Macromolecular structural changes in contact metamorphosed inertinite-rich coals from the No. 2 Seam, Witbank Coalfield (South Africa): Insights from petrography, NMR and XRD

Abstract

The response of inertinite-rich Witbank coals (South Africa) to rapid heating was evaluated using petrography, selected Nuclear Magnetic Resonance (NMR) and X-Ray Diffraction (XRD) structural parameters. A total of thirteen (13) coal samples were collected from the No. 2 Seam; a set of six (6) samples from the western and the eastern sides of a ~ 0.4 m thick dolerite dyke emplaced into the coal seam at 0.25 m intervals. An unaltered coal (Un-C; the 13th sample), collected away from the dyke but within the same seam at the mine, was included for comparison. All 13 coal samples were dominated by inertinite. Semifusinite was most abundant in the samples from the western side of the dyke, whereas the proportion of inertodetrinite was highest in samples from the eastern side. Due to very low vitrinite contents, mean random total reflectance (%RoTmr) was used to compare the maturity of the inertinite-rich coals. A decrease in volatile matter was correlated with an increase in mean random total reflectance (%RoTmr; measured on semifusinite, inertodetrinite, and vitrinite), the latter used as a potential maturity indicator for the thermally altered inertinite-rich coals. Mean random total reflectance rose from a background value of 1.52%RoTmr (for Un-C) to 2.83%RoTmr for the coal sample at the western coal-dyke contact (0.0 m). The corresponding reflectance values for the thermally altered coals from the eastern side were less consistent, decreasing closest to the dyke (1.93%RoTmr for the sample at 0.0 m); this trend is also reflected in the NMR and XRD parameters. Eight (8) samples were selected for the NMR analysis, representative of the maceral composition and maturities of the coals investigated. For Un-C, the fraction of aromatic carbons (fa) was 0.88 (average number of carbons per aromatic cluster (C) = 17), and the interplanar spacing (d002) was 3.48 Å (with a crystallite height of 22.09 Å). For the thermally altered coals from the western side, fa decreased from 0.96 at the coal-dyke contact (C = 26 for sample at 0.0 m) to 0.92 for the sample at 1.25 m from the dyke (C = 20). For samples from the eastern side, fa increased from 0.91 (C = 19 for the sample at 0.25 m) to 0.93 (C = 23 for sample at 0.5 m), before decreasing to 0.89 further from the dyke (C = 18 for sample at 1.25 m). In general, the d002 values for the thermally altered coal samples were larger than for graphite. Similarly, only marginal increases in crystallite heights were observed. Although the dyke induced coal maturation and the resultant increase in fa, the overall lack of graphitic order in the thermally altered coals was ascribed to the limited thermal energy provided by the relatively thin dyke; increased heat input would be required to effect significant structural changes in the inertinite-rich coals. Differences between the two sets of thermally altered coal samples were attributed to the emplacement dynamics of the igneous intrusion, which require further investigation.