Hrebelna Y. Synthesis, physicochemical properties and application of carboncarbon nanocomposites based on natural graphite and carbon nanotubes

Українська версія

Thesis for the degree of Doctor of Philosophy (PhD)

State registration number

0824U003079

Thesis Registration Form

0824U003079.pdf

Applicant for

Specialization

  • 102 - Хімія

22-10-2024

Specialized Academic Board

ДФ 26.210.6866

Chuiko Institute of Surface Chemistry of NAS of Ukraine

Essay

The dissertation is devoted to the development of methods for the synthesis of: thermally expanded graphite (EG) of high purity (carbon content more than 99.75% wt.) from flotation-enriched graphite (carbon content 94% wt.), composite systems EG-carbon nanotubes (EG–CNT ) based on a binder (aqueous solution of acrylic copolymer with isodecyl alcohol ethoxylate surfactant) and without binders by oxidized modification of CNTs and intercalation of natural graphite with concentrated sulfuric acid; continuous synthesis of graphene nanoparticles (GNP) and GNT–CNT compositions by anodic oxidation of EG foil and EG–CNT system without a binder in a weakly alkaline electrolyte in regulated regimes, to significantly reduce the cost of the process of obtaining effective wear-resistant sealing materials from high-purity EG, stable suspensions of GNT and GNP–CNT, as effective fillers of polymeric materials, the basis of highly thermally conductive films, their optimization in terms of composition and content, elucidation of the nature of the interaction of partially oxidized graphene planes between themselves and cleaning reagents. It has been experimentally shown that the combination into one process of the synthesis of oxidized graphite (intercalation of graphite by anodic treatment in concentrated sulfuric acid or a solution of potassium dichromate in concentrated sulfuric acid, followed by hydrolysis), and chemical cleaning using as cleaning reagents solutions of ammonium bifluoride in sulfate or hydrochloric acid and trilon B in an alkaline buffer, allows to obtain thermally expanded graphite of high purity, with a carbon content of more than 99.75% wt. The methods of X-ray phase analysis and thermogravimetry show that the interaction of oxidized graphite (a residual compound of intercalation of graphite with sulfuric acid) with cleaning reagents does not reduce the ability to expand. The magnitude of the mass loss of oxidized graphite according to various variants of chemical post-cleaning and the temperature range of such loss remain practically unchanged. Adding of the elastic CNT component into the composition of the EG–CNT composite material both with the use of a binder (CNT dispersion in an aqueous solution of an acrylic copolymer with isodecyl alcohol ethoxylate, the so-called "permanent stickiness glue", in accordance with the technological regulations for the production of stuffing), and joint oxidation natural graphite with CNT by anodic treatment or chemical oxidation with a solution of potassium dichromate in concentrated sulfuric acid in quantities from 0.1 to 1.0% wt. increases the mechanical characteristics, namely the recoverability by 18 – 38%, and taking into account the reduction of wear, it increases the service life of the seals by almost two times. A method of electrochemical synthesis of graphene nanoparticles or GNP–CNT composites has been developed, which involves moving with a controlled mechanical device at a speed of 0.5-3.0 cm/hour a tape with glass fiber-reinforced EG foil or a EG–CNT foil, which is the anode, through a bath of electrolyte solution (potassium hydroxide), separated by a membrane into anodic and cathodic space, with an electric field strength of 2-30 V/cm, electrolytic delamination of the graphite tape. The speed of movement of the potassium hydroxide electrolyte solution is regulated by controlling the optical density of the resulting suspension of GNP or GNP–CNT. The method makes it possible to implement a two-level system for controlling the dimensions (thickness and area) of GNP or GNP–CNT using as a precursor dense materials from EG or EG–CNT (with adjustable structure parameters) and anodic oxidation with membrane separation, control of process modes (concentration, speed, current density, time). Using the methods of quantum chemical calculations carried out using the GAMESS program (US) using the density functional theory (DFT) method with the B3LYP functional and the 6-31G(d,p) basis set, taking into account the Grimme D3 dispersion correction within the PCM polarization continuum, were found some geometric and energetical parametrs. Keywords: graphite intercalation compounds, expanded graphite, thermo-gravimetry, X-ray diffraction, recoverability, graphene nanoparticles, density functional method, cluster approximation.

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Research papers

Yu . V . Hrebelna , E . M . Demianenk o , M . I . Terets , V V . Lobanov , S V . Zhuravskyi , O M . Ignatenko , K O . Ivanenko , Yu V . Gornikov , M . T . Kartel , Yu . I . Sements ov . Syn- thesis and physico chemical properties of high quality expande d graphite // Himia, Fiz ika ta Tehnologia Poverhni, 2024. Vol.15, Issue 3, P. 378 389 https://doi.org/10.15407/hftp15.03.378

Yu V . Grebelna , E M . Demianenko , M I . Terets , Yu I . Sementso v , V V . Loban ov , A G . Grebenyuk , V S . Kuts , S V . Zhuravskyi , O V . Khora , M T . Kartel Quantu m chemical studies of the inter action of partially oxidized graphene like planes with each other Physics and chemistry of solid state V. 24, No. 2 (2023) pp. 269 277 Sec- tion: Chemistry DOI: 10.15330/pcss.24.2.269 277

Yu . V . Hrebelna , E . M . Demianenko , M . I . Terets , A . G . Grebenyuk , Yu . I . Semen- tsov , N . V . Sigareva , S . M . Makhno , M . T . Kartel. Theoretical study on the interaction of polychlorotrifluoroethylene fragments with graphene like planes // Himia, Fizika ta Tehnologia Poverhni, 2023. Vol.14, Issue 4, P. 534 545. https://doi.org/10.15407/hftp14.04.534

Morozovsky N.V., Barabash Yu.M., Grebelna Yu.V., Kartel M.T., Sementsov Yu.І., Dovbeshko G.I. Nonstationary thermophysical characterization of exfoliated graphite w ith carbon nanotubes composites // Low Temperature Physics, 49 (5), pp. 553 567 (2023). DOI 10.1063/10.0017817

V.M. Gun’ko, Yu.I. Sementsov, L.S. Andr iyko, Yu.M. Nychyporuk, O.I. Oranska, O.K. Matkovsky, Yu.V. Grebel’na , B. Charmas, J. Skubiszewska Zięba, M.T. Kartel . 2D nanostructured carbons: effects of oxidation and packing disordering. // Хімія, фізика та технологія поверхні. 2023. Т. 14. № 3. С. 27 5 299. ISSN 2079 1704.

Kodryk A., Nikulin A., Titenko A., Kirchu F., Sementsov Yu., Ivanenko K., Grebel’na Yu., Pokropivny A., Vaseashta A. Hydrocarbons Removal from Contami- nated Water by Using Expanded Graphite Sorbents. In: Vaseashta A., Maftei C. (ed s) Water Safety, Security and Sustainability. Advanced Sciences and Technologies for Security Applications. Spring er, Cham. 2021. pp 523 545. https://doi.org/10.1007/ 9 978 978--33--030030--7600876008--3_223_22

Sementsov Yu. Grebel’na Yu ., Strelchuk V., Dovbeshko G., Zhurav skyi S., Ma- khno S., Wang Bo, Kartel M. Ca rbon Carbon Composition “Expand ed Gra phite Multiwalled Carbon Nano tubes” International Journal of Mate rials Science and Applications. Vol. 8, No. 6, 2019, pp. 127 134. doi: 10.11648/j.ijmsa.20190806.16

Karte l M., Dovbeshko G., Karachevtseva L., Makhno S., Aleksyeyeva T., Grebel’na Yu ., Styopkin V., Wang Bo, Stubrov Yu, Sementsov Yu. Lamellar tures from graphene nanoparticles produced by anode oxidation. Advanced Materials Letters 2017, 8(3), p.212 216 ht tps://doi.org/ 10.5185/ amlett.2017.1428

Махно С.М., Лісова О.М., Гуня Г.М., Гребельна Ю.В ., Семенцов ЮІ, Картель М.Т . Властивості синтезованих графенів та системи поліхлортрифторетилен графени // Фізика і хімія твердого тіла. 2016. T. 17. № 3. С. 421 425.

Патент КНР CN 114134520B, від 09 грудня 2022 р. Заявка ZL 2021 1 1391432.6 від 23.11.2021 Електрохімічний спосіб приготування суспензії вуглецевих нанотрубок і графену. Дін Ан; Ван Бо; Ван Дунсін; Лі Тяньцзюнь; Семенцов ЮІ; Махно СМ; Картель М Т, Гождзінський СМ; Іваненко КО; Гребельна ЮВ

Патент України № 127634 , від 09.11.2023р. Заявка №a 2021 02263 від 28.04.2021 Бюл. № 45 від 08.11.2023 Спосіб електрохімічного одержання суспензії графену з вуглецевими нанотрубка Семенцов Ю І Махно С М Картель М Т Гождзінський С М Іваненко К О Гребельна Ю В Дін Анг, Ван Бо, Ван Дунсин, Ли Тяньцзюнь

Патент України № 123379 від 25.03.2021 Заявка № a201909143 від 06.08.2019. Бюл. № 12/2021 від 24.03.2021 Спосіб виготовлення композитного вугле цевого матеріалу Семенцов Ю. І., Гребельна Ю. В., Картель М. Т., Махно С. М., Журавський С.В., Ван Бо, Дин Анг.

Патент України № 123525. Заявка № a 201909142 від 06.08.2019. Бюл. № 15/2021 від14.04.2021 Спосіб виготовлення композитного вуглецевого матер іалу для графітової фольги . Семенцов Ю. І., Гребельна Ю. В ., Картель М. Т., Махно 10 С. М., Ігнатенко О.М., С. М., Ігнатенко О.М., Ван Бо, Дин АнгВан Бо, Дин Анг

Yu.V. Hrebelna , E.M. Demianenko, M.I. Terets, A.G. Grebenyuk, Yu.I. tsov, N.V. Sigareva, S.M. Makhno, M.T. Kartel Theoretical study on the interaction of polychlorotrifluoroethylene fragments with graphene like planes. Book of abstracts of Ukr ainian Conference with Interna tional Participation “Chemistry, Physics and Tech- nology of Surface” Kyiv, 2023. 11 12 October, 2023, Kyiv, Ukraine, P. 64.

Yu.V. Hrebelna , E.M. Demianenko, M.I. Terets, K.O. Ivanenko, Y. Shi, N.V. Vitiuk, M.T. Kartel, Yu.I. Sementsov Expanded graphite carbon nanotubes nano- composite materials. Book of abstracts of Ukrainian Conference with International Pa rticipation “Chemistry, Physics and Technology of Surface” Kyiv, 2023. 11 12 October, 2023, Kyiv, Ukraine, P. 65.

M.T. Kartel, V.S. Tolmachova, O.A Cherniuk., Yu. V. Hrebelna , Yu.I. Sementsov. Expanded graphite as the best sorbent for hydrocarbons // 2023 IOP Conf. Ser.: Earth Environ. Sci. 1126 012025. doi:10.1088/1755 1315/1126/1/012025 17. K. Ivanenko, D. Wang, E. Demianenko, Y. Grebel'na M. Kartel and Y. Semen- tsov . Expanded Graphite Carbon Nanotubes Nanocomposite Materials . 2023 IEEE 13th Inter national Conference Nanomaterials: Applications & Properties (NAP), Bratislava, Slovakia, 2023, pp. IMT03 1 IMT03 6, doi: 10.1109/NAP59739.2023.10310835.

Sementsov Yu .І., Ivanenko K O ., Grebelna Yu V ., Kartel M T ., Karachevtseva L A ., Makhno S M ., Zhur avskyi S V ., Wang Bo , Yang Weiyou Obtaining technology of hybrid nano materials carbon nanotubes graphene nanoparticles . Materials Inter- national Meeting “Clusters and Nanostruc tured Materials” (CNM 6). Uzhgorod Vodograj Ukraine, 5 9 October 2020. P. 141 145

Yuli Shi, Stanislav Makhno, Mariya Terets, Yuliia Hrebelna , Kateryna Ivanenko, Mykola Kartel, Eugeniy Demianenko, Smail Hamamda and Yurii Sementsov. The carbon nanotubes, graphene nano particles their oxygen modified forms and compo- sites. The 2nd International Confer ence of Nanotechnology for Environmental Protec- tion and Clean Energy Production (IC NEP’2023). October 09 10, 2023, Constantine 11 – – Algeria. P. 54Algeria. P. 54--5555

Grebelna J V .., Makhno S M ., Sementsov Yu I Kartel M T Carbon carbon compo- site mat erial thermo expanded graphite carbon nanotubes. International research and practice conference “Nanotechnology and Nanomaterials (NANO 2019)2019): Book of ab- stracts Ukrainian Conference with International participation , Lviv , 23 30 August 2019. Р. 161

Morozovsky N.V. V.; Barabash Yu.M.; Grebelna Yu.V. V.; Kartel M.T.; Sementsov Yu.І.; Dovbeshko G.I. Non stationary thermophysical characterization of exfoliated graphite with carbon nanotubes composites Repository: arXiv9. December 2022. ISSN 23318422. DOI 10.48550/arXiv.2212.05036 arXiv:2212.05036 [condmat.mtrl sci] (or arXiv:2212.05036v1 [condmat.mtrlsci] for this version) https://doi.org/10.48550/arXiv.2212.05036

Mista V., Dovbesh ko G., Boiko V., Sementsov Yu., Grebel’na Yu ., Kartel M., Strek W. Nonlinear optical and thermophysical properties of exfoliated graphite/cnt nanocomposite as photocatalytic target for methanol reforming. Abstracts book of 21st International Conference on Dynamical Processes in Excited States of Solids (DPC 2022). September 04 09, 2022, Wrocław, Poland. P. 71 (P 12)

N.V. Morozovsky, Yu.M. Barabash, G.I. Dovbeshko, Yu.V. Grebelna , M.T. tel, Yu.I. Sementsov, J. Macutkevic, J. Banis. Thermophysical and electrophysical of exfoliated graphite carbon nanotubes composites International Advanced Re search Workshop “Thermal Conductivity of solid states at low temperature” in the f rame of the II International Ad vanced Study Conference “Condensed matter & low t empera- ture physics” CM&LTP 2021, 8 June 2021 Kharkiv, Ukraine Workshop, Program Book of Abstracts, Kharkiv 2021, p. 15

Morozovsky N V ., Barabash Yu M ., Dovbeshko G I Grebelna Yu V .., Kartel M T ., Sementsov Yu . Estimation of thermal diffusivity of expanded graphite carbon nano- tubes composites by heat pulse and thermowave methods. International research and practice conference “Nanotechnology and Nanomaterials (NANO 2018)2018): Book of ab- stracts Ukrainian Conferenc e with International participation , Kyiv , 27 30 August 2018. 12 Р. 3 Р. 35454..

Yu. Grebelna , S.Makhno, Yu. Sementsov. An effective method for graphene platelets production by anode oxidation of expanded graphite. Book of abstracts of Ukrainian Conference wit h International Participation “Chemistry, Physics and Tec h- nology of Surface” 17 18 May, 2016, Kyiv, Ukraine, P. 144

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