Журналы →  Tsvetnye Metally →  2023 →  №8 →  Назад

Marking the 250th anniversary of the Empress Catherine II St Petersburg Mining University and the 20th anniversary of the Nanophysics & Nanomaterials International Conference
MATERIALS SCIENCE
Название Inorganic synthesis of highly hydrophobic metals containing surface compounds with electron acceptor modifiers: process features
DOI 10.17580/tsm.2023.08.11
Автор Kushchenko A. N., Syrkov A. G., Ngo Q. K.
Информация об авторе

Empress Catherine II Saint Petersburg Mining University, Saint Petersburg, Russia:

A. N. Kushchenko, Assistant Lecturer at the Department of General and Technical Physics, Candidate of Technical Sciences, e-mail: Kuschenko_AN@pers.spmi.ru
A. G. Syrkov, Professor at the Department of General and Technical Physics, Doctor of Technical Sciences, e-mail: Syrkov_AG@pers.spmi.ru
Q. K. Ngo, Postgraduate Student at the Department of Chemical Technology and Energy Processing, e-mail: ngoquockhanh292@mail.ru

Реферат

Using the technique of solid-state hydride synthesis, which is based on the reduction of solid compounds of metals in a flow-type reactor with volatile element-hydrogen compounds in the region of thermal stability of the latter, the authors obtained dispersed 3D metal products applied to silica substrates. The surface of such products contains chemosorbed molecules of various silicon hydride reducing agents. For the first time the reduction properties of silicon hydride reagents were correlated with their nucleophilic properties, which were analyzed on the basis of quantum-chemical calculations, performed with the help of HyperChem. The study confirmed a symbatic relationship at the initial stage of NiCl2 reduction between the nucleophilic properties of the studied reagents with a Si – H bond in the molecule structure and the degree of reduction reached. It was found that, with all the other conditions being equal and depending on the type of the reducing agent, the degree of reduction rises in the following row: vapour of methyldichlorosilane, vapour of methyl hydride siloxane, vapour of ethyl hydride siloxane, monosilane. The experiments revealed a much greater efficiency of methyldichlorosilane rather than monosilane for the reduction of oxide material. The former chlorinates the oxide and thus makes its reduction easier and more efficient. Depending on the type of metal and the initial solid-phase material, reduction in the methyldichlorosilane vapour helps control the specific surface of the metal product in the range of 40 to 120 m2/g. It is demonstrated that a metal product (M = Cu, Ni, Fe) with a highly hydrophobic surface is formed as the result of consecutive reduction of the initial compounds (material) in the methyldichlorosilane vapour and in methane. This paper describes the first consistent study that relied on X-ray photoelectron spectroscopy to understand the adjustability of the electron binding energy of the characteristic level of metal (M2p3/2) reduced by solid-state hydride synthesis on silica substrates. Depending on the type of reducing agent used, the binding energy of the M2p3/2 level of metal on silica gel, which reflects the degree of stabilization on substrate, rises following the sequence H2, CH4, NH3, CH3SiHCl2, SiH4. Silica gel samples coated with nickel by solid-state hydride synthesis were found to manifest the strongest hydrophobic properties, comparable to the properties of the superhydrophobic organosilicon adsorbent of polymethylsiloxane. Samples of porous glass coated with copper in the same conditions have a good hydrophobicity, stability and improved emission characteristics and can compete with nanocarbon structures as an innovative material for cold cathodes.

Ключевые слова Metallurgy of nickel, copper, metal reduction on silica substrates, solid-state hydride synthesis, nanotechnology, nucleophilic properties, moisture resistance
Библиографический список

1. Mineev G. G., Mineeva T. S., Zhuchkov I. A., Zelinskaya E. V. Theory of metallurgical processes. Irkutsk : Izdatelstvo IrGTU, 2010. 524 p.
2. Sizyakov V. M., Polyakov P. V., Bazhin V. Yu. Production of aluminium and its alloys in Russia: Current trends and strategic objectives. Tsvetnye Metally. 2022. No. 7. pp. 16–23.
3. Quiroz Cabascango V. E., Bazhin V. Yu. Nickel oxide reduction in CO/CO2 gas mixtures in reverberatory furnaces. IOP Conference Series: Metrological Support of Innovative Technologies. 2020. Vol. 1515. 022028. DOI: 10.1088/1742-6596/1515/2/022028
4. Brichkin V. N., Vorobiev A. G., Bazhin V. Yu. Mining Institute’s metallurgists: a tradition serving the Country, science and production industry. Tsvetnye Metally. 2020. No. 10. pp. 4–13.
5. New Materials. Preparation, properties and applications in the aspect of nanotechnology. New York : Nova Science Publishers, Inc., 2020. 249 p.
6. Applied Aspects of Nano-Physics and Nano-Engineering. New York : Nova Science Publishers, Inc., 2019. 308 p.
7. Sosnov E. A., Malkov A. A., Malygin A. A. The nanotechnology of monomolecular layering in the production of inorganic and hybrid materials for different applications (Review). I Molecular layering method: How it originated
and evolved. Zhurnal prikladnoy khimii. 2021. No. 8. pp. 967–986. DOI: 10.31857/S0044461821080028
8. Sosnov E. A., Malkov A. A., Malygin A. A. The nanotechnology of monomolecular layering in the production of inorganic and hybrid materials for different applications (Review). II. The process of molecular layering and its potential commercialization and development in the 21st century. Zhurnal prikladnoy khimii. 2021. No. 9. pp. 1104–1137. DOI: 10.31857/S0044461821090024
9. Tsvetkov G. M., Maksarov D. V., Chasovskoy O. V. On V. B. Aleskovskiy’s concepts in the field of nanotechnology and directed synthesis of solids. Proceedings of the Nanophysics and Nanomaterials International Conference. 23–24 November 2022, Saint Petersburg, Russia. St Petersburg : Sankt-Petersburgskiy gornyi universitet, 2022. pp. 332–337.
10. Aleskovskiy V. B. The chemistry of supramolecular compounds. St Petersburg : Izdatelstvo SPbTU, 1996. 256 p.
11. Academicians of the victory. St Petersburg : Nauchnoe izdatelstvo biograficheskoy mezhdunarodnoy entsiklopedii “Gumanistika”, 2020. pp. 29–31.
12. Syrkov A. G., Kushchenko A. N., Silivanov M. O., Taraban V. V. Nanostructured regulation of the surface properties and hydrophobicity of nickel and iron by solid-state reduction and modifying methods. Tsvetnye Metally. 2022. No. 5. pp. 54–59.
13. Yachmenova L. A. Developing an energy and resource saving technology for producing metal products using reducer-modifier hydrides: Extended abstract of dissertation of Candidate of Technical Sciences. St Petersburg, 2021. 23 p.
14. Silivanov M. O. Adsorption and acidity/basicity properties of metals with organo hydride siloxane and ammonium compounds on the surface and their influence on the antifriction effect: Extended abstract of dissertation of Candidate of Technical Sciences. St Petersburg, 2018. 24 p.
15. Aleskovskiy V. B. Quantum synthesis. Zhurnal prikladnoy khimii. 2007. Vol. 80, No. 1. pp. 1761–1767.
16. Smirnov V. M., Zemtsova E. G., Belikov A. A. et al. Chemical design of quasi-one-dimensional organoferric nanostructures fixed to an inorganic matrix and understanding their magnetic properties. Doklady Akademii nauk. 2007. Vol. 413, No. 6. pp. 776–780.
17. Pak V. N., Lapatin N. A., Pronin V. P., Yachmenova L. A. Obtaining and electronic emission of planar structures of metallic copper on a porous ceramic substrate. Tsvetnye Metally. 2021. No. 5. pp. 55–59.
18. Boynovich L. B. Superhydrophobic coatings as a new class of polyfunctional materials. Vestnik RAN. 2013. Vol. 83, No. 1. pp. 10–22.
19. Baake E., Shpenst V. A. Recent scientific research on electrothermal metallurgical processes. Journal of Mining Institute. 2019. Vol. 240. pp. 660–668.
20. Pozhidaeva S. D., Ageeva L. S., Ivanov A. M. Comparative analysis of zinc and tin oxidation with acids at room temperatures. Journal of Mining Institute. 2019. Vol. 235. pp. 38–46. DOI: 10.31897/pmi.2019.1.38
21. Zhao Y., Xu J. B., Hu J. M. et al. Electrodeposited superhydrophobic silica films coembedded with template and corrosion inhibitor for active corrosion protection. Applied Surface Science. 2020. Vol. 508. 145242. DOI: 10.1016/j.apsusc.2019.145242
22. Kantyukov R. R., Zapevalov D. N., Vagapov R. K. Analysis of application and impact of carbon state of oil and gas facilities. Journal of Mining Institute. 2021. Vol. 250. pp. 578–586.
23. Thanasekaran P., Su C. H., Liu Y. H., Lu K. L. Hydrophobic metalorganic frameworks and derived composites for microelectronics applications. Chemistry – A European Journal. 2021. Vol. 27. pp. 16543–16563. DOI: 10.1002/chem.202100241
24. Litvinenko V. S., Tsvetkov P. S., Dvoynikov M. V., Buslaev G. V. Barriers to implementation of hydrogen initiatives in the context of global energy sustainable development. Journal of Mining Institute. 2020. Vol. 244. pp. 421–431. DOI: 10.31897/pmi.2020.4.5
25. Vinogradova A. A. Ways to control the antifriction properties of tribotechnical materials containing low-dimensional modifiers of metal additions, accounting for non-linear effects: Extended abstract of dissertation of Candidate of Technical Sciences. St Petersburg, 2017. 20 p.
26. Anderson H. H. Reactions of triethylsilane and dimethylsilane with inorganic palids an acids. Journal of the American Chemical Society. 1958. Vol. 60, No. 19. pp. 5083–5087.
27. Slinyakova I. B., Denisova T. I. Organosilicon adsorbents: Production, properties, application. Kyiv : Naukova dumka, 1988. 192 p.
28. Makhova L. V. Hydride solid-state synthesis and the structural and chemical features of Si – C-bearing metallic substances: Extended abstract of dissertation of Candidate of Technical Sciences. St Petersburg, 1993. 22 p.
29. Clark T. Computer chemistry. Moscow : Mir, 1990. 383 p.
30. Musina D. T., Kabirov V. R., Khanh N. Q. Electrophilic and nucleophilic modifiers as a factor of formation of lipophilic properties of surface – modified materials. Materials Science Forum. 2021. Vol. 1040. pp. 94–100.
31. Kabirov V. R., Musina D. T., Ngo Quoc Khanh. Understanding the electrophilic-nucleophilic properties of oligohydride ethyl siloxane – an active component of the hydrophobizing organosilicon liquid GKZh-94. Proceedings of the Nanophysics and Nanomaterials International Conference. 25–26 November 2020, Saint Petersburg, Russia. St Petersburg : Sankt-Peterburgskiy gornyi universitet, 2020. pp. 163–173.
32. Kriklivyi D. I., Klimovich N. A. Examining the activity of gas reductants and methods of selecting them in high-temperature oxidation-reduction processes. Zhurnal prikladnoy khimii. 1991. Vol. 64, No. 11. pp. 2242–2249.
33. Yang Z., Liu X., Tian Y. Novel metal-organic super-hydrophobic surface fabricated by nanosecond laser irradiation in solution. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2020. Vol. 587. 124343. DOI: 10.1016/j.colsurfa.2019.124343
34. Su D. Y., Hsu C. C., Lai W. H., Tsai F. Y. Fabrication, mechanisms, and properties of high-performance flexible transparent conductive gas-barrier films based on Ag nanowires and Atomic Layer Deposition. ACS Applied Materials & Interfaces. 2019. Vol. 11, No. 37. pp. 34212–34221. DOI: 10.1021/acsami.9b09772
35. Chen R., Shan B., Liu X., Cao K. Catalysts via Atomic Layer Deposition. Recent Advances in Nanoparticle Catalysis. Molecular Catalysis. Vol. 1. Springer, Cham., 2020. pp. 69–105. DOI: 10.1007/978-3-030-45823-2_3
36. Voznyakovskiy A. P., Fursey A. A., Voznyakovskiy A. A. et al. Lowthreshold field electron emission from a two-dimensional carbon structure. Pisma v zhurnal tekhnicheskoy fiziki. 2019. Vol. 45, No. 9. pp. 46–49. DOI: 10.21883/PJTF.2019.09.47715.17705
37. Korneev S. I. Global overview of the non-ferrous metals market. Tsvetnye Metally. 2020. No. 7. pp. 4–7.
38. Ginzburg V. L. About science, myself and others. Moscow : Izdatelstvo fiziko-matematicheskoy literatury, 2003. 544 p.
39. Lutskiy D. S., Ignatovich A. S. Understanding the hydrometallurgical recovery of copper and rhenium when processing off-grade copper concentrates. Journal of Mining Institute. 2021. Vol. 251. P. 723–729. DOI: 10.31897/PMI.2021.5.11
40. Cheremisina E., Cheremisina O., Ponomareva M., Bolotov V., Fedorov A. Kinetic features of the hydrogen sulfide sorption on the ferro-manganese material. Metals. 2021. Vol. 11. P. 90. DOI: 10.3390/met11010090
41. Litvinova T. E., Kashurin R., Lutskiy D. Complex formation of rare-earth elements in carbonate–alkaline media. 2023. Materials. Vol. 16. P. 3140. DOI: 10.3390/ma16083140
42. Bolobov V. I., Chupin S. A., Mishin I. I. et al. Grain size reduction in the material structure as an effective method of increasing the wear resistance of quick-wear elements of mining equipment. New Materials: Preparation, Properties and Applications in the Aspect of Nanotechnology. 2020. pp. 29–38.
43. Smerdov R. S., Mustafaev A. S., Spivak Yu. M. et al. Composite nanostructured materials for plasma energetic systems. Applied Aspects of Nano-Physics and Nano-Engineering. 2019. pp. 229–236.

Полный текст статьи Inorganic synthesis of highly hydrophobic metals containing surface compounds with electron acceptor modifiers: process features
Назад