhibits a three-layered structure in the thickness direction. It is considered that an adsorption layer consisting of molecular chains that are strongly adsorbed onto the solid substrate is formed at the interface with the substrate, which is not swollen with water vapor compared with the bulk-like layer above it. The adsorption layer is considered to exhibit significantly slower dynamics than the bulk. Furthermore, a surface layer that swells excessively compared with the underneath bulk-like layer is found. This excess swelling of the surface layer may be related to a higher mobility of the molecular chains or lower crystallinity at the surface region compared to the underneath bulk-like layer. Meanwhile, for the PVA film with a much lower degree of saponification, a thin layer with a slightly lower degree of swelling than the bulk-like layer above it can be detected at the interface between the film and substrate only under a high humidity condition. This layer is considered to be the adsorption layer composed of molecular chains loosely adsorbed onto the Si substrate.
