Treatment of U contaminated waste generated from nuclear fuel fabrication process, 1; Ce(IV) recovery by temperature swing extraction with monoamides

岩本 敏広; 齋藤 まどか*; 高畠 容子; 渡部 創; 渡部 雅之; 成瀬 惇喜*; 塚原 剛彦*

Proceedings of 30th International Conference on Nuclear Engineering (ICONE30) (Internet), 4 Pages, 2023/05

モノアミド抽出剤と温度応答性ポリマーを用いたゲル化抽出技術のウラン廃棄物処理への適用性の検討を行った。異なる構造を有する3種類のモノアミド抽出剤を用いた模擬溶液の分離試験により、溶液中のCe(IV)をゲル化抽出法により選択的に回収されることが示された。これらの試験結果をもとに、ゲル化抽出法に適したモノアミド抽出剤を選定した。

Possible pathway of zeolite formation through alkali activation chemistry of metakaolin for geopolymer-zeolite composite materials; ATR-FTIR study

Onutai, S.; 佐藤 淳也; 大杉 武史

Journal of Solid State Chemistry, 319, p.123808_1 - 123808_10, 2023/03

https://doi.org/10.1016/j.jssc.2022.123808

The process of zeolite formation for geopolymer-zeolite composites can be explained using ATR/FTIR spectroscopy. The process consists of the dissolution of silica and alumina precursors from the alkali activation process of metakaolin with NaOH solution. Thereafter, the formation of hydrated aluminosilicate primary units and secondary units occurs. Finally, the units are reorganized and crystallized into the zeolite structure. The increase in the alkali activator concentrations promotes the high dissolution of raw materials. Na cations play an important role in dissolution and synthesis. The higher the alkali activator concentration, the higher the tetrahedron condensation rate and the greater the degree of structure ordering. The phases in alkali activation of metakaolin with different NaOH concentrations (Na/Al) at 1.18, 2.03, and 3.05 were zeolite-A, zeolite-X, and sodalite zeolite. Finally, the possible pathway of zeolite formation was explained and deduced.

Emulsification of low viscosity oil in alkali-activated materials

Reeb, C.*; Davy, C. A.*; Pierlot, C.*; Bertin, M.*; Cantarel, V.; Lambertin, D.*

Cement and Concrete Research, 162, p.106963_1 - 106963_16, 2022/12

https://doi.org/10.1016/j.cemconres.2022.106963

Significant amounts of low viscosity mineral oil (20 %vol) are successfully immobilized in alkali-activated materials (AAM), either based on metakaolin or blast furnace slag. Surfactants are required to stabilize of the oil emulsion. Visual observation, torque measurement and rheology evidence two distinct groups of surfactants. One group contributes to structuring the oil/AAM fresh mix, with greater torque and viscosity than without surfactant; the other includes non-structuring surfactants, without change in torque or viscosity. Each group depends on the AAM considered. Whatever the AAM and the surfactant, the interfacial tension between oil/activating solution and the oil droplet size decrease significantly. Therefore, although contributing to stabilize the emulsion, interfacial tension alone does not explain the two distinct behaviors. Characterization of diluted ternary suspensions (solid particles-oil-AS) relates the structuring effect to interactions between oil and solid particles, through the surfactant polar head groups and non-polar hydrocarbon tails. An original mechanism explaining structuration is discussed.

燃料デブリ取出し時における放射性核種飛散防止技術の開発(委託研究); 令和2年度英知を結集した原子力科学技術・人材育成推進事業

廃炉環境国際共同研究センター; 東京大学*

JAEA-Review 2022-010, 155 Pages, 2022/06

JAEA-Review-2022-010.pdf:9.78MB

日本原子力研究開発機構(JAEA)廃炉環境国際共同研究センター(CLADS)では、令和2年度英知を結集した原子力科学技術・人材育成推進事業(以下、「本事業」という)を実施している。本事業は、東京電力ホールディングス株式会社福島第一原子力発電所の廃炉等をはじめとした原子力分野の課題解決に貢献するため、国内外の英知を結集し、様々な分野の知見や経験を、従前の機関や分野の壁を越えて緊密に融合・連携させた基礎的・基盤的研究及び人材育成を推進することを目的としている。平成30年度の新規採択課題から実施主体を文部科学省からJAEAに移行することで、JAEAとアカデミアとの連携を強化し、廃炉に資する中長期的な研究開発・人材育成をより安定的かつ継続的に実施する体制を構築した。本研究は、研究課題のうち、平成30年度に採択された「燃料デブリ取出し時における放射性核種飛散防止技術の開発」の平成30年度から令和3年度の研究成果について取りまとめたものである(令和3年度まで契約延長)。本課題は令和3年度が最終年度となるため4年度分の成果を取りまとめた。本研究は、東京電力ホールディングス株式会社福島第一原子力発電所の燃料デブリ取出し時に発生する放射性微粒子を着実に閉じ込めるために、気相及び液相における微粒子の挙動を明らかにするとともに、微粒子飛散防止技術を開発することを目的としている。具体的には、微粒子飛散防止技術として、(1)スプレー水等を利用して最小限の水で微粒子飛散を抑制する方法、及び(2)燃料デブリを固化して取り出すことで微粒子飛散を抑制する方法について、実験及びシミュレーションにより評価し、実機適用可能性を評価した。

Structural changes in pH-responsive gelatin/hydroxypropyl methylcellulose phthalate blends aimed at drug-release systems

野上 聡*; 門田 和紀*; 内山 博雅*; 有馬 寛*; 岩瀬 裕希*; 富永 大輝*; 山田 武*; 高田 慎一; 柴山 充弘*; 戸塚 裕一*

International Journal of Biological Macromolecules, 190, p.989 - 998, 2021/11

https://doi.org/10.1016/j.ijbiomac.2021.09.074

The present study aimed to investigate the thermal-and pH-dependent gelation behavior of gelatin/HPMCP blends using ultraviolet (UV) spectrophotometry, viscoelasticity, and dynamic light scattering (DLS). We found that the release of lisinopril from gelatin/HPMCP gels can be inhibited at low pH. UV spectrophotometric analysis showed that pH had a significant effect on the transparency of aqueous HPMCP systems and gelatin/ HPMCP gels. The viscoelastic patterns of gelatin/HPMCP at pH 4.6 considerably differed from those of gelatin/ HPMCP at pH 5.2 and 6.0. DLS measurements showed that HPMCP molecules in low concentrations underwent strong aggregation below pH 4.8. Such HPMCP aggregation induces a physical barrier in the matrix structures of the gelatin/HPMCP gels, which inhibits the drug release at pH 1.2. This hydrogel delivery system using polymer blends of gelatin/HPMCP can be used in oral gel formulations with pH-responsive properties.

Microparticles with diverse sizes and morphologies from mechanical and laser cutting of fuel debris simulants and geopolymer as a covering material

Zhou, Q.*; 斉藤 拓巳*; 鈴木 誠矢; 矢野 公彦; 鈴木 俊一*

Journal of Nuclear Science and Technology, 58(4), p.461 - 472, 2021/04

https://doi.org/10.1080/00223131.2020.1869623

During the decommissioning of Fukushima Daiichi Nuclear Power Plant, the dismantling of massive fuel debris is important for the defueling process. The production and dispersion of radioactive microparticles highly depends on the cutting technique implemented. Previous studies have been conducted on the development of cutting techniques and the treatment of radioactive particles generation during the cutting process. Besides, adequate understanding of the microparticle products during the cuttings of fuel debris is of vital necessity. Nowadays, geopolymer application is proposed as a covering material during the fuel debris retrieval in order to keep the structural integrity of damaged components. In this study, the microparticle products during mechanical and laser cutting of fuel debris simulants (Hafnium oxide and Tungsten(IV) oxide pellets) and geopolymer material were investigated. The cuttings have been carried out for samples of the simulants, geopolymer, and simulants with geopolymer covering. The generated particles were collected and investigated by laser diffraction particle size analyzer and Scanning Electron Microscope with X-ray spectrometry. Particles with diverse sizes and morphologies were observed from the products of each sample. It also appears that particles with unique sizes and morphologies can generate from the laser cuttings due to the thermal effect of laser cutting.

燃料デブリ取出し時における放射性核種飛散防止技術の開発(委託研究); 令和元年度英知を結集した原子力科学技術・人材育成推進事業

廃炉環境国際共同研究センター; 東京大学*

JAEA-Review 2020-043, 116 Pages, 2021/01

JAEA-Review-2020-043.pdf:7.74MB

日本原子力研究開発機構(JAEA)廃炉環境国際共同研究センター(CLADS)では、令和元年度英知を結集した原子力科学技術・人材育成推進事業(以下、「本事業」という)を実施している。本事業は、東京電力ホールディングス福島第一原子力発電所の廃炉等をはじめとした原子力分野の課題解決に貢献するため、国内外の英知を結集し、様々な分野の知見や経験を、従前の機関や分野の壁を越えて緊密に融合・連携させた基礎的・基盤的研究及び人材育成を推進することを目的としている。平成30年度の新規採択課題から実施主体を文部科学省からJAEAに移行することで、JAEAとアカデミアとの連携を強化し、廃炉に資する中長期的な研究開発・人材育成をより安定的かつ継続的に実施する体制を構築した。本研究は、研究課題のうち、平成30年度に採択された「燃料デブリ取出し時における放射性核種飛散防止技術の開発」の令和元年度の研究成果について取りまとめたものである。本研究は、微粒子飛散を効果的に抑制する技術を開発しており、実験の結果、水ミストを使ってスプレイする方法がエアロゾル除去効率と除去率を改善する上で効果的かつ適用可能な手法であることが分かった。また燃料デブリを固めて切断時に微粒子飛散を抑制する手法として、ジオポリマーによる固化手法に注目し、同材の強度、熱伝導率や切断粉の特徴を把握するとともに、RPV施工時における温度分布や流動に関するシミュレーションを実施した。

Water distribution in Nafion thin films on hydrophilic and hydrophobic carbon substrates

伊藤 華苗; 原田 雅史*; 山田 悟史*; 工藤 憲治*; 青木 裕之; 金谷 利治*

Langmuir, 36(43), p.12830 - 12837, 2020/11

https://doi.org/10.1021/acs.langmuir.0c01917

We performed HO and DO double contrast neutron reflectivity measurements on 25-nm-thick Nafion thin films on hydrophilic and hydrophobic carbon in water and 80% relative humidity vapor to investigate the depth profile of the water and Nafion distribution. We found a dense Nafion layer at the air or water interface regardless of the carbon hydrophilicity. On the other hand, a water-rich Nafion dense layer was observed at the carbon interface only for hydrophilic carbon. The double contrast measurements provided quantitative information about the depth profile but simultaneously indicated that the sum of the volume occupancies of water and Nafion in the film was less than unity. We assessed the problem based on two possibilities: voids in the film or "residual water", which cannot be exchanged or is difficult to exchange with water outside.

Preparation, characterization, and dilute solution properties of four-branched cage-shaped poly(ethylene oxide)

野田 昂志*; 土肥 侑也*; 太田 豊*; 高田 慎一; 高野 敦志*; 松下 裕秀*

Journal of Polymer Science, 58(15), p.2098 - 2107, 2020/08

https://doi.org/10.1002/pol.20200286

A four-branched cage-shaped poly(ethylene oxide) (4C-PEO) was prepared by a coupling reaction at very dilute condition between two kinds of end-functional four-armed star-shaped PEOs having amino and -hydroxysuccinimide groups on their four ends, followed by purification using -cyclodextrin (-CD). The raw coupling reaction product shows multiple peaks including various high molecular weight multimeric products in size-exclusion chromatography measurements, while the product after -CD purification shows a single peak eluted slightly earlier than the precursor star PEOs. These results suggest that the targeted 4C-PEO polymer was successfully isolated through the -CD purification. Small-angle neutron scattering (SANS) measurements of the final product in dilute solution were conducted, and its chain conformation was evaluated from the scattering profile in comparison with linear and star polymers.

Nanostructures and viscosities of nafion dispersions in water/ethanol from dilute to concentrated regimes

Gupit, C. I.*; Li, X.*; Maekawa, Ryosuke*; Hasegawa, Naoki*; 岩瀬 裕希*; 高田 慎一; 柴山 充弘*

Macromolecules, 53(4), p.1464 - 1473, 2020/02

https://doi.org/10.1021/acs.macromol.9b02314

The present work involved a systematic analysis of both the structural and rheological properties of Nafion dispersions carefully prepared using a standard procedure, ranging from dilute (0.1 wt %) to highly concentrated (30 wt %) conditions. Small-angle X-ray scattering confirmed the cylindrical structure of Nafion in dispersion and the unique interactions of Nafion particles acting as polyelectrolytes. Three different scaling relationships involving the zero-shear viscosities of the Nafion dispersions were determined for specific concentration regimes. However, at the upper concentration limit of approximately 30 wt %, the viscosity greatly deviated from these scaling relationships and significant shear thinning was observed. Simultaneous analyses using rheology and small-angle neutron scattering determined fully isotropic spatial correlations on a length scale of less than 60 nm, even when high shear was applied.