of non-ohmic contacts in the composite, which was demonstrated for composites modified by MWCNTs with AR values ranging from 36 to 3000. Therefore, the MWCNT percolation threshold largely depends on measurement conditions and on the sample's "history". We demonstrated that cyclic I–V measurements can be used to characterize the nature of the contacts between the nanotubes in polymer composites, in particular, to determine the presence of non-ohmic and ohmic contacts, transformations of the former into the latter, and to control the conductivity of MWCNT based composites using electric fields with a strength higher than 1 V/mm.
The suggested method for activation of isolated contacts between nanotubes can be used for controlled modification of MWCNT based composites for production of functional materials or devices on their basis (e.g. pressure sensors or deformation sensors, etc.) [1,2].
Acknowledgments. The work was carried out within the framework of the RFBR project No. 20-33-70120.
References:
[1] Moseenkov S.I., et al., Journal of Structural Chemistry. 2020. V.61. N4. P. 628–639.
[2] Moseenkov S.I., et al., eXPRESS Polymer Letters. 2019. V.13. N12. P. 1057–1070.
The electric resistivity and piezoresistive response of functional carbon nanocomposites
Hassaan A. Butt, Stepan V. Lomov, Iskander S. Akhatov, Sergey G. Abaimov
Centre for Design, Manufacturing and Materials
Skolkovo Institute of Science and Technology, Moscow, Russia
Functional nanocomposites are allowing fundamental changes to the way system and material monitoring and testing takes place, both during manufacturing as well as during composite usage lifecycle [1, 2]. One such application of these materials is the replacing of traditional sensors for deformation sensing, allowing the reduction in cost and weight of systems and potential usage has already been highlighted in fields such as the automotive, aerospace, renewable energy and sensor manufacturing sectors [3, 4].
In recent years, nano-carbon particles, in particular, carbon nanotubes and graphene/derivatives, have been under intense scientific scrutiny as additives for composite manufacturing, not only increasing the mechanical properties of composites but allowing the final composites to be electrically conductive and piezoresistive in nature [5, 6].
In this work, industrial masterbatches have been used to manufacture functional nanocomposites and evaluate their feasibility for large scale production of strain sensing thermoplastic nanocomposites. Masterbatches are high weight/volume fraction compounds premixed with nanoadditives in a selected matrix and provide a safe medium for implementing nanomaterials on an industrial scale. From a safety, production line modification and financial standpoint, masterbatches are the most feasible implementation medium for large scale production. However, very few publications deal masterbatch-based nanocomposites and of those available, even fewer deal with piezoresistivity or self-diagnostics.
Six types of carbon nanoparticle masterbatches were employed during this study, each type containing either single-wall carbon nanotubes (SWCNT), multi-wall carbon nanotubes (02 types, MWCNT), graphene (G), reduced graphene oxide (RGO) or nitrogen doped graphene (NDG). These particles were added to an epoxy matrix at three weight percentages of interest, 0.5 %, 1.0 % and 2 %. The electrical and piezoresistive properties of the formulated nanocomposites were studied, with higher weight fractions yielding higher electrical conductivities whereas the same yielded lower piezoresistive response. Carbon nanotube (CNT) based nanocomposites outperformed graphene/derivative nanocomposites in terms of electrical conductance, showing resistivities between 2 – 106 Ohm∙cm as compared to G/RGO/NDG samples, with values between 1011-1012 Ohm∙cm. CNT based nanocomposites showed strain based gauge factors between ~2–7, while graphene/derivative nanocomposites showed extremely high resistivities infeasible for piezoresistive monitoring at the studied weight percentages. A clear relationship between the attained electrical conductance of CNT nanocomposites and their strain sensing ability (gauge factor) has also been established, with the dependency following a semi-logarithmic system; GF=A*log(R0)+B.
References
1. Lee, J. and B.L. Wardle. Nanoengineered In Situ Cure Status Monitoring Technique Based on Carbon Nanotube Network. in AIAA Scitech 2019 Forum. 2019. San Diego, California.
2. Cao X., et al., Strain sensing behaviors of epoxy nanocomposites with carbon nanotubes under cyclic deformation. Polymer, 2017. 112: p. 1–9.
3. Kumar A., K. Sharma, and A.R. Dixit, Carbon nanotube- and graphene-reinforced multiphase polymeric composites: review on their properties and applications. Journal of Materials Science, 2019. 55(7): p. 2682–2724.
4. Camilli L. and Passacantando M., Advances on sensors based on carbon nanotubes. Chemosensors, 2018. 6(4): p. 62–80.
5. Atif R., I. Shyha, and F. Inam, Mechanical, thermal, and electrical properties of graphene-epoxy nanocomposites-A Review. Polymers, 2016. 8(8): p. 281–317.
6. Caradonna A., et al., Electrical and thermal conductivity of epoxy-carbon filler composites processed by calendaring. Materials (Basel), 2019. 12(9): p. 1–17.
Anisotropic electrical conductivity in graphene films with vertically aligned single-walled carbon nanotubes: new advances in mechanisms and applications
Glukhova O.E.1,2, Slepchenkov M.M. 1
1 – Saratov State University, Saratov, Russia
2 – I.M. Sechenov First Moscow State Medical University, Moscow, Russia
In this paper, we suggest an idea of a new approach to control the electrical conductivity and its anisotropy in graphene-nanotube films with vertically oriented single-walled carbon nanotubes (SWCNTs) seamlessly connected to graphene. The basis of this approach is the phenomenon of aromaticity occurred in the hexagons of armchair-type SWCNTs at a certain nanotube length, which induces the oscillations of electronic characteristics with increasing the SWCNT length [1]. The proposed idea was tested on the example of two graphene nanomesh (GNM) atomistic models with nanoholes for SWCNTs with the chirality (6,6) and (9,9) in the case of sequentially increasing the SWCNT length. These types of SWCNTs were revealed using original approach called “virtual growing”, which shown that among the armchair SWCNTs with a diameter of 0.6–1.2 nm, the energetically favorable SWCNT- graphene junction will be formed with the SWCNTs (6,6) and (9,9). The calculations of geometric parameters of graphene-nanotube atomistic models were obtained using the self-consistent charge density functional tight-binding (SCC-DFTB) method [2]. The calculations of the electron transmission function T(E) and electrical conductivity G were carried out at 300 K using the Landauer-Buttiker formalism [3]. It was found that the nanoholes in monolayer graphene form conducting pathways in one direction, inducing anisotropy of the conducting properties. The anisotropy of the G value reaches 5 times. The formation of SWCNTs in the nanoholes does not remove anisotropy, amplifying it up to 7 times. The value of electrical conductivity G is strongly influenced by the length of the formed nanotube. It was found that a sharp increase in the value of G occurs at a certain length of 0.615 nm, 0.984 nm, 1.353 nm, and so on with in steps of 0.369 nm. These values of the SWCNT length were determined by the number of atomic layers in the SWCNT framework that is a multiple of three. Especially noticeable jumps in electrical conductivity occur for the armchair direction of electron transport. Thus, by adjusting the SWCNT length, it is possible to enhance or weaken the anisotropy of the conductive properties of graphene-nanotube films.
Acknowledgement. This work was supported by the Ministry of Science and Higher Education of the Russian Federation, grant FSRR-2020-0004.
References:
[1] F. Buonocore, F. Trani, D. Ninno, A. Di Matteo, G. Cantele, G. Iadonisi, Nanotechnology,