Investigation of structure and electrical properties of graphene-containing shungite by data of electric force microscopy with the sequence analysis employment. Abstract

Zhurnal Radioelektroniki - Journal of Radio Electronics. eISSN 1684-1719. 2020. No. 1
Contents

Full text in Russian (pdf)
Russian page

DOI 10.30898/1684-1719.2020.1.9

UDC 537.874; 537.624

INVESTIGATION OF STRUCTURE AND ELECTRICAL PROPERTIES OF GRAPHENE-CONTAINING SHUNGITE BY DATA OF ELECTRO-FORCE MICROSCOPY WITH THE SEQUENCE ANALYSIS EMPLOYMENT

I .V. Antonets ¹, E. A. Golubev ², V. G. Shavrov ³, V. I. Shcheglov ³

¹Syktyvkar State University, Oktyabrskiy prosp. 55, Syktyvkar 167001, Russia

² Geology Institute Komy SC UrD RAS, Pervomaiskaya 54, Syktyvkar 167982, Russia

³Kotelnikov Institute of Radioengineering and Electronics of Russian Academy of Sciences, Mokhovaya 11-7, Moscow 125009, Russia

The paper is received on January 14, 2020

Abstract. The investigation of the structure and electro-conductive properties of graphene-containing shungite which is used for manufacturing electromagnetic field screens is carried out. The investigation is executed by using the electro-force spectroscopy method which data are interpreted with the aid of sequence analysis. It is shown that the measuring spreading resistance by this method when scanning the flat surface of shungite specimen allows obtaining the flat chart of carbon allocation. The conductivity charts which are obtained by this method over the specimen surface are processed by using the binary discretization mechanism. The allocation of local conductivity over the surface of specimen is presented in the view of two-dimension binary chart which consists of square cells net having two strong distinguished values of conductivity – large and small. It is noted that the cells which have large conductivity correspond to well conducting carbon and the cells which have small conductivity correspond to not well conducting quarts. The graphic presentation is made of binary chart in the appearance of square field containing square cells where the cells having large conductivity marked as black checks and the cells having small conductivity marked as white checks. Discretized binary charts 8 by 8 cells in size were obtained for seven shungite samples selected in the range of carbon concentration changes from 3 to 97%. It is noted that a binary chart can be considered as a set of lines consisting of sequences of rectangular pulses of one and the other sign following each other. As a tool for studying such strings, it is proposed to use Walsh functions defined along the length of the string, which are a set of successive pulses of unit length with an amplitude equal to plus or minus one. As a method of identifying Walsh functions convenient for analyzing binary charts, it is proposed to number them according to a sequentially increasing number of zero intersections, called the sequent. It is established that a complete set of linearly independent orthogonal Walsh functions provides the possibility of expanding the configuration of any row of a binary chart into them. A methodology for generating Walsh functions is proposed, which is based on the generation of a sequence of binary numbers increasing by one. A step function is formed from each binary number, consisting of unit pulses with an amplitude equal to plus or minus one. From the resulting set of step functions, those satisfying the orthogonality condition are selected, which are further ordered by increasing sequence numbers. The proposed procedure was implemented for a zero-starting sequence of 256 first binary numbers containing eight bits. As a result, a set of eight first Walsh functions was formed, corresponding to eight values of sequences from zero to seven, orthogonal to each other and ordered by the number of zero intersections, that is, by their sequences, which was used later for the analysis of binary charts. A method is proposed for the formation of a spectral chart, which consists in digitizing binary charts with the values plus and minus one, followed by the expansion of the lines of the digitized chart according to the Walsh functions, sorted by increasing their sequences. We studied the transformation of the spectral chart when the binary chart is rotated with a step of 90 degrees around the normal axis passing through its center. Despite the strong difference between the resulting spectral charts from each other, there are two possibilities for obtaining generalized characteristics related to the conductivity chart and the parameters of the sample as a whole. It was found that at any turn of the chart, the sum of all elements of the first column remains constant, which is one of the generalized characteristics of the chart. Another possibility of obtaining generalized information from the spectral chart is realized by summing the elements of the map in columns without regard to the sign, that is, modulo. It is shown that the sums over all columns is not changed when the chart is rotated 180^o and when rotated 90^o (or to 270^o) the sums for some columns acquires different values. It is noted that this changing says about the anisotropic character of carbon distribution in the chart area. As a measure of anisotropy it is proposed to obtain the whole quantity of zero intersections for all spectral functions above the whole chart for one or another of its orientation. The total sums of intersections are calculated at the initial position of the chaert and its rotation by 90 °. The definition of the anisotropy coefficient of carbon distribution is introduced as the ratio of the smaller of the values obtained from the chart to the larger. As an example, the anisotropy coefficient is determined for a sample with a volumetric carbon content of 53% and a surface content of 65%. It is shown that in this case, the carbon distribution anisotropy coefficient obtained from the chart is 5%.

The relationship between the structure of the spectra and the carbon concentration is investigated, for which the sums in the columns are found taking into account the sign of the expansion coefficients of the binary chart strings for samples with different concentrations. It is shown that the first coefficient of the spectrum, corresponding to its constant component, provided that the sign changes and the origin of the order of the coefficients for different samples is set to zero, reflects the planar carbon concentration with an accuracy of 10%. The analysis of the sum of the moduli of the coefficients of the spectra corresponding to the sequence numbers of the sequences is carried out. The normalized value of the number of zero crossings for a complete set of spectrum components is calculated. It is shown that the quotient of dividing the total length of the string by the normalized number of intersections determines the length of the part of the string consisting of the same elements - carbon or quartz. It is established that the ratio of this part length to the length of line is the characteristic of the whole disunity of structure. It this case the information about character dimension of carbon part gives the possibility to interpret the shungite structure on the basis of models having periodic lattice character (“cubes with percolation”, “sand with liquid”), which leads to significant simplification of the necessary mathematical apparatus. The carbon content of the column sums of the absolute values of the row expansion coefficients of the binary chart was reduced for all values of the sequent except zero. It was shown that the dependence of the concentration-averaged coefficients on the concentration, taking into account the shift in concentration by 0.1844 rel.units, coincides with the dependence of the conductivity on the same concentration with an accuracy of no worse than 10%. Based on the results of the work, some practical recommendations are given on measuring shungite parameters by the method of electric power microscopy using sequential analysis of binary charts. Carbon concentration, structure fragmentation, and schungite conductivity were noted as parameters accessible to measurement. Recommendations are given for obtaining integral parameters, in particular, the need to increase the area of the chart and the order of spectrum decomposition is noted.

Key words: carbon, shungite, electro-conductivity.

References

1. Lutsev L.V., Nikolaichuk G.A., Petrov V.V., Yakovlev S.V. Multipurpose radio-absorbing materials on the basis of magnetic nanostructure: obtaining, properties, application. Nano-tehnika – Nano-engineering. 2008. No.10. P.37-43. (In Russian)

2. Kazantseva N.E., Ryvkina N.G., Chmutin I.A. Promising materials for microwave absorbers. Journal of Communications Technology and Electronics. 2003. Vol.48. No.2. P.173-184.

3. Ostrovsky O.S., Odarenko E.N., Shmatko A.A. Protective screens and absorbers of electromagnetic waves. Fizicheskaya injeneriya poverhnosti - Physical engineering of surface. 2003. Vol.1. No.2. P.161-172. (In Russian)

4. Antonov A.S., Panina L.V., Sarichev A.K. High-frequency magnetic permeability of composite materials containing the carbon-iron. Technical Physics. The Russian Journal of Applied Physics. 1989. Vol.59. No.6. P.88-94. (In Russian)

5. Vinogradov A.P. Elektrodinamika kompozitnykh materialov [Electrodynamics of composite materials]. Moscow, URSS Publ. 2001. (In Russian)

6. Vendik I.B., Vendik O.G. Meta-materials ant its application in microwave engineering. Technical Physics. The Russian Journal of Applied Physics. 2013. Vol.58. No.1. P.1-24. DOI: https://doi.org/10.1134/S1063784213010234.

7. Smith D.R., Padilla W.J., Vier D.C., Nemat-Nasser S.C., Schultz S. Composite medium with simultaneously negative permeability and permittivity. Phys. Rev. Lett. 2000. Vol.84. No.18. P.4184-4187.

8. Pendry J.B. Negative refraction makes a perfect lens. Phys. Rev. Lett. 2000. Vol.85. No.18. P.3966-3969.

9. Borisov P.A. Karelskie shungity. [Karelian shungites]. Petrozavodsk, Karelia Publ. 1956. (In Russian)

10. Philippov M.M. Shungitenosnyyee poroyi onezhskyi struktury [Shungite-containing rocks of Onega structure]. Petrozavodsk. Karelian SC RAS. 2002. (In Russian)

11. Sokolov V.A., Kalinin Yu.K., Gukkiev E.F. Shungiyi – novoe uglerodistoye sirye [Shungites – new carbon raw material]. Petrozavodsk, Karelia Publ. 1984. 176 p. (In Russian)

12. Philippov M.M., Medvedev P.P., Romashkin A.E. About nature of South Karelia shungites. Litologia i poleznie iskopaemie – Lithology and useful minerals. 1998. ¹3. P.323-332. (In Russian).

13. Melezhik V.A., Filippov M.M., Romashkin A.E. A giant paleoproterozoic deposit of shungite in NW Russia. Ore Geology Reviews. 2004. Vol.24. P.135-154.

14. Moshnikov I.A., Kovalevsky V.V., Lazareva T.N., Petrov A.V. Ispolzovanie shungitovih porod v sozdanii padioekraniruyushchih kompozitsionnih materialov. [The shungite rocks employment in creation of radio-screening composite materials]. Materials of conference “Geodynamics, magmatizm, sedimentogenes and minerageniya of north-west of Russia”. Petrozavodsk. Geological Institute of KarSC RAS. 2007. P.272-274. (In Russian)

15. Linkov L.M., Makhmud M.Sh., Kryshtopova E.A. The electromagnetic radiation screens on basis of powder-like shungite. Bulletin of Polotsk State university. Series C. Main sciences. Novopolotsk. Polotsk State University. 2012. No. 4. P.103-108. (In Russian)

16. Linkov L.M., Borbotko T.V., Kryshtopova E.A. The radio-absorption properties of nickel-containing powdery shungite. Technical Physics Letters. 2009. Vol.35. No.9. P.44-48. (In Russian)

17. Rodionov V.V. Mehanizmi vzaimodeystviya SVCh izluchenia s nanostrukturirovannimi uglerodsodershashchimi materialami. [The mechanisms of interaction of VHF-radiation with nanostructused carbon-contained materials]. PhD-thesis. Kursk. 2014. (In Russian).

18. Emelyanov S.G., Kuzmenko A.P., Rodionov V.V., Dobromyslov M.B. Mechanisms of microwave absorption in carbon compounds from shungite. Journal of Nano- and Electronic Physics. 2013. Vol.5. No.4. P.04023-1 04023-3.

19. Kuzmenko A.P., Rodionov V.V., Kharseev V.A. Hyperfullerene carbon nane structures as a powder fill for absorption of microwave radiation. Nanotekhnologiya - Nano-technology. 2013. No.4. P.35-36. (In Russian)

20. Kuzmenko A.P., Rodionov V.V., Emelyanov S.G., Chervyakov L.M., Dobromyslov M.B. Microwave properties of carbon nanotubes grown by pyrolysis of ethanol on nickel catalyst. Journal of Nano- and Electronic Physics. 2014. Vol.6. No.3. P.03037-1 03037-2.

21. Boiprav O.V., Ayad H.A.E., Lynkov L.M. Radioshielding properties of nickel-containing activated carbon. Technical Physics Letters. 2019. Vol.45. No.12. P.635-637.

22. Savenkov G.G., Morozov V.A., Ukraintseva T.V., Kats V.M., Zegrya G.G., Ilyushin M.A. The effect of shungite additives on electric discharge in ammonium perchlorate. Technical Physics Letters. 2019. Vol.45. No.19. P.1001-1003.

23. Golubev Ye.A., Antonets I.V., Shcheglov V.I. Model'nyye predstavleniya mikrostruktury, elektroprovodyashchikh i SVCH-svoystv shungitov [Model presentation of microstructure, electroconductivity and microwave properties of shungite]. Syktyvkar. Sykyivkar State University. 2017. (In Russian)

24. Golubev Ye.A., Antonets I.V., Shcheglov V.I. Static and dynamic conductivity of nanostructured carbonaceous shungite geomaterials. Materials Chemistry and Physics. 2019. Vol. 226. No.3. P.195-203.

25. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Dynamic microwave conductivity of graphene-based shungite. Technical Physics Letters. 2018. Vol.44. No.5. P.371-373.

26. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. The investigation of conductivity of graphene-containing shungite by waveguide method. Book of papers of International symposium “Perspective materials and technologies”. Vitsebsk. Belarus. 2017. P.6-9. (In Russian)

27. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Dynamic conductivity of graphene-containing shungite in microwave region. Book of papers of conference “Phase transitions, critical and nonlinear phenomena in condensed media”. Institute of Physics of Dagestan Scientific Centre RAS. Makhachala. 2017. P.432-436. (In Russian)

28. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Dynamic conductivity of graphene-containing shungite in microwave region. Book of papers of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI. 2017. P.135-147. (In Russian).

29. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Influence of substratum on the reflection and propagation properties of two layer conducting structure. Book of papers of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI. 2017. P.166-182. (In Russian)

30. Kovalevsky V.V. Struktura uglerodnogo veshchestva i genezis shungitovykh porod. [Structure of carbon substance and extraction of shungite rocks]. Doctor-thesis. Petrozavodsk. 2007. (In Russian).

31. Sheka E.F., Golubev E.A. Technical graphene (reduced graphene oxide) and its natural analog (shungite). Technical Physics. The Russian Journal of Applied Physics. 2016. Vol.61. No.7. P.1032-1038.

32. Golubev E.A., Ulyashev V.V., Veligshanin A.A. Porosity and structure parameters of Karelian shungite by data of small-angle dispersion of synchrotron radiation and microscopy. Kristallografia – Crystallography. 2016. Vol.61. No.1. P.74-85. (In Russian).

33. Morosov S.V., Novoselov K.S., Geim A.K. Electron transport in graphene. Phys. Usp. 2008. Vol.51. No.7. P.744-748.

34. Hill E.W., Geim A.K., Novoselov K., Schedin F., Blake P. Graphene spin valve devices. IEEE Trans. Magn. 2006. Vol.42. No.10. P.2694-2696.

35. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Influence of shungite structure parameters on its electro-conductivity properties. Zhurnal Radio electroniki – Journal of Radio Electronics. 2017. ¹5. Available at: http://jre.cplire.ru/jre/may17/11/text.pdf (In Russian)

36. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. The model presentation of microstructure, conductivity and microwave properties of graphene-containing shungite. Zhurnal Radio electroniki – Journal of Radio Electronics. 2017. No.9. Available at: http://jre.cplire.ru/jre/sep17/8/text.pdf (In Russian)

37. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. The model presentation of shungite microstructure in connection of its electro-conducting properties. Book of papers of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI. 2017. P.148-165. (In Russian)

38. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Application of two-component media to valuation of shungite electrical conductivity. Book of papers of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI. 2017. P.183-193. (In Russian)

39. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Application of electro-forced spectroscopy for geometrical simulation of shungite structure. Book of papers of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI. 2017. P.194-206. (In Russian)

40. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Investigation of structure properties of graphene-containing shungite by the data of x-ray spectrum analysis. Zhurnal Radio electroniki – Journal of Radio Electronics. 2017. No.4. Available at: http://jre.cplire.ru/jre/apr19/1/text.pdf (In Russian)

41. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. The application of harmonic analysis of x-ray spectroscopy data for investigation of graphene-containing shungite structure. Book of papers of XXVII International conference «Electromagnetic field and materials (fundamental physical investigations)». Moscow, NIU MEI. 2019. P.227-237. (In Russian)

42. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. The integral conductivity discrete model of graphene-containing shungite. Book of papers of XXVII International conference «Electromagnetic field and materials (fundamental physical investigations)». Moscow, NIU MEI. 2019. P.238-245. (In Russian)

43. Makeeva G.S., Golovanov O.A., Rinkevich A.B. A probabilistic model and electrodynamic analysis of the resonance interaction of electromagnetic waves with magnetic 3D nanocomposites. Journal of Communications Technology and Electronics. 2014. Vol.59. No.2. P.139-144.

44. Golovanov O.A., Makeeva G.S., Rinkevich A.B. Interaction of terahertz electromagnetic waves with periodic gratings of graphene micro- and nanoribbons. // Technical Physics. The Russian Journal of Applied Physics. 2016. Vol.61. No.2. P.274-282.

45.Makeeva G.S., Golovanov O.A. Matematicheskoye modelirovaniye elektronnoupravlyayemykh ustroystv teragertsovogo diapazona na osnove grafena i uglerodnykh nanotrubok [Mathematical simulation of electron-guided designs of thera-cycle frequency range on the basis of graphene and carbon nano-tubes]. Penza. Penza State University. 2018. (In Russian)

46. Goldstein D., Jakovits H. Prakticheskaya rastrovaya elektronnaya mikroskopiya [Practical Scanning Electron Microscopy]. Moscow, Nauka Publ. 1978. (In Russian)

47. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Investigation of electrical and structural properties of shungite based on the conductivity cards analysis. Book of papers of XXVI International conference «Electromagnetic field and materials (fundamental physical investigations)». Moscow, NIU MEI. 2018. P.293-302. (In Russian)

48. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Investigation of structure and electrical properties of graphene-containing shungite by data of electro-force spectroscopy. Part 1. Concentration of carbon. Zhurnal Radio electroniki – Journal of Radio Electronics. 2018. No.8. Available at: http://jre.cplire.ru/jre/aug18/5/text.pdf (In Russian)

49. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Investigation of structure and electrical properties of graphene-containing shungite by data of electro-force spectroscopy. Part 2. Discretization of structure. Zhurnal Radio electroniki – Journal of Radio Electronics. 2018. ¹8. Available at: http://jre.cplire.ru/jre/aug18/6/text.pdf (In Russian)

50. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Investigation of structure and electrical properties of graphene-containing shungite by data of electro-force spectroscopy. Part 3. Integral conductivity. Zhurnal Radio electroniki – Journal of Radio Electronics. 2018. No.8. Available at: http://jre.cplire.ru/jre/sep18/1/text.pdf (In Russian)

51. Gonorovsky I.S. Radiotekhnicheskiye tsepi i signaly [Radio engineering circuits and signals]. Moscow, Radio i Svyaz’ Publ. 1986 (In Russian)

52. Harmuth H.F. Sequency Theory. Foundations and Applications. N.Y.: Ac. Press. 1977.

53. Suzev V.V. Osnovy teorii tsifrovoy obrabotki signalov [Foundations of numerical signal processing]. Moscow, RTSoft Publ. 2014 (In Russian)

For citation:

Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I.   Investigation of structure and electrical properties of graphene-containing shungite by data of electric force microscopy with the sequence analysis employment. Zhurnal Radioelektroniki – Journal of Radio Electronics. 2020. No. 1. Available at http://jre.cplire.ru/jre/jan20/9/text.pdf. DOI  10.30898/1684-1719.2020.1.9