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論文

Phase diagram of the polystyrene/near-critical water system

柴田 基樹*; 竹中 幹人*; 元川 竜平; 熊田 高之; 上田 祐生; 宮崎 司*; 中西 洋平*; 阿部 淳*; 岩瀬 裕希*; 柴山 充弘*; et al.

Polymer, 340, p.129203_1 - 129203_7, 2025/12

 被引用回数:0 パーセンタイル:0.00(Polymer Science)

The development of effective plastic degradation methods is crucial to address environmental pollution. Hydrothermal liquefaction using near-critical water is a promising technology, but the fundamental dissolution and decomposition mechanisms remain poorly understood. This study investigates the thermodynamics of a polystyrene (PS)/water system under near-critical conditions to elucidate this mechanism. We performed in situ small-angle neutron scattering (SANS) to observe the swelling of PS particles in deuterated water (D$$_{2}$$O) at various temperatures under pressures of 10 MPa and 25 MPa. By applying the $${Flory-Huggins-Staverman}$$ (FHS) theory to the swelling data, We quantitatively determined the Flory-Huggins interaction parameter as a function of temperature and pressure by applying the FHS theory to the swelling data. Based on these results, we constructed a phase diagram of the PS/D$$_{2}$$O system. The diagram reveals that miscibility increases with increasing pressure. This work provides a thermodynamical properties of water solutions of polymers under near-critical conditions for optimizing industrial hydrothermal recycling processes.

論文

Residual stresses of small-bore butt-welded piping measured by quantum beam hybrid method

鈴木 賢治*; 三浦 靖史*; 豊川 秀訓*; 城 鮎美*; 菖蒲 敬久; 諸岡 聡; 柴山 由樹

Quantum Beam Science (Internet), 9(2), p.15_1 - 15_15, 2025/06

In this study, austenitic stainless steel pipes with a small diameter (100A) were butt-welded and the residual stress was measured using high energy synchrotron radiation X-rays and neutron. The welding residual stress is asymmetrical with respect to the welding line and has unevenness due to the crystal grains. Large axial residual stress occurs from the HAZ near the penetration bead toward the weld part. A simulation of a butt-welded pipe was performed using the finite element method. In the half model of the welded pipe, the butt-plane was assumed to keep a plane. The simulated residual stress by the half model was larger than that by the whole model. To perform an accurate simulation, the whole butt-welded piping must be modeled. The real tensile stress area from the HAZ near the penetration bead toward the weld was not obtained by the simulation.

論文

Stress and plastic strain partitioning behaviors and those contributions to martensitic transformation of retained austenite in medium manganese and transformation-induced plasticity-aided bainitic ferrite steels

北條 智彦*; 小山 元道*; 熊井 麦弥*; Zhou, Y.*; 柴山 由樹; 城 鮎美*; 菖蒲 敬久; 齋藤 寛之*; 味戸 沙耶*; 秋山 英二*

ISIJ International, 65(2), p.284 - 296, 2025/02

 被引用回数:0 パーセンタイル:0.00(Metallurgy & Metallurgical Engineering)

Stress and plastic strain distributions and those partitioning behaviors of ferrite and retained austenite were investigated in the medium manganese (Mn) and the transformation-induced plasticity-aided bainitic ferrite (TBF) steels, and the martensitic transformation behaviors of retained austenite during Luders elongation and work hardening were analyzed using synchrotron X-ray diffraction at SPring-8. The stress and plastic strain of retained austenite and volume fraction of retained austenite were remarkably changed during Luders deformation in the medium Mn steel, implying that the medium Mn steel possessed inhomogeneous deformation at the parallel part of the tensile specimen. On the other hand, the distributions of the stress, plastic strain and volume fraction of retained austenite were homogeneous and the homogeneous deformation occurred at the parallel part of the tensile specimen at the plastic deformation regime with work hardening in the medium Mn and TBF steels. The martensitic transformation of retained austenite at uders deformation in the medium Mn steel was possessed owing to the application of high stress and preferential deformation at retained austenite, resulting in a significant increase in the plastic deformation and reduction of stress in the retained austenite. The martensitic transformation of retained austenite at the plastic deformation regime with work hardening was induced by the high dislocation density and newly applied plastic deformation in retained austenite in the medium Mn steel whereas the TBF steel possessed gradual transformation of retained austenite which is applied high tensile stress and moderate plastic deformation.

論文

Stress-controlled hydrogen embrittlement failure in U-bend high-strength steel

柴山 由樹; 北條 智彦*; 小山 元道*; 秋山 英二*

International Journal of Hydrogen Energy, 88, p.1010 - 1016, 2024/10

 被引用回数:10 パーセンタイル:66.01(Chemistry, Physical)

The effect of plastic deformation on the hydrogen embrittlement behavior of high-strength martensitic steels was investigated using a U-bend test. The hydrogen embrittlement susceptibility appeared to be enhanced with increasing plastic strain. Based on fractographic and stress-strain analyses, the maximum principal stress dominated the hydrogen embrittlement fracture. Although the apparent enhancement with increasing plastic deformation was observed, the origin of the enhancement was increased residual stress arising from the evolution of graded plastic strain during U-bending. We conclude that residual stress rather than plastic strain induced by plastic deformation strongly affects hydrogen embrittlement susceptibility in deformed high-strength steel components.

論文

Microstructures and hardness of BCC phase iron-based high entropy alloy Fe-Mn-Cr-V-Al-C

若井 栄一; 能登 裕之*; 柴山 環樹*; 古谷 一幸*; 安堂 正己*; 鎌田 貴晴*; 石田 卓*; 牧村 俊助*

Materials Characterization, 211, p.113881_1 - 113881_10, 2024/05

 被引用回数:12 パーセンタイル:84.87(Materials Science, Multidisciplinary)

大強度加速器標的や原子力の分野や航空機と自動車の磁気モーターの応用のために、CoおよびNi元素を含まないbcc結晶構造を持つ鉄基高エントロピー合金(HEA) Fe-20Mn-15Cr-10V-10Al-2.5C (at%)の微細構造、機械的特性及び照射硬化挙動を調べた。この合金は、1150$$^{circ}$$Cで2時間焼ならしした後、水焼入れし、800$$^{circ}$$Cで10分間加熱した後、再び水焼入れした。この合金はbcc相を持ち、粒界に沿って2-3$$mu$$mのバナジウム炭化物が配列していた。また、ビッカース硬度は520Hvで純タングステンよりも硬かいことが分かった。走査型透過電子顕微鏡による位相差コントラスト法により磁区構造を観察したところ、粒子内のミクロサイズの磁区と表面近傍にサブミクロサイズの磁区が形成されており、この磁気特性は魅力的であった。母相中には、ナノスケール(20nm)の元素分布が観察され、原子レベル領域での結晶格子の乱れの存在が見られた。この材料は、300$$^{circ}$$Cおよび500$$^{circ}$$Cで1dpaまで照射硬化が起こらず、非常に高い耐放射線性能が確認された。これは、照射によって引き起こされるナノスケールの濃度変化とHEA内の歪み緩和によるものであると推測された。これらの緒特性は、多分野の応用において非常に魅力的な特性である。

論文

Freeze-crosslinking approach for preparing carboxymethyl cellulose nanofiber/zirconium hydrogels as fluoride adsorbents

関根 由莉奈; 南川 卓也; 杉田 剛; 永川 栄泰*; 柴山 由樹; 元川 竜平; 深澤 倫子*

Nanoscale, 16(19), p.9400 - 9405, 2024/05

 被引用回数:5 パーセンタイル:56.05(Chemistry, Multidisciplinary)

凍結架橋法により強靱なカルボキシメチルセルロースナノファイバー(CMF)/ジルコニウム(Zr)複合ハイドロゲルを開発した。本ハイドロゲルは、Zrを含むHCl溶液を凍結CMFに添加し、それを解凍することによって調製した。作製したハイドロゲルはフッ化物に対して高い吸着性を示した。本研究により、ハイドロゲルと金属の複合体の開発に有用な知見を得た。

論文

Nanocellulose hydrogels formed via crystalline transformation from cellulose I to II and subsequent freeze cross-linking reaction

関根 由莉奈; 南川 卓也; 廣井 孝介; 大場 洋次郎*; 永川 栄泰*; 杉田 剛; 柴山 由樹; 深澤 倫子*

Carbohydrate Polymers, 327, p.121538_1 - 121538_11, 2024/03

 被引用回数:20 パーセンタイル:91.36(Chemistry, Applied)

セルロースの結晶転移とその後の凍結架橋反応によってナノセルロース(NC)から形成された、無毒で強靱なNCゲルを開発した。低濃度のNaOHの使用と凍結を併用すると、凍結濃縮によりセルロースIからIIへのNCの結晶相転移が誘導されることを見出した。結晶相転移後、凍結濃縮層(FCL)内のNCとCA間の架橋により、強力なNCネットワーク構造が形成され、高い機械的強度を備えたNCハイドロゲルが形成した。凍結架橋したNCハイドロゲルは、NC-NaOHゾルと粉末吸着剤を混合することにより吸着剤を内部空間に容易に保持し、高い重金属除去効率を示した。この結果は、機能性材料の開発における化学修飾されていないセルロースの多用途性を示し、実用化の可能性を示すものである。

論文

Effect of hydrogen on fatigue life and fracture morphologies of TRIP-aided martensitic steels with added nitrogen

北條 智彦*; 長坂 明彦*; 小林 純也*; 柴山 由樹; 秋山 英二*

Metals, 14(3), p.346_1 - 346_19, 2024/03

 被引用回数:1 パーセンタイル:12.38(Materials Science, Multidisciplinary)

The effects of hydrogen on the tensile properties, fatigue life, and tensile and fatigue fracture morphologies of nitrogen-added ultrahigh-strength transformation-induced plasticity (TRIP)-aided martensitic (TM) steels were investigated. The total elongation and number of cycles to failure (Nf) of the hydrogen-charged TM steels decreased with the addition of nitrogen; in particular, adding 100 ppm of nitrogen decreased the total elongation and Nf of the TM steels. The quasi-cleavage cracking around the AlN occurred near the sample surface, which is the crack propagation region, although dimples appeared at the center of the fracture surface in the tensile samples. The initial fatigue crack initiated at the AlN precipitate or matrix/AlN interface, located at the notch root. During crack propagation, new cracks were initiated at the AlN precipitates or matrix/AlN interfaces, while quasi-cleavage crack regions were observed around the AlN precipitates. The decrease in the total elongation and Nf of the hydrogen-charged TM steel with 100 ppm of added nitrogen might be attributable to the crack initiation around the AlN precipitates formed by a large amount of hydrogen trapped at the AlN precipitates and matrix/AlN interfaces, and to the dense distribution of AlN, which promoted crack linkage.

論文

Hydrogen embrittlement property of a 1.5 GPa dual-phase steel evaluated using U-bending test; A Comparison with tempered martensitic steel with identical tensile strength

千葉 柊矢*; 小山 元道*; 北條 智彦*; 味戸 沙耶*; 柴山 由樹; Varanasi, R. S.*; 秋山 英二*

ISIJ International, 64(4), p.706 - 713, 2024/02

 被引用回数:2 パーセンタイル:24.60(Metallurgy & Metallurgical Engineering)

The hydrogen embrittlement susceptibilities of 1.5 GPa-class dual-phase (DP) and tempered martensitic steels were comparatively evaluated using U-bending test. The U-bending tests showed no differences in hydrogen embrittlement susceptibility between the two steels. The martensitic and DP steels exhibited intergranular and quasi-cleavage fractures, respectively. The crack initiation site reached the outer surface of the specimen with increasing bolt-tightening displacement. Although qualitative trends were observed between the positions of the maximum principal stress peak and the crack initiation site, the two positions significantly differed, particularly in the DP steel. This difference could arise from premature hydrogen diffusion and the plastic strain effect.

論文

Unstable stress-triaxiality development and contrasting weakening in two types of high-strength transformation-induced plasticity (TRIP) steels; Insights from a new compact tensile testing method

松野 崇*; 藤田 大樹*; 松田 知子*; 柴山 由樹; 北條 智彦*; 渡邊 育夢*

Journal of Materials Processing Technology, 322, p.118174_1 - 118174_16, 2023/12

 被引用回数:13 パーセンタイル:68.24(Engineering, Industrial)

変態誘起塑性(TRIP)鋼の加工硬化における高応力三軸度の影響は、特にオーステナイト体積率の測定結果から幅広く知られている。プレス成形プロセスにおける材料の破壊予測のためには、このTRIP挙動を明らかにすることが重要である。しかし、高応力三軸度条件における流動応力の形成メカニズムは未解明である。本研究では、TRIP鋼の応力三軸度誘起による加工硬化挙動を調査するため、微小ノッチ付き丸棒を用いた新たな引張試験手法を開発した。測微法を用いて試験片をモデル化し、有限要素解析によって引張試験中の流動応力の同定に成功した。また、開発した引張試験手法と放射光X線回折を組み合わせ、応力形成挙動をその場測定した。TRIP型ベイニティックフェライト鋼では、流動応力と応力三軸性が不安定に増加し、加工硬化指数が低下して、より高い応力三軸性が誘起されることを明らかにした。一方、TRIP型マルテンサイト鋼は、鋭いノッチの場合、加工硬化指数の急激な減少によって特徴づけられる弱化挙動を示した。X線回折の結果から、鋼材内部の微視組織の不均一性がオーステナイト相に非常に高い静水圧応力をもたらすことで、これらの対照的な挙動が説明できると結論づけた。本研究結果は、応力三軸度を考慮したTRIP鋼のプレス成形プロセスに関する枠組みについて、新たに応力三軸度を考慮した枠組みが必要であることが示唆される。

論文

Recent improvement and evaluation of radiation resistance and magnetic properties of high entropy alloys and their applications

若井 栄一; 能登 裕之*; 柴山 環樹*; 古谷 一幸*; 涌井 隆; 安堂 正己*; 牧村 俊助*; 石田 卓*

Science Talks (Internet), 8, p.100278_1 - 100278_4, 2023/12

高エントロピー合金は、その固有の特性により高い強度と良好な延性を併せ持つ傾向にある。本物質はより高性能な将来の一般産業用途だけでなく、原子力や放射線環境下での放射線影響機器の耐久性や適用範囲を高めるためにも、有望な新物質として考えられており、近年、急激に注目がされ始めている。本研究では、高エネルギー加速器ターゲットシステム部品, 原子炉, 核融合炉等の放射線下で使用される新機能材料として応用を目指し、低放射能元素(Ni, Coを含まない)からなる2種類の高エントロピー合金(Fe-Mn-V-Cr-Al-C、Fe-Si-W-Cr-V)の作製とその基本特性評価を行った。本研究で開発中の2つの材料は、次の点でそれぞれユニークな性質を持つ。前者は高強度・低放射化という特徴を共有する新しい構造材料や磁気特性として、ハイパワーモーター系材料の基礎研究として発展することが期待される。一方で、後者は、金属元素の中で最も高い融点を持つタングステンと、かなり高融点のバナジウムを混合して合金の融点を上げ、かつ高強度な合金を設計することで、新しい工学分野での新機能材料としての応用が期待されるものと考えられるものである。

論文

Structural changes of polystyrene particles in subcritical and supercritical water revealed by in situ small-angle neutron scattering

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:6 パーセンタイル:35.52(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$$_{2}$$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 D$$_{2}$$O 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 D$$_{2}$$O-rich regions.

論文

高強度薄鋼板の水素脆化メカニズム

北條 智彦*; 柴山 由樹; 味戸 沙耶*; 小山 元道*; 秋山 英二*

まてりあ, 61(7), p.413 - 418, 2022/07

本稿では自動車用高強度鋼板の水素脆化研究の紹介、および著者らの最近の研究成果の紹介を行った。自動車用高強度鋼板は優れた延性やプレス成形性を確保するため、微細組織を鋼中に微細均一に残留$$gamma$$を存在させた複相組織とすることが検討されており、水素脆化挙動に及ぼす微細組織の影響をより複雑化する。また、曲げ加工、深絞り加工、穴広げ加工、せん断加工等のプレス成形様式によって変形様式が大きく異なり、高強度鋼板に付与される塑性ひずみ、残留応力が異なるため、プレス加工も高強度鋼板の水素脆化特性評価を複雑化する因子となっている。自動車用高強度鋼板の水素脆化特性評価、水素脆化挙動の詳細な解析は、微細組織の複相化の効果、応力、塑性ひずみの効果を複合的に考慮する必要があり、これまでの高力ボルトの水素脆化研究から得られた知見をもとに、今後、自動車用高強度鋼板の耐水素脆化特性に関する研究がさらに進むことが期待される。

論文

Comparative study of stress and strain partitioning behaviors in medium manganese and transformation-induced plasticity-aided bainitic ferrite steels

北條 智彦*; 小山 元道*; 熊井 麦弥*; 柴山 由樹; 城 鮎美*; 菖蒲 敬久; 齋藤 寛之*; 味戸 沙耶*; 秋山 英二*

Scripta Materialia, 210, p.114463_1 - 114463_5, 2022/03

 被引用回数:25 パーセンタイル:81.62(Nanoscience & Nanotechnology)

The origins of the superior work hardening capability of medium manganese (M-Mn) and conventional transformation-induced plasticity-aided bainitic ferrite (TBF) steels of similar tensile strength and elongation are comparatively investigated via synchrotron X-ray diffraction measurements. The M-Mn steel undergoes preferential plastic deformation in austenite; its superior work hardening capability and associated uniform elongation are attributed to the high rates of martensitic transformation and dislocation accumulation per strain in the retained austenite. By contrast, the excellent work hardening behavior and uniform elongation of the TBF steel are attributed to the sustained transformability until the occurrence of a large strain and significant stress partitioning between the face-centered cubic (FCC) and body-centered cubic (BCC) phases due to the high austenite phase stability and high resistance to slip deformation of austenite.

論文

In situ neutron reflectometry analysis of interfacial structure formation between phenolic resin and silica during curing

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:3 パーセンタイル:11.15(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 180$$^{circ}$$C, 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.

論文

張出し成形した焼戻しマルテンサイト鋼板の水素脆化に及ぼす残留応力の影響

西村 隼杜*; 北條 智彦*; 味戸 沙耶*; 柴山 由樹*; 小山 元道*; 齋藤 寛之*; 城 鮎美*; 安田 良*; 菖蒲 敬久; 秋山 英二*

鉄と鋼, 107(9), p.760 - 768, 2021/09

 被引用回数:0 パーセンタイル:0.00(Metallurgy & Metallurgical Engineering)

本研究では、球頭パンチを用いて張出し加工を施した引張強さ1000MPa級の一般的な焼戻しマルテンサイト鋼をプレス成形部品のモデルサンプルとして採用し、その水素脆化特性を評価した。残留応力分布は、SPring-8のBL14B1の白色X線を用いたエネルギー分散XRDによって求めた。さらにFEMを用いて張出し加工後の試験片の残留応力、および塑性ひずみ分布を解析した。その結果、水素チャージにより張出し試験片の張出し側のFoot部で、面対称に2つのき裂が発生し、半径方向に伝播すること、XRDとFEMにより得られた残留応力分布によると、円周方向の引張応力はFoot部で最大値を示し、この円周方向の最大引張応力が作用した位置はき裂発生位置とよく一致し、応力がき裂発生の要因となっていることなどが示唆された。

論文

Effects of residual stress on hydrogen embrittlement of a stretch-formed tempered martensitic steel sheet

西村 隼杜*; 北條 智彦*; 味戸 沙耶*; 柴山 由樹*; 小山 元道*; 齋藤 寛之*; 城 鮎美*; 安田 良*; 菖蒲 敬久; 秋山 英二*

ISIJ International, 61(4), p.1170 - 1178, 2021/04

 被引用回数:12 パーセンタイル:48.53(Metallurgy & Metallurgical Engineering)

The effects of residual stress on the hydrogen embrittlement behavior of a tempered martensitic steel sheet with 1-GPa-class tensile strength stretch-formed by a hemisphere punch simulating press-formed automotive structural parts were investigated. Cracking on the stretch-formed specimen induced by potentiostatic hydrogen charging was initiated in the foot of the impression of the specimen and propagated to the radial direction both toward the hillside and the plain. The mixture of quasi cleavage and intergranular fractures were observed whole through the fracture surface. Residual stress in the stretch-formed specimens was analyzed by using energy-dispersive X-ray diffraction method utilizing the synchrotron X-ray radiation at SPring-8. In addition, stress and plastic strain distributions in the specimen were analyzed by using Finite Element Method (FEM). These analyses depicted that the high tensile stress in the circumferential direction was in the foot of the impression, corresponding to the direction of the crack growth. The FEM analysis revealed that the high triaxial stress was in the foot suggesting accumulation of hydrogen. It was considered that the preferential crack initiation at the foot was promoted by the high residual stress in the circumferential direction and the hydrogen accumulation due to stress-induced diffusion.

論文

Effects of stress and plastic strain on hydrogen embrittlement fracture of a U-bent martensitic steel sheet

柴山 由樹; 北條 智彦*; 小山 元道*; 齋藤 寛之*; 城 鮎美*; 安田 良*; 菖蒲 敬久; 松野 崇*; 秋山 英二*

ISIJ International, 61(4), p.1322 - 1329, 2021/04

 被引用回数:9 パーセンタイル:38.61(Metallurgy & Metallurgical Engineering)

The effects of stress and plastic strain distributions on the hydrogen embrittlement fracture of the U-bent martensitic steel sheet specimen were investigated. The hydrogen embrittlement testing of the U-bent specimen was performed. Fracture morphology mainly consisting of intergranular fracture was found inside the hydrogen charged U-bent specimen, which indicated that the crack initiation took place in the interior, and shear lips were found near both surfaces of the U-bent sheet. The synchrotron X-ray diffraction measurement and the finite element simulation were utilized to analyze the stress and plastic strain distributions in the thickness direction of the U-bent specimen. The elastic strain distributions obtained by the measurement showed a good agreement with the simulation. The crack initiation site of the hydrogen-charged U-bent specimen was considered to be correspondent with the region where the tensile stress was the highest, suggesting that the maximum tensile stress predominantly determine the crack initiation.

論文

Interfacial cross-link inhomogeneity of a phenolic resin on a silica surface as revealed by X-ray and neutron reflection measurements

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:10 パーセンタイル:29.66(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 D$$_{2}$$O for the NR analysis in which the coherent neutron scattering length density (SLD) largely changed owing to the D$$_{2}$$O 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.

論文

Diffusion behavior of methanol molecules confined in cross-linked phenolic resins studied using neutron scattering and molecular dynamics simulations

首藤 靖幸*; 和泉 篤士*; 萩田 克美*; 山田 武*; 柴田 薫; 柴山 充弘*

Macromolecules, 51(16), p.6334 - 6343, 2018/08

 被引用回数:17 パーセンタイル:47.34(Polymer Science)

The dynamics of methanol confined in highly cross-linked phenolic resins was investigated using incoherent quasielastic neutron scattering (QENS) and atomistic molecular dynamics (MD) simulations. The QENS analysis for adeuterated phenolic resin and both deuterated and nondeuterated methanol indicated the presence of resin dynamics induced by methanol invasion and confined diffusion of the methanol molecules. QENS results suggested that methanol had a diffusion coefficient of 1.6 $$times$$ 10$$^{-6}$$ cm$$^{2}$$/s, which is 1 order of magnitude smaller than the bulk value (2.3 $$times$$ 10$$^{-5}$$ cm$$^{2}$$/s. The MD trajectories also showed that the methanol diffusion was limited by the resin network, consistent with QENS results in terms of the diffusion coefficient and diffusion-like behavior.

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