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Thermal Oxidation Kinetics of Graphene-Micro Powders in Oxygen Flow

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Powder Metallurgy and Metal Ceramics Aims and scope

The oxidizing properties of graphene-micro powders in a purified oxygen flow were measured (vO2 = 5.21 ⋅ 10–4 mole ⋅ sec–1 = const). The graphene powders were certified by the manufacturer (Center for Advanced 2D Materials, Innovation Development Laboratories, National University of Singapore). The following methods were used to test the powders: fractionated sequential oxidation over time at set temperature maxima of the CO2 release rate and gradual heating, like that provided by DTA, at a rate of ~20 K/min. The amount of extracted carbon as CO2 was recorded every minute. The repeated sequence of fractionated temperature oxidation of parallel graphene samples determined the characteristic decomposition (oxidation) of three fractions at temperatures of 953, 1003, and 1043 ± 10 K. The oxidation results showed that the graphene powders were satisfactorily homogeneous, and their oxidation proceeded in the same way as in stacked, conical, and tubular carbon nanofibers at 923, 973, and 1013 ± 10 K. Three similar morphological components of graphene microparticles were visually identified in scanning electron microscopy images as planar, conical, and tubular. The average sizes of graphene microparticles were three orders of magnitude greater than the average diameters of the same fibrous nanoforms. The oxidation mechanism for carbon nanoforms and microforms in air has two states. The first stage involves peripheral oxidation of graphene particles (wait state): absorption of oxygen molecules by the surface of 2D graphene (≥234 K), migration to the edge (perimeter) carbon atoms, recombination of oxygen molecules with perimeter carbon, and saturation of broken carbon bonds with bridged oxygen (2–) bonds. The second stage (thermokinetic state) includes CO cleavage in heating and oxidation of CO to CO2 (oxidation, decay, combustion). The wait state is maintained by the thermokinetic process. The sizes of microparticles and the specific concentration of edge perimeter pairs of carbon and oxygen atoms on the periphery of graphene platelets influence the oxidation rate and oxidation temperature of powder fractions. The shift of oxidation temperatures for morphological graphene forms in comparison with fibrous nanoforms is +(30–50 K) on average. The procedure for purification of graphene powders promotes the transition of the most active planar particles into coiled forms. The kinetic temperature dependence for the oxidation of purified graphene represents a stepped S-shaped curve with saturation. The initial rates of carbon oxidation, voxC = 4.57 × × 10–8 mole ⋅ sec–1, were recorded at 823 K. In entry into the exponential range of measurements (873–983 K), the oxidation reaction rates voxC of the graphene micropowder increase from 9.99 × × 10–8 to 1.5 ⋅ 10–6 mole ⋅ sec–1 and the oxidation reaction rate constants koxC from 1.91 ⋅ 10–4 to 1.51 ⋅ 10–3. The activation characteristics are Ea.oxC = 168 ± 10 kJ ⋅ mole–1 and frequency characteristics are A0 = 6.06 ⋅ 105 to 7.40 · 106 sec–1. The oxidation rate varied from 1.92 ⋅ 10–6 to 1.06 ⋅ 10–6 mole ⋅ sec–1 after the inflection point at 983 K and up to 1073 K and from 8.89 ⋅ 10–7 to 3.30 · 10–8 mole · sec–1 at 1093 K. Subsequently, up to 1123 K, the carbon oxidation rate became zero when the sample burned completely. The known theoretically calculated activation energy of graphite oxidation is 172 kJ · mole–1. The experimental results are within the theoretical values. Preliminary measurements for multiwalled nanotubes and intragranular inclusions of graphite and free nanosized carbon (onions, graphite platelets, conical fibers, and tubes) of commercial B15–xCx boron carbide powders are close to the above data.

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Notes

  1. The example shown in the figure additionally indicates the need to apply v(Т/хв)–up-stop-up temperature rise programs for the development of DTA (DTG) methods. This is required for sets of close-temperature endothermic and exothermic effects of reactions that proceed over time. This will help to deal with the superposition and allow an actual analysis of thin thermal properties of samples with time. The approximate methods such as decomposition into Gaussian components and Kissinger thermokinetic calculations will thus become irrelevant.

  2. Note that the oxidation curves (Fig. 1a–c) show low-intensity peaks Tox = 923, 973, and 1013 K. The micropowder probalbly contains also a submicron fraction of the morphological graphnene forms found.

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Authors and Affiliations

  1. Frantsevich Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kyiv, Ukraine

    V.V. Garbuz, V.A. Petrova, T.A. Silinskaya, L.N. Kuzmenko & T.M. Terentyeva

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  1. V.V. Garbuz
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Translated from Poroshkova Metallurgiya, Vol. 60, Nos. 5–6 (539), pp. 42–50, 2021.

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Garbuz, V., Petrova, V., Silinskaya, T. et al. Thermal Oxidation Kinetics of Graphene-Micro Powders in Oxygen Flow. Powder Metall Met Ceram 60, 291–297 (2021). https://doi.org/10.1007/s11106-021-00239-9

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