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MINERALS ENGINEERING · 2020 · IF 3.795

A recovery strategy of Sm, Co for waste SmCo magnets by fatty acid based ionic liquids

Qianwen Chen,Shuainan Ni,Guanghua Ai,Tao Zhang,Xiaoqi Sun

Cleaner and lower-cost recovery and separation of samarium(III) and cobalt(II) from waste SmCo magnets can effectively alleviate supply risks of the strategic metals. Based on this goal, a family of renewable, low-cost, biocompatible, non-toxic fatty acid-based ionic liquids (FAILs), including [N1888][DA], [N1888][LA] and [N1888][PA] were synthesized and developed for the separation of Sm(III)/Co(II) from samarium-cobalt simulated solution. The effect factors, i.e. equilibrium time, FAIL molar concentration, salting-out agent concentration and initial pH of aqueous solution were investigated. The extraction mechanism was proposed to be ion association by slope analysis and FT-IR. Under the optimized extraction conditions, a higher purity CoCl 2 (99.5%) product was obtained by a simple extraction-stripping-washing process with the consumption of Na 2 C 2 O 4 and NH 3 ·H 2 O. The produced salty wastewater with lower concentration from the process could be recycled. Sm 2 O 3 with a purity of 99% were obtained by roasting the Sm 2 (C 2 O 4 ) 3 at 800 °C for two hours. The whole process was simple and sustainable, illustrating its potential for industrial applications.

研究领域: 材料科学 · 环境科学
✓ 已验证 DOI 高影响因子
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HYDROMETALLURGY · 2022 · IF 4.217

Recovery of samarium(III) and cobalt(II) in synthetic nitric acid solutions using carboxyl functionalized ionic liquids and application to recycling SmCo permanent magnets

Xiayu Liang,Qingle Zeng

Samarium (Sm), as one of the lanthanide elements, has a broad application prospect in the synthesis of samarium cobalt permanent magnet materials with high temperature stability, corrosion resistance and oxidation resistance . Due to the unlimited demand of Sm(III), recycling of Sm(III) waste is an effective method to balance economy and supply. In this paper, three novel morpholine carboxylic acid ionic liquids (ILs) were rationally designed and successfully synthesized for the extraction of Sm(III). The effects of alkyl chain length of the ionic liquids, solution acidity, contact time, extractant concentration and temperature were tested in terms of the extraction performances. The results revealed that [(CH 2 ) 7 COOHmor][NTf 2 ] had the optimal extraction capacity, as well as the extraction efficiency of Sm increased with the increase of pH, reaching >99.9% when the pH was 1.8. In addition, the extraction equilibrium could be achieved within 1 min. Moreover, the slope analysis and FTIR spectral studies proposed a cation exchange extraction mechanism for Sm(III) by [(CH 2 ) 7 COOHmor][NTf 2 ]. The loaded Sm(III) in organic phase was easy to strip with 0.05 mol/L of HNO 3 , and the [(CH 2 ) 7 COOHmor][NTf 2 ] remained stable after 5 cycles. The research of transition metal extraction revealed that Sm(III) could be selectively separated from Ni(II) and Co(II) by adjusting the pH value of the solution. Finally, under the optimized extraction conditions, Sm 2 O 3 with 83.9% yield was obtained by the extraction-stripping-precipitation-calcination process, through the large-scale recovery applications of the simulated waste liquid .

研究领域: 化学工程 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 27 ·12146-12152 · IF 2.7

Potentiometric study of the interaction of Sm3+ and O2− ions: thermodynamic properties of samarium compounds in molten NaCl–2CsCl eutectic

Henan Zhang,Qi Liu,Alena Novoselova,Valeri Smolenski,Kewei Jiang,Yongde Yan,Milin Zhang,Jun Wang

The reactions of oxygen and samarium ions in molten NaCl–2CsCl eutectic in the temperature range of 823–913 K have been investigated by potentiometric titration in an inert gas atmosphere. The activity of oxygen ions in the studied melts was monitored using a standard YZME (indicator) electrode based on Y2O3-stabilized ZrO2 with a solid–electrolyte membrane. The titration of Sm3+ by O2− ions demonstrated the formation of insoluble SmOCl compounds in the investigated region. The mechanism of formation of SmOCl and Sm2O3 was established by the analysis of potentiometric titration curves. Subsequently, the solubility of SmOCl and Sm2O3 in the melt was calculated using the material balance equation and solubility constant equation. Finally, the basic thermodynamic properties of SmOCl and Sm2O3 in molten NaCl–2CsCl eutectic were calculated, and the properties of samarium in the melt were summarized using the Pourbaix-type (E-pO2−) diagram to determine the kinds of stabilized samarium compounds. Furthermore, the optimal chlorination conditions can be obtained from the E-pO2− diagram of Sm.

研究领域: 化学 · 材料科学
✓ 已验证 DOI 高影响因子
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Journal of Advanced Ceramics · 2021 ·Vol. 10 ·期 6 ·1389-1397 · IF 6.707

Reaction products of Sm2Zr2O7 with calcium-magnesium-aluminum-silicate (CMAS) and their evolution

Wang Yinghua,Ma Zhuang,Liu Ling,Liu Yanbo

During flight, many silicates (sand, dust, debris, fly ash, etc.) are ingested by an engine. They melt at high operating temperatures on the surface of thermal barrier coatings (TBCs) to form calcium-magnesium-aluminum-silicate (CMAS) amorphous settling. CMAS corrodes TBCs and causes many problems, such as composition segregation, degradation, cracking, and disbanding. As a new generation of TBC candidate materials, rare-earth zirconates (such as Sm 2 Zr 2 O 7 ) have good CMAS resistance properties. The reaction products of Sm 2 Zr 2 O 7 and CMAS and their subsequent changes were studied by the reaction of Sm 2 Zr 2 O 7 and excess CMAS at 1350 °C. After 1 h of reaction, Sm 2 Zr 2 O 7 powders were not completely corroded. The reaction products were Sm-apatite and c-ZrO 2 solid solution. After 4 h of reaction, all Sm 2 Zr 2 O 7 powders were completely corroded. After 24 h of reaction, Sm-apatite disappeared, and the c-ZrO 2 solid solution remained.

研究领域: 材料科学 · 航空工程
✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2018 · IF 3.057

Grain size effect on the electrical conductivity of submicron Sm-heavily-doped ceria

Q.B. Chen,B. Meng,M.Y. Zhao,H. Xie,L.F. Bian,X. Yang

In order to investigate the grain size effect on the electrical conductivity of the submicron samarium-heavily-doped ceria , the Ce 0.8 Sm 0.2 O 1.9 (SDC20) ceramics with grain sizes from 128 nm to 533 nm were prepared by sintering at 1000–1300 °C in the air atmosphere. The crystalline structure, micro-morphology, density and electrical conductivity of the SDC20 ceramics were measured and characterized by XRD , SEM, TEM, Archimedes method and electrochemical impedance spectrum, respectively. All the sintered samples show the single SDC phase, low porosity and clean grain boundary without any impurities. The grain sizes of SDC ceramics grow continuously with the rising sintering temperature , and the relative densities increase as the sintering temperature rises from 1000 °C to 1200 °C and then decrease with the temperature from 1200 °C to 1300 °C. The specific grain boundary conductivity of SDC keeps decreasing while the grain and apparent grain boundary conductivities increase during the whole grain size range of 128–533 nm.

CAS / MDL: 10294-41-4 13759-83-6
研究领域: 材料科学 · 电化学
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JOURNAL OF RARE EARTHS · 2022 · IF 4.632

Neodymium and samarium codoped PLZT ferroelectric ceramics for potential betavoltaic nuclear batteries

Zhixiong Song,Jizhen Liu,Liyan Xue,Zhengming Jiang,Fan Yang

In this work, neodymium (Nd) and samarium (Sm) codoped lead lanthanum zirconate titanate (PLZT) ceramics were prepared by a high-temperature solid-state method. The samples were characterized by X-ray diffraction, scanning electron microscopy and ferroelectric analysis. Rare earth-doped PLZT ceramics show good phase formation. An appropriate rare earth element doping amount increases the densities of PLZT ceramics and reduces their resistivities, which is due to the role of rare earth elements in grain refinement. However, the increase in the amount of grain boundaries caused by grain refinement also affects domain inversion. Therefore, with increasing doping concentration, the remnant polarization of PLZT gradually decreases, and the doping of rare earth elements also slightly reduces the band gap of PLZT. Under irradiation with an X-ray simulated beta source with a particle energy of 10 keV (between the average energies of the beta particles of 3 H and 63 Ni), the ceramic sheets in this work produce current densities of up to 1.38 nA/cm 2 . This indicates that Nd and Sm codoped PLZT ceramics have a certain potential for application in betavoltaic batteries .

研究领域: 材料科学 · 核能工程
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JOURNAL OF CHEMICAL SCIENCES · 2022 ·Vol. 134 ·期 3 ·1-11 · IF 2.15

High-performance scavenging of Nd (III) and Sm (III) from water by a copper-based metal-organic framework HKUST-1

LIU XIAOJUAN,LI MINGMING,YANG SHUMING,YANG YAYA,NIE JIANG,XUE YUBING,OUYANG YINGGEN,XIAO SONGTAO

The increasing demand for neodymium (III) and samarium (III) due to their extensive high-tech applications has drawn much attention to their recovery. In this work, the copper-based metal-organic framework HKUST-1 was prepared and used for the adsorption of neodymium (III) and samarium (III) in the media of an aqueous solution. The maximum adsorption capacity of the material for neodymium (III) and samarium (III) was 284.11 and 503.45 mg g −1 at a pH of 5.5, respectively. The adsorption removal rate could achieve nearly 100% at the solid-to-liquid ratio of 1.0 g L −1 , which is relatively excellent among such adsorbents used for rare earth elements uptake. The mechanism and reversibility of neodymium (III) and samarium (III) adsorption were systematically investigated by X-ray diffraction, Fourier transforms infrared spectroscopy, Raman spectra, and X-ray photoelectron spectroscopy, suggesting that the mechanism for the adsorption was ion exchange and complexation between trivalent rare-earth ions and the oxygen atom in the hydroxyl group. The reason behind the material displaying a more robust affinity for samarium (III) may be caused by the energy difference between f n and f n+1 states of samarium (III) was larger than that of neodymium (III), thus forming stronger covalent bonding. Graphical abstract HKUST-1 exhibited high adsorption capacity towards Nd (III) and Sm (III). The reason behind the material displaying a more robust affinity for Sm(III) was caused by that the energy difference between f n and f n+1 states of Sm(III) was larger than that of Nd(III), thus forming stronger covalent bonding.

研究领域: 材料科学 · 环境科学
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ENERGY & FUELS · 2020 · IF 3.421

Synergistic Effects of the Zr and Sm Co-doped Fe2O3/CeO2 Oxygen Carrier for Chemical Looping Hydrogen Generation

Shiwei Ma,Shiyi Chen,Huijun Ge,Tao Song,Ping Lu,Wenguo Xiang

CeO2 is a typical fluorite oxide with desirable lattice oxygen conductivity and can be applied as an active support for the Fe-based oxygen carrier in chemical looping hydrogen generation (CLHG). However, Fe2O3/CeO2 always suffers from low thermal stability and sintering. Doping foreign cations could be a proper way to improve its reactivity and cyclic stability. In this work, Zr4+ and Sm3+, with a smaller ionic radius and lower valence than Ce4+, respectively, were doped into Fe2O3/CeO2 using the co-precipitation method, and the doping effects on the reactivity and redox stability of Fe2O3/CeO2 in CLHG were investigated. Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 provided the best redox reactivity, and the purity of generated hydrogen for all oxygen carriers reached nearly 100% (the detection limit of CO/CO2 was 0.01% in volume). The reactivity followed the sequence Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 > Fe2O3/Ce0.8Sm0.2O1.9 > Fe2O3/Ce0.75Zr0.25O2 > Fe2O3/CeO2. However, the concentration of oxygen vacancy was ranked as Fe2O3/Ce0.8Sm0.2O1.9 > Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 > Fe2O3/Ce0.75Zr0.25O2 > Fe2O3/CeO2. The Zr doping boosted the reactivity of Fe2O3/CeO2 mainly by enhancing its sintering resistance, whereas the Sm doping achieved it mainly by promoting the oxygen conductivity, whose ability to improve the thermal stability of Fe2O3/CeO2 was rather limited. Both Zr and Sm doping could suppress the outward migration of Fe cations in the particles, resulting in higher sintering resistance. Furthermore, Zr and Sm could dissolve into CeO2 for prepared Fe2O3/Ce0.6Sm0.15Zr0.25O1.925; however, the bleeding out of both dopants was observed with Sm0.5Zr0.5O1.75 formation, which could be detrimental to the redox stability of the oxygen carrier.

研究领域: 材料科学 · 能源工程
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CERAMICS INTERNATIONAL · 2017 · IF 2.986

Structural transformation and multiferroic properties of Sm and Ti co-doped BiFeO3 ceramics with Fe vacancies

Yanhong Gu,Jianguo Zhao,Weiying Zhang,Haiwu Zheng,Laimei Liu,Wanping Chen

Sm and Ti co-doped BiFeO 3 (BFO) ceramics with Fe vacancies—Bi 0.86 Sm 0.14 FeO 3 , Bi 0.86 Sm 0.14 Fe 0.99 Ti 0.01 O 3 , and Bi 0.86 Sm 0.14 Fe 0.9 Ti 0.05 O 3 —were prepared by a solid-state method using a rapid liquid process. X-ray diffraction indicated that all samples exhibited a rhombohedral structure with a minor secondary phase. The structural transformation from a rhombohedral (space group: R 3 c ) to orthorhombic structure (space group: Pnma ) was observed in the sample of Bi 0.86 Sm 0.14 Fe 0.9 Ti 0.05 O 3 , which was also confirmed by Raman scattering spectra. Microstructural investigations with scanning electron microscopy showed a reduction in grain size with doping of BFO. The dielectric loss of Bi 0.86 Sm 0.14 Fe 0.9 Ti 0.05 O 3 reaches 0.05 (at 100   Hz) owing to the introduction of Ti and Fe vacancies. Ferroelectromagnetic measurements revealed the existence of ferroelectricity with a remanent polarization of 0.24   µC/cm 2 in Bi 0.86 Sm 0.14 FeO 3 , paraelectricity in Bi 0.86 Sm 0.14 Fe 0.9 Ti 0.05 O 3 , and weak ferromagnetism with a remanent magnetization of 0.2   emu/g in Bi 0.86 Sm 0.14 Fe 0.99 Ti 0.01 O 3 . The two composition-driven phases exist simultaneously and the different coercive field might be related to the jumps in the ferromagnetic hysteresis loops. Both the ferroelectric and magnetic properties were shown to correlate with the composition-driven structural evolution.

研究领域: 材料科学 · 物理学
✓ 已验证 DOI 高影响因子
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Selective electro-oxidative separation of Sm, Yb, and Eu in low-temperature molten salt AlCl3-NaCl

Jiazhuang Chen,Yuke Zhong,Dongdong Wang,Mei Li,Wei Han,Yalan Liu,Weiqun Shi

The variable valence rare earth elements are difficult to separate due to their similar properties and intermediate valence states in molten salts. In order to realize their efficient and selectivity separation, the properties and separation methods of Sm, Yb, and Eu have been investigated in a low-temperature AlCl 3 -NaCl molten salt. It has been found that the oxidation reactions of different Ln(II) to Ln(III) have different potentials. The Ln(II)/Ln(III) reaction is also irreversible when the AlCl 3 content is less than 50 mol%, Ln(III) exists in the form of LnCl 3 precipitation. Therefore, selectively modulating the valence of Sm, Yb, and Eu by electrochemical methods can achieve their separation. The LnCl 3 produced from the Ln(II) electro-oxidation precipitates and separates from the other unoxidized soluble Ln(II) in AlCl 3 -NaCl melt. The efficient separation of Ln(II) in AlCl 3 -NaCl can be achieved by pulse potentiostatic electrolysis. Under these conditions, the separation factors of Sm-Eu, Sm-Yb, and Yb-Eu can reach 10 3 . The maximum removal of Ln(II) exceeded 99 % with a maximum current efficiency of more than 90 %. Most importantly, the separation of variable valence rare earth elements has been realized in a low-temperature AlCl 3 -NaCl melt.

CAS / MDL: 7446-70-0
研究领域: 冶金学 · 材料科学
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Electrochemical Extraction of Fission Element Samarium from Molten NaCl-2CsCl Eutectic Salt Using the Liquid Gallium Cathode

Henan Zhang,Kewei Jiang,Wantong Li,Qi Liu,Jing Yu,Jiahui Zhu,Yongde Yan,Milin Zhang,Jun Wang

The effective extraction of neutron poison samarium from nuclear waste to prevent reactions with metallic uranium is crucial for the sustainable development of nuclear energy. The electrochemical recovery of samarium on the liquid gallium cathode from the NaCl-2CsCl molten salts has been investigated by a variety of electrochemical techniques, and its electrochemical reduction properties and kinetic parameters have been provided. It was revealed that the reduction reaction on the Mo cathode of Ga(III) to Ga(0) and Sm(III) to Sm(II) is a two-step and one-step reaction process, respectively, and both reactions are reversible. The diffusion coefficients of Ga(III)/Ga(II) and Sm(III)/Sm(II) were identified, and the activation energies were 20.07 and 42.96 kJ mol–1, respectively. Simultaneously, the codeposition mechanism of Ga(III) and Sm(III) on the Mo cathode was systematically investigated, and the potential and types of formation of binary intermetallic compounds were explored. Subsequently, it was determined that there are two main reaction processes for Sm(III) on the liquid Ga cathode, and the deposition potential of Sm becomes more positive due to the formation of the alloy. The exchange current density values of Sm(III)/Sm(Ga) obtained by both linear polarity (LP) and Tafel techniques increased with temperature, meanwhile the charge transfer resistance decreased, as well as the transfer coefficient. In addition, the apparent electrode potential of Sm(III)/Sm(Ga) was also calculated. Based on the electrochemical analysis, the fission element Sm was deposited on the liquid Ga cathode by potentiostatic electrolysis at a suitable potential, and the alloy products were verified by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. Ultimately, the highest separation efficiency of Sm on the liquid Ga cathode reached 92.43% according to the analysis of inductively coupled plasma atomic emission spectrometry (ICP-AES) results.

研究领域: 核能工程 · 电化学
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Photoluminescence of Sm3+ and Eu3+ co-doped La2O3–Ga2O3 glasses fabricated by an aerodynamic levitation furnace

Ying Li,Yong Hong Ma,Aihua Mao,Xiwei Qi

A series of transparent (1- y )La 2 O 3 –Ga 2 O 3 - y Sm 2 O 3 - x Eu 2 O 3 (where x  = 0, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, and y  = 0, 0.04) were successfully synthesized using a containerless solidification process. Co-doping with Sm 3+ and Eu 3+ enhanced the energy absorption of Eu 3+ , notably improving the characteristic emission peak 5 D 0 - 7 F 2 of Eu 3+ . The peak emission intensity for y  = 0.04 was observed at x  = 0.08, attributable to the concentration quenching of Eu 3+ ions. As the concentration of Eu 3+ increased, the energy transfer effect on emission intensity diminished. Attributed to the energy transfer between Sm 3+ and Eu 3+ , Sm 3+ may primarily serve as the sensitizer, and Eu 3+ as the activator. According to the Dexter theory, which suggests that the interaction between activator ions and their adjacent ions is the primary mechanism of energy transfer and quenching among Eu 3+ ions and adjacent ions, an increase in Eu 3+ concentration leads to a decrease in the distance between Eu 3+ and adjacent ions, strengthening their interaction, and potentially inducing concentration quenching. Furthermore, with an increase in Eu 3+ concentration, the CIE chromaticity coordinates for the samples co-doped with Sm 3+ and Eu 3+ shifted significantly, enhancing the color purity of the emitted light and bringing it closer to the NTSC color standard coordinates (0.67, 0.33).

研究领域: 材料科学 · 光学
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