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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Volova, Tatiana G., Zhila, Natalia O., Kiselev, Evgeniy G., Sukovatyi, Aleksey G., Lukyanenko A. V., Shishatskaya, Ekaterina I.
Заглавие : Biodegradable polyhydroxyalkanoates with a different set of valerate monomers: Chemical structure and physicochemical properties
Колич.характеристики :21 с
Место публикации : Int. J. Mol. Sci. - 2023. - Vol. 24, Is. 18. - Ст.14082. - ISSN 16616596 (ISSN), DOI 10.3390/ijms241814082. - ISSN 14220067 (eISSN)
Примечания : Cited References: 99. - The study was funded by the Russian Science Foundation (project no. 23-64-10007)
Аннотация: The properties, features of thermal behavior and crystallization of copolymers containing various types of valerate monomers were studied depending on the set and ratio of monomers. We synthesized and studied the properties of three-component copolymers containing unusual monomers 4-hydroxyvalerate (4HV) and 3-hydroxy-4-methylvalerate (3H4MV), in addition to the usual 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) monomers. The results showed that P(3HB-co-3HV-co-4HV) and P(3HB-co-3HV-co-3H4MV) terpolymers tended to increase thermal stability, especially for methylated samples, including an increase in the gap between melting point (Tmelt) and thermal degradation temperature (Tdegr), an increase in the melting point and glass transition temperature, as well as a lower degree of crystallinity (40–46%) compared with P(3HB-co-3HV) (58–66%). The copolymer crystallization kinetics depended on the set and ratio of monomers. For terpolymers during exothermic crystallization, higher rates of spherulite formation (Gmax) were registered, reaching, depending on the ratio of monomers, 1.6–2.0 µm/min, which was several times higher than the Gmax index (0.52 µm/min) for the P(3HB-co-3HV) copolymer. The revealed differences in the thermal properties and crystallization kinetics of terpolymers indicate that they are promising polymers for processing into high quality products from melts.
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Вид документа : Статья из журнала
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Автор(ы) : Volova, Tatiana G., Uspenskaya, Mayya V., Kiselev, Evgeniy G., Sukovatyi, Aleksey G., Zhila, Natalia O., Vasiliev A. D., Shishatskaya, Ekaterina I.
Заглавие : Effect of monomers of 3-hydroxyhexanoate on properties of copolymers poly(3-hydroxybutyrate-co 3-hydroxyhexanoate)
Место публикации : Polymers. - 2023. - Vol. 15, Is. 13. - Ст.2890. - ISSN 20734360 (eISSN), DOI 10.3390/polym15132890
Примечания : Cited References: 99. - The study was funded by the Russian Science Foundation (project No 23-64-10007)
Аннотация: The properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) P(3HB-co-3HHx) copolymers with different ratios of monomers synthesized by the wild-type strain Cupriavidus necator B-10646 on sugars, and an industrial sample from Kaneka synthesized by the recombinant strain C. necator NSDG-ΔfadB1 on soybean oil, were studied in a comparative aspect and in relation to poly(3-hydroxybutyrate) P(3HB). The copolymer samples, regardless of the synthesis conditions or the ratio of monomers, had reduced values of crystallinity degree (50–60%) and weight average molecular weight (415–520 kDa), and increased values of polydispersity (2.8–4.3) compared to P(3HB) (70–76%, 720 kDa, and 2.2). The industrial sample had differences in its thermal behavior, including a lower glass transition temperature (−2.4 °C), two peaks in its crystallization and melting regions, a lower melting point (Tmelt) (112/141 °C), and a more pronounced gap between Tmelt and the temperature of thermal degradation (Tdegr). The process, shape, and size of the spherulites formed during the isothermal crystallization of P(3HB) and P(3HB-co-3HHx) were generally similar, but differed in the maximum growth rate of the spherulites during exothermic crystallization, which was 3.5–3.7 μm/min for P(3HB), and 0.06–1.25 for the P(3HB-co-3HHx) samples. The results from studying the thermal properties and the crystallization mechanism of P(3HB-co-3HHx) copolymers are important for improving the technologies for processing polymer products from melts.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Zharkov S. M., Yumashev V. V., Moiseenko E. T., Altunin R. R., Solovyov L. A., Volochaev M. N., Zeer G. M., Nikolaeva N. S., Belousov O. V.
Заглавие : Thermokinetic study of aluminum-induced crystallization of a-Si: The effect of Al layer thickness
Колич.характеристики :24 с
Место публикации : Nanomaterials. - 2023. - Vol. 13, Is. 22. - Ст.2925. - ISSN 20794991 (eISSN), DOI 10.3390/nano13222925
Примечания : Cited References: 70. - This work was supported by the Russian Science Foundation under grant #22-13-00313
Аннотация: The effect of the aluminum layer on the kinetics and mechanism of aluminum-induced crystallization (AIC) of amorphous silicon (a-Si) in (Al/a-Si)n multilayered films was studied using a complex of in situ methods (simultaneous thermal analysis, transmission electron microscopy, electron diffraction, and four-point probe resistance measurement) and ex situ methods (X-ray diffraction and optical microscopy). An increase in the thickness of the aluminum layer from 10 to 80 nm was found to result in a decrease in the value of the apparent activation energy Ea of silicon crystallization from 137 to 117 kJ/mol (as estimated by the Kissinger method) as well as an increase in the crystallization heat from 12.3 to 16.0 kJ/(mol Si). The detailed kinetic analysis showed that the change in the thickness of an individual Al layer could lead to a qualitative change in the mechanism of aluminum-induced silicon crystallization: with the thickness of Al ≤ 20 nm. The process followed two parallel routes described by the n-th order reaction equation with autocatalysis (Cn-X) and the Avrami–Erofeev equation (An): with an increase in the thickness of Al ≥ 40 nm, the process occurred in two consecutive steps. The first one can be described by the n-th order reaction equation with autocatalysis (Cn-X), and the second one can be described by the n-th order reaction equation (Fn). The change in the mechanism of amorphous silicon crystallization was assumed to be due to the influence of the degree of Al defects at the initial state on the kinetics of the crystallization process.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Sinyakova E. F., Vasilyeva I. G., Oreshonkov A. S., Goryainov S. V., Karmanov N. S.
Заглавие : Formation of noble metal phases (Pt, Pd, Rh, Ru, Ir, Au, Ag) in the process of fractional crystallization of the CuFeS2 melt
Место публикации : Minerals. - 2022. - Vol. 12, Is. 9. - Ст.1136. - ISSN 2075163X (ISSN), DOI 10.3390/min12091136
Примечания : Cited References: 61. - This work was supported by the Russian Federation state assignment of Sobolev Institute of Geology and Mineralogy of SB RAS, Nikolaev Institute of Inorganic Chemistry SB RAS, and Kirensky Institute of Physics of Federal Research Center KSC SB RAS. The grant number is projects II.1.64. and 40330-2016-0001
Аннотация: The quasi-equilibrium directional crystallization of the melt composition (at. %): Cu 24.998, Fe 25.001, S 49.983, with Ag 0.002, Pd 0.003, Ru 0.004, Rh 0.006, and Au, Pt, Ir (each as 0.001) was carried out. The crystallized cylindrical ingot consisted of two primary zones and three secondary zones with different chemical and phase compositions. The compositions of the primary zones corresponded to high-temperature intermediate solid solution (zone I) and liquid enriched in sulfur (zone II). The compositions of the secondary zones corresponded to low-temperature intermediate solid solution and chalcopyrite (zone Ia), the same intermediate solid solution with chalcopyrite and bornite (zone Ib), and again with bornite, chalcocite, and idaite (zone II). We plotted the distribution curves of Fe, Cu, and S along the ingot, calculated the distribution coefficients of the components during directional crystallization, and clearly showed that, from the initial stoichiometric composition CuFeS2, the intermediate solid solution enriched in Fe and depleted in S is crystallized. Based on the data of directional crystallization and thermal analysis, a cross section was constructed in the intermediate solid solution-sulfide melt region of the Cu-Fe-S system. With solubility in the solid Cu-Fe sulfides lying below detection limit of scanning electron microscopy/energy-dispersive X-ray spectrometry (SEM/EDS), noble elements occurred as individual phases of a size more often <10 µm. They were identified as Ag, RuS2, PdS, Au* (an Au based alloy), (Rh, Ir, Ru)3S8, (Rh, Ir)3S8, Rh3S8, and (Cu, Fe)~2(Pt, Rh)1S~5 phases by electron microprobe. Based on ab initio calculations of crystal structure, electronic band structure, and lattice dynamics of idealized laurite RuS2 phase and the idealized Ir3S8, Rh3S8, and Ru3S8 phases, the interpretation of Raman spectrum of the cation-mixed (Ru, Rh, Ir)S2 sulfide was presented for the first time.
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Вид документа : Статья из сборника (однотомник)
Шифр издания :
Автор(ы) : Molokeev M. S., Bovina A. F., Shabanova K. A., Kokh D., Velikanov D. A., Eremin E. V., Bezmaternykh L. N., Moshkina E. M.
Заглавие : Peculiarities and comparison of Cu2MBO5 (M = Fe, Mn, Cr) ludwigites crystallization in Bi2O3-MoO3-Na2O-B2O3 multicomponent fluxes
Коллективы : Российская академия наук, Физико-технический институт им. Е.К. Завойского ФИЦ Казанского научного центра РАН, Казанский (Приволжский) федеральный университет, Euro-Asian Symposium "Trends in MAGnetism", "Trends in MAGnetism", Euro-Asian Symposium
Место публикации : VIII Euro-Asian symposium "Trends in magnetism" (EASTMAG-2022): Book of abstracts/ program com. S. G. Ovchinnikov [et al.]. - 2022. - Vol. 2, Sect. G: Frustrated and disordered magnetism. - Ст.G.P8. - P.25-26. - ISBN 978-5-94469-051-7
Примечания : Cited References: 6. - The study was supported by the Russian Science Foundation (grant No. 22-12-20019)
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Вид документа : Статья из журнала
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Автор(ы) : Hu T., Ning L., Gao Y., Qiao J., Song E., Chen Z., Zhou Y., Wang J., Molokeev M. S., Ke X., Xia Z., Zhang Q.
Заглавие : Glass crystallization making red phosphor for high-power warm white lighting
Место публикации : Light Sci. Appl. - 2021. - Vol. 10, Is. 1. - Ст.56. - ISSN 20955545 (ISSN), DOI 10.1038/s41377-021-00498-6
Примечания : Cited References: 50. - The present work was supported by the National Natural Science Foundations of China (Grant Nos. 51972118, 51961145101, 51722202 and 11974022), the Guangzhou Science & Technology Project (202007020005), the Fundamental Research Funds for the Central Universities (D2190980), and the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01X137)
Аннотация: Rapid development of solid-state lighting technology requires new materials with highly efficient and stable luminescence, and especially relies on blue light pumped red phosphors for improved light quality. Herein, we discovered an unprecedented red-emitting Mg2Al4Si5O18:Eu2+ composite phosphor (λex = 450 nm, λem = 620 nm) via the crystallization of MgO–Al2O3–SiO2 aluminosilicate glass. Combined experimental measurement and first-principles calculations verify that Eu2+ dopants insert at the vacant channel of Mg2Al4Si5O18 crystal with six-fold coordination responsible for the peculiar red emission. Importantly, the resulting phosphor exhibits high internal/external quantum efficiency of 94.5/70.6%, and stable emission against thermal quenching, which reaches industry production. The maximum luminous flux and luminous efficiency of the constructed laser driven red emitting device reaches as high as 274 lm and 54 lm W−1, respectively. The combinations of extraordinary optical properties coupled with economically favorable and innovative preparation method indicate, that the Mg2Al4Si5O18:Eu2+ composite phosphor will provide a significant step towards the development of high-power solid-state lighting.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Коржнева, Ксения Евгеньевна, Исаенко Л. И., Елисеев, Александр Павлович, Молокеев, Максим Сергеевич
Заглавие : Экспериментальное исследование процессов кристаллизации K2Ba(NO3)4 из раствор-расплава
Место публикации : Фундамент. пробл. совр. материаловед. - 2018. - Т. 15, № 1. - С. 11-15. - ISSN 1811-1416, DOI 10.25712/ASTU.1811-1416.2018.01.001
Примечания : Библиогр.: 7. - Работа выполнена в рамках государственного задания, проект № 0330 - 2016 - 0008 и при поддержке Российского фонда фундаментальных исследований (грант № 18-32-00359).
Ключевые слова (''Своб.индексиров.''): рост из раствор-расплава--двойные соединения--нецентросимметричные кристаллы k2ba(no3)4--рентгенофазовый и термический анализы--оптическое пропускание--growth from solution-melt--double compounds--noncentrosymmetrical crystals k2ba(no3)4--x-ray diffraction and thermal analysis--optical transmittance
Аннотация: С развитием технологий неуклонно возрастает потребность в высокоэффективных функциональных материалах. Поэтому все более важной и актуальной становится задача разработки принципов и алгоритмов поиска этих материалов. В настоящее время системы двойных нитратов привлекают внимание исследователей тем, что в этой группе существуют двойные соединения с нецентросимметричной структурой, которые рассматриваются как перспективные нелинейные материалы для коротковолнового диапазона. В результате проведенных ранее исследований из водных растворов были получены кристаллы K2Ba(NO3)4. Было выявлено, что K2Ba(NO3)4 при температуре 197,3 оС разлагается на KNO3 и Ba(NO3)2. Из-за большого количества дефектов (дендриты, зарастание основными гранями роста) оптическое качество этих кристаллов оказалось невысоким. Что обусловило необходимость поиска новых методик выращивания, обеспечивающих получение качественных оптически прозрачных кристаллов. Поэтому нами исследовались процессы кристаллизации K2Ba(NO3)4 из раствор-расплава. Подобран растворитель состава LiNO3-CsNO3-KNO3 с температурой эвтектик ниже температуры разложения двойного соединения. Выращены прозрачные кристаллы K2Ba(NO3)4 размером до 0,7 мм, определена их структура, показано отсутствие у них центра симметрии. На данных кристаллах были сняты спектры оптического пропускания. Исследование двух спектров данного соединения выращенного разными методами показало, что кристаллы, полученные из водных растворов, прозрачен от 0,25 мкм до 2,2 мкм, при этом наблюдается пик поглощения с максимум 0,3 мкм. Кристаллы, выращенные методом из раствор-расплава, прозрачны от 0,3 мкм до 2,2 мкм. Ширина запрещенной зоны составляет около 5 эВ.With the development of technology, the need for highly efficient functional materials is steadily increasing. Therefore, the developing of principles and algorithms for these materials' search becomes more and more important and actual. Currently systems of double nitrates attract researchers attention due to the double compounds with a noncentrosymmetric structure which are considered as promising nonlinear materials for the short-wave range. As a result of previous studies K2Ba(NO3)4 crystals were obtained from aqueous solutions. It was found that K2Ba(NO3)4 decomposes on KNO3 and Ba(NO3)2 at the temperature of 197.3 oC. Due to the large amount of defects (dendrites, overgrowing by the main growth facets), the optical quality of these crystals was not high. This necessitated the search for new growth techniques that provide the production of high-quality optically transparent crystals. Therefore, we investigated the processes of crystallization of K2Ba(NO3)4 from a solution-melt. A solvent of the LiNO3-CsNO3-KNO3 composition with a eutectic temperature below the decomposition temperature of the double compound was chosen. Transparent crystals of K2Ba(NO3)4 up to 0.7 mm in size were grown, their structure was determined, and the absence of center of symmetry was shown. The optical transmission spectra were investigated on these crystals. The study of two spectra of this compound grown by different methods showed that crystals obtained from aqueous solutions are transparent from 0.25 μm to 2.2 μm, with an absorption peak with a maximum of 0.3 μm. Crystals grown by the solution-melt method are transparent from 0.3 μm to 2.2 μm. The width of the band gap is about 5 eV.
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Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Wang X., Li J. -G., Molokeev M. S., Wang X., Liu W., Zhu Q., Tanaka H., Suzuta K., Kim B. -N., Sakka Y.
Заглавие : Hydrothermal crystallization of a Ln2(OH)4SO4·nH2O layered compound for a wide range of Ln (Ln = La-Dy), thermolysis, and facile transformation into oxysulfate and oxysulfide phosphors
Место публикации : RSC Adv.: Royal Society of Chemistry, 2017. - Vol. 7, Is. 22. - P.13331-13339. - ISSN 20462069 (ISSN), DOI 10.1039/c7ra00645d
Примечания : Cited References: 54. - This work was partly supported by the National Natural Science Foundation of China (Grants No. 51672039, 51172038, and 51302032), the Fundamental Research Fund for the Central Universities (Grant No. N140204002), the Grants-in-Aid for Scientific Research (KAKENHI No. 26420686), and the Russian Foundation for Basic Research (15-52-53080). Xuejiao Wang acknowledges the financial support received from the China Scholarship Council for her overseas Ph. D. study at the National Institute of Materials Science (Contract No. 201406080035).
Ключевые слова (''Своб.индексиров.''): dysprosium--hydrothermal synthesis--light emission--phase structure--phosphors--rare earth elements--acceleration voltages--chemical compositions--electron beam irradiation--hydrothermal conditions--hydrothermal crystallization--lanthanide contraction--photoluminescence properties--structure refinements--dysprosium compounds
Аннотация: The synthesis of a layered Ln2(OH)4SO4·nH2O material (Ln-241) with a smaller lanthanide ion (Dy3+) was successfully achieved through the optimization of the hydrothermal conditions, and the effect of lanthanide contraction on the chemical composition, phase structure, and crystallite/particle morphology of the products was investigated and discussed. Structure refinement showed that the lattice parameters (a, b, and c), cell volume, and axis angle across the series (Ln = La-Dy) monotonously decrease as the size of Ln3+ decreases. Comparative TG/DTA analysis in air indicated that the dehydroxylation temperature of Ln-241 tends to increase, whereas the dehydration and desulfurization temperatures decrease as the size of Ln3+ decreases, thus narrowing the stable temperature range for Ln2O2SO4. Taking advantage of the fact that Ln-241 has exactly the same Ln/S molar ratio as Ln2O2SO4 and Ln2O2S, the latter two groups of important compounds (excluding Ce) were facilely transformed from the former via the removal of water by calcination. The photoluminescence properties of Eu3+ and Tb3+, in terms of excitation, emission, fluorescence decay, quantum yield, and emission color, were investigated and compared for the two hosts Gd2O2S and Gd2O2SO4, and the (Gd0.99Tb0.01)2O2S phosphor was shown to be stable under electron beam irradiation in the studied range and exhibited an increasingly higher emission brightness as the acceleration voltage (up to 7 kV) or beam current (up to 50 μA) increased.
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Вид документа : Статья из журнала
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Автор(ы) : Wang, Xuejiao, Molokeev M. S., Zhu, Q.i., Li, Ji-Guang
Заглавие : Controlled hydrothermal crystallization of anhydrous Ln2(OH)4SO4 (Ln = Eu-Lu, Y) as a new family of layered rare earth metal hydroxides
Место публикации : Chem. - A Eur. J. - 2017. - Vol. 23, Is. 63. - P.16034-16043. - ISSN 0947-6539, DOI 10.1002/chem.201703282. - ISSN 1521-3765(eISSN)
Примечания : Cited References:54. - This work is supported in part by the National Natural Science Foundation of China (Grants Nos. 51702020, and 51672039), Doctoral Research Fund of Liaoning Province (Grant No. 20170520103) and the Russian Foundation for Basic Research (17-52-53031). X.W. acknowledges the financial support from the China Scholarship Council for her overseas Ph.D. study (Contract No. 201406080035).
Предметные рубрики: ANION-EXCHANGE MATERIALS
BOND-VALENCE PARAMETERS
X-RAY-DIFFRACTION
Ключевые слова (''Своб.индексиров.''): hydrothermal synthesis--layered compounds--luminescence--oxide sulfates--rare earths
Аннотация: Anhydrous hydroxide sulfates Ln2(OH)4SO4 (Ln=Eu–Lu, Y) were hydrothermally synthesized as a new family of layered rare earth metal hydroxides (LRHs). They crystallize in the monoclinic system (space group C2/m) with structures built up by alternate stacking of interlayer SO42− and the two-dimensional host layer composed of tricapped [LnO9] trigonal prisms along the a axis. In distinct contrast to the recently discovered hydrated LRHs Ln2(OH)4SO4⋅2 H2O, which only exist for Ln=La–Dy, the host layers of the anhydrous phase are linked together by sharing edges instead of an O node of the SO42− tetrahedron. Rietveld refinement showed that the cell dimension tends to decrease for smaller Ln3+, while the axis angle (β=98.78–100.31°) behaves oppositely. Comparative thermogravimetric/differential thermal analysis in air revealed that the dehydroxylation and desulfurization temperatures become gradually higher and lower, respectively, for smaller Ln3+, and thus the temperature range of Ln2O2SO4 existence is narrowed. The newly discovered Ln2(OH)4SO4, together with their hydrated counterparts, allow for the first time green synthesis of Ln2O2SO4 with water as the only exhaust for the full spectrum of lanthanides. Calcining Ln2(OH)4SO4 in H2 yielded phase-pure Ln2O2S for Eu and Gd and a mixture of Ln2O2S and Ln2O3 for the other Ln. The effects of the lanthanide contraction were clearly revealed, and photoluminescence was found for the anhydrous LRHs of Eu and Tb.
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10.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Ji H., Wang L., Cho Y., Hirosaki N., Molokeev M. S., Xia Z., Huang Z., Xie R.-J.
Заглавие : New Y2BaAl4SiO12:Ce3+ yellow microcrystal-glass powder phosphor with high thermal emission stability
Место публикации : J. Mater. Chem. C: Royal Society of Chemistry, 2016. - Vol. 4, Is. 41. - P.9872-9878. - ISSN 20507534 (ISSN), DOI 10.1039/c6tc03422e
Примечания : Cited References: 32. - This study was partially supported by the National Natural Science Foundation of China (Grant No. 51272259, 51572232 and 51561135015). R. X. was also partially supported by the JSPS KAKENHI (No. 15K06448). M. M. and Z. X. were also partially supported by the Russian Foundation for Basic Research (No. 15-52-53080). H. J. thanks the China Scholarship Council (CSC) for scholarship support.
Ключевые слова (''Своб.индексиров.''): aluminum--crystal structure--crystallization--glass--laser applications--light emission--microcrystals--phosphors--precipitation (chemical)--quenching--silicon--silicon oxides--single crystals--structural design--crystalline nature--crystallization behavior--emission intensity--microcrystal glass--morphology structures--phase formation behavior--structure analysis--temperature increase--cerium
Аннотация: To decrease the rare earth element usage and synthesis cost of Y3Al5O12:Ce phosphor, the Y2BaAl4SiO12 compound is developed as a new host for Ce3+ employing the solid solution design strategy. The design uses polyhedron substitution where YO8/AlO4 are partially replaced by BaO8/SiO4, respectively. Structure analysis of Y2BaAl4SiO12 proves that it successfully preserves the garnet structure, crystallizing in the cubic Iad space group with a = b = c = 12.00680(5) Å. Barium (Ba) atoms occupy the Y site and silicon (Si) atoms occupy the Al site in the AlO4 tetrahedrons. An expanded study on Y2MAl4SiO12 (M = Ba, Ca, Mg, Sr) series shows a cation size (of M)-dependent phase formation behavior. The lattice stability can be related with the M type in the M–Si pair and substitution level of M–Si for Y–Al. Doping Ce3+ into Y2BaAl4SiO12 yields bright yellow photoluminescence peaking at around 537 nm upon excitation by 460 nm light. The emission intensity is quite stable against thermal quenching whereas the peak wavelength shows a slight red-shift as the ambient temperature increases. The crystallization behavior of Y2BaAl4SiO12 is suggested as melt-assisted precipitation/growth based on cathodoluminescence analysis. The highly crystalline nature of the microcrystals explains the stable emission against thermal quenching. This study may provide an inspiring insight into preparing phosphor with new morphology-structure of “microcrystal-glass powder phosphor”, which distinguishes it from conventional “ceramic powder phosphor” or “single-crystal phosphor”.
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