"JOURNAL OF RADIO ELECTRONICS" (Zhurnal Radioelektroniki ISSN 1684-1719, N 8, 2018

contents of issue      DOI  10.30898/1684-1719.2018.8.5     full text in Russian (pdf)  

Investigation of structure and electrical properties of graphene-containing shungite by data of electro-force spectroscopy.

Part 1. Concentration of carbon


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

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

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

3 Kotel’nikov Institute of Radio Engineering and Electronics of RAS, Mokhovaya 11-7, Moscow 125009, Russia


The paper is received on July 29, 2018


Abstract. The investigation of structure properties of natural graphene-containing material shungite is performed. The specimens for investigation were found from deposits from Karelia and Onega-region in Russia (Shunga, Zazjogino, Maksovo, Chebolaksha). The central object of investigations was the volume concentration of conducting carbon which is separated by nonconducting quarts seams. In the most important method of carbon concentration determination it was choose the nondestructive electric-force spectroscopy method. As a control it was choose the express-analysis method which is consist in chemical analysis of weight concentration of carbon in the gases which are received by shungite burning in tube stove. In the reason of physical sense the result of express-analysis is the weight carbon concentration in burned specimen. But the electro-force spectroscopy method is able to found only surface properties of material. With the purpose of possibility to comparison of results founded by both methods it was proposed the method of recalculation of weight concentration to volume concentration. In the basis of recalculation it was made the supposition about volume equality of volume carbon atom and volume quarts components – atoms of silicon and oxygen. It is discussed the correctness of this supposition. It is noted that its acceptance bring to perfectly plausible results which are harmony with experiments. The investigated specimens were made by the mechanical cutting of plates from volume shungite pieces having length to several centimeters which are found from different deposits with following grinding and polishing of made flat surface. It was investigated in all 32 specimens having weight carbon concentration (determined by express-analysis method) from 3 to 96 per cent. The analysis of specimen properties was made by atom-force microscope. The electric properties of specimen were found by measuring of spreading of electric current between the cantilever point edge and specimen surface. The typical dimension of investigated regions of specimen was 20 to 20 micrometers. On the some specimens the measuring were made in smaller ground right until 3 to 3 micrometers. The space precision of microscope was 0,03 micrometers. The results of measuring were two-color conductivity maps which was the near to chaotic alternation of white and black regions. In this case the white regions corresponds to conducting carbon and black regions corresponds to nonconducting quarts. For the describe of founded conductivity maps it was discussed two before proposed models of shungite structure – “cubes with percolation” and “sand with liquid”. It is discussed the peculiarities of both models which found its points in conductivity maps. For more detailed investigation of carbon space structure distribution the maps were subjected to binomial processing. For this case on the map was putted the square net consist of square cells having dimension 20 to 20 cells. After this procedure the so cells which black region was more the half of cell area were painted to black color and cells which black region was less the half of cell area were painted to white color. The received by the same manner binomial maps having 400 cells were subjected to statistic processing. For this case the total area occupied by cells of white or black color is calculated. The results of this calculation is the space characteristic of carbon distribution over the specimen area. It was found that these calculated values of white and black areas have large scattering which value is so large as some times. For the founding of total statistic law it was proposed two system of specimen grouping – by the value of whole white or black cells areas on the conductivity maps and by the value of volume carbon concentration which was received by express-analysis method. It was shown that the first method can give some unity of samples by the regions of conductivity maps but the concentration scattering is not removed. The second method gives some increasing of scattering by the size of regions on conductivity maps but good co-ordinate specimens by carbon concentration. By this reason in the general investigation method was choose the second method which make possibility of breaking whole specimens quantity to nine groups divided by carbon concentration more or less steady in the interval from 5 to 97 per-cents. For the founding of correction of binomial statistical analysis there was made the investigation of net steps influence to distribution of cells so and other colors. It was shown that the net steps influence is in large degree for this phase which concentration is less then other phase concentration. In the other cases it may be think that the results of conductivity maps breaking from the net steps are depended not more then some per-cents. In the these work frame it was recognized the optimal net consist of 20 to 20 cells on so and other coordinates. In the result the whole net contains 400 cells. It was measured the parameters of received field which is the quantity of white and black cells over the each individual specimen. In agreement with established specimens grouping it was made the statistical processing of received results with calculation of arithmetical average and quadratic deviation. It was shown that when the carbon concentration is increased the quantity of white cells is increased and black decreased. This tendency describes the relative area of appropriate phases. So it is shown that also by equal carbon concentration the structure parameters of conductivity maps has large difference which is reaches several times but this difference is decreased when the concentration is increased. In the possible reason of this large difference is established the nearly to chaotic character of space distribution of carbon and quarts parts of shungite which is determined by its natural origin. It was investigated the quantity of white cells in bicolor conductivity maps fields over the groups from the volume carbon concentration. By way of approach to received results it was proposed the empiric formula as a quadratic polynomial which was calculated by the least quadratic method. With the data of concentration and fields areas it was constructed the equation system which was resolved with the help of office program «Excel» through the construction of reverse matrix. This system solution took place the numerical coefficients of unknown quadratic polynomial. By the graphic construction of this polynomial it was shown that its is very nearly to straight line which describes the linear connection between the carbon concentration and white cells quantity. It is found that this approximate dependence is slightly exceed abovementioned straight line and convexity in top to the side of more concentration. In the possible reason of this difference it is made the proposition about not whole confidence of correction degree of recount of weight concentration to volume also by the reason exceeding of silicon atoms volume above carbon and oxygen atoms volume. The graphic construction of this dependence for black cells made the same curve but have convexity to bottom in the comparison of straight line which is correspond to linear connection between carbon concentration and cells quantity. It was shown that the summa both these curves is equal to whole quantity of cells in field which is equal to 400 units. For the purpose of surface distribution comparison between white and black cells over the field area it was made the recalculation of surface concentration into volume. In suppose of structure unification in the surface and volume of specimen it was shown that for recalculation of surface carbon concentration into volume carbon concentration the surface concentration value must be raised to the power of 3/2. It was made the comparison of carbon concentrations which was received by two methods: by the conductivity maps and by express-analysis method. It was shown that electro-force spectroscopy method in comparison with express-analysis method gives the values of concentration which are enough near but slightly decreased about the value of 11%. On the basis of graphic interpretation by the least quadratic method it is found the empirical dependence of distinction between the results which were received both methods from volume carbon concentration. It is shown that the approximate function is near to straight line which is arranged slightly lower then zero level which is correspond to equality both concentrations. By the volume concentration increases the distinction  between both values received by both methods is decreased. It is shown that when the concentrations are near zero the methods distinction is about 12% and when the concentration appropriate to 100% the distinction decreases to 2-3%. It is shown that the high proximity of both method results allows to regard electro-force spectroscopy method as the suitable instrument for carbon concentration determination in shungite without the destruction of specimen. It was proposed the analytical dependence which made be able to calculate carbon concentration from electro-force spectroscopy method. It is proposed some practical recommendations about using of this method. As a significant demand for the works development it is established the necessity of further investigations of shungite deposits in expedition conditions. 

Key words: carbon, shungite, electro-conductivity.


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. (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.

3. 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.

4. Linkov L.M., Makhmud M.Sh., Kryshtopova E.A. Ekrani elektromagnitnogo izluchenia na osnove poroshkoobraznogo shungite. [The electromagnetic radiation screens on basis of powder-like shungite].  Bulletin of Polotsk State university. Series C. Main sciences. Novopolotsk: PSU. 2012. No.4. P.103. (In Russian). 

5. Philippov M.M. Shungiteonosnie porodi onegskoi structure. [Shungite-containing rocks of Onega structure]. Petrozavodsk, Karelian SC RAS. 2002.  (In Russian)

6. Sokolov V.A., Kalinin Yu.K., Dukkiev E.F. (egitor). Shungity – novoe uglerodistoe syrye [Shungites – new carbon raw material]. Petrozavodsk, Karelia Publ., 1984. 

7. 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.

8. 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. (In Russian).

9. 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.

10. Makeeva G.S., Golovanov O.A. Mathematical modeling of electronics-controlled theracycle-microwave devices based on grapheme and carbon nano-tubes. Penza. Published by PSU. 2018.

11. Mironov V.L. The foundations of scan-probe-microscopy. Technosfera. 2005. 

12. Banerjee S., Sardar M., Gayathri N., Tyagi A.K., Baldev Raj. Enhanced conductivity in grapheme layers and at their edges.  APL. 2006. Vol.88. No.6. P.062111.

13. Golubev E.A. Electro-physical properties and structure peculiarities of shungite (natural nano-structured carbon).  Physics of Solid State. 2013. Vol.55. No.5. P.1078-1086.   https://doi.org/10.1134/S1063783413050107

14. Shumilova T.G., Golubev Ye.A., Mayer J., Shevchuk S.S., Radaev V.A., Isaenko S.I., Tkachev S.N.  Carbon. 2017. Vol.114. P.724.  

15. Pavlov L.P. Metody izmereniya parametrov poluprovodnikovykh materialov [Measurement methods of semiconductor materials parameters]. Moscow, Vysshaya Shkola Publ., 1987 (In Russian)

16. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Dynamic microwave conductivity of graphene-based shungite.  Technical Physics Letters. 2018. V.44. ¹5. P.371. 

17. 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).

18. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. The investigation of conductivity of graphene-contained shungite by wave-guide method.  Transactions of International symposium «Perspective materials and technologies». Vitebsk. Belarus. 2017. P.6. (In Russian).

19. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I. Dynamical conductivity of graphen-contained shungite in microwave region.  Transactions of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI Publ.,  2017. P.135.

20. 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.  Transactions of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI Publ.,  2017. P.148.

21. 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.  Transactions of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI Publ., 2017. P.166.

22. Antonets I.V., Golubev E.A., Shavrov V.G., Shcheglov V.I.  Application of two-component media to valuation of shungite electrical conductivity.  Transactions of XXV International conference «Electromagnetic field and materials». Moscow, NIU MEI Publ., 2017. P.183.

23. Vorobyeva L.F. Teoriya I praktika khimicheskogo analiza pochv [Theory and practice of soil chemical analysis]. Moscow, GEOS Publ.,  2006. (In Russian)

24. Glinka N.L. Obshchaya khimiya [General chemistry]. Leningrad, Khimiya Publ., 1976. (In Russian)

25. 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. No.5. Available at: http://jre.cplire.ru/jre/may17/11/text.pdf (In Russian).

26. Golubev E.A., Antonets I.V., Shcheglov V.I.  Model’nye predstavleniya mikrostruktury, elektroprovodyaschikh I microwave properties of shungite [Model presentation of micro-structure, electro-conducting and microwave properties of shungite]. Syktyvkar, Syktyvkar State University (SyktSU). 2017. (In Russian)

27. Venttsel E.S. Teoriya veroyatnostei [Theory of probability]. Moscow, Nauka. 1964. (In Russian)

28. Demidovich B.P., Maron I.A., Shuvalova E. Z. Chislennye metody analiza [Numerical methods of analysis]. Moscow, Fizmatgiz Publ., 1963. (In Russian)


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

DOI  10.30898/1684-1719.2018.8.5