The role of shear strain in the graphitization of a high-volatile bituminous and an anthracitic coal

Abstract

A ‘soft’ carbon-based high-volatile bituminous ( R o max=0.68%) coal and a ‘hard’ carbon-based Pennsylvania anthracite ( R o max=5.27%) were deformed in the steady state at high temperatures and pressures in a series of coaxial and simple shear deformation experiments designed to constrain the role of shear strain and strain energy in the graphitization process. Tests were carried out in a Griggs-t type solid (NaCl) medium apparatus at T=400–900°C, constant displacement rates of 10 -5−10 -6 s −1, at confining pressures of 0.6 GPa (coaxial) or 0.8 and 1.0 GPa (simple shear). Coaxial samples were shortened up to 50%, whereas shear strains up to 4.9 were attained in simple shear tests. Experiments lasted up to 118 h. Deformed, high-volatile bituminous coal was extensively coked and no correlation between strain and R o max, bireflectance or coal texture was observed in any samples. With increasing temperature, R o max and bireflectance increase in highly anisotropic, coarse mosaic units, but remain essentially constant in the fine granular mosaic, which becomes more abundant at higher temperatures. Graphite-like reflectances are observed locally only in highly reactive macerals and in pyrolytic carbon veins. The degree of molecular ordering attained in deformed bituminous coal samples appears to be determined by the heating-pressurization path rather than by subsequent deformation. Graphitization did not occur in coaxially deformed anthracite. Nonetheless, dramatic molecular ordering occurs at T>700°C, with average bireflectance values increasing from 1.68% at 700°C to 6.36% at 900°C. Anisotropy is greatest in zones of high strain at all temperatures. In anthracite samples deformed in simple shear over the 600–900°C range at 1.0 GPa, the average R o max values increase up to 11.9%, whereas average bireflectance values increase up to 10.7%. Bireflectance increases with progressive bedding rotation and, thus, with increasing shear strain. Graphitization occurs in several anthracite samples deformed in simple shear at 900°C. X-ray diffraction and transmission electron microscopy of highly anisotropic material in one sample confirms the presence of graphite with d 002=0.3363 nm. These data strongly suggest that shear strain, through its tendency to align basic structural units, is the factor responsible for the natural transformation of anthracite to graphite at temperatures far below the 2200°C required in hydrostatic heating experiments at ambient pressure.