The structure of the plastic layer in coals of different caking capacity was studied using the X-ray method and the influence of the plastic layer structure on the mechanism of coke formation was determined. It is shown that the transportation of the plastic mass in the gas-saturated zone of the plastic layer has a decisive influence on the decrease in volume of the coal charge and on obtaining a denser residue during carbonization. When heating poorly caking and non-caking coals an increase in the charge volume takes place. Using the quantitative X-ray phase analysis an ordered phase amount (C(cryst)) was found in solid residues of carbonization and the parameters d(002). L(c) and L(a) were determined. It is shown that the gas-saturated zone is generated in the plastic layer only when structural transformations in coals take place at the pre-plastic stage without changing the ratio between the number of carbon atoms in the ordered and non-ordered phases. The transition of well caking coal into the plastic state is accompanied by the activation of segmental and conformal movement of side chains and separate macromolecular fragments of the coal organic mass. In the course of grain swelling of non-caking coal its crystallites degrade. The conclusions drawn on the basis of X-ray studies were confirmed by the EPR-spectroscopy of residues corresponding to plastic zones in coals of different caking capacity. (C) 2004 Elsevier Ltd. All rights reserved.