Macroscopic observation of thermal behavior of concentrated solution of coal extracts

The solvent extracts of Upper Freeport and Illinois No.6 coals were mixed with N-methyl-2-pyrolidinon (NMP) and annealed at 353 K to produce the gelatinous materials. Differential scanning calorimetric measurements revealed that the materials can hold significant amounts of nonfreezable NMP (as much as 3 g NMP per 1 g coal extracts) which disperse in the materials on a molecular scale, indicating the materials are not phase separated. The thermal behaviors were measured macroscopically as a function of the extract concentration using a needle penetrometer during heating from 223 to 360 K. The penetration–temperature curves were analyzed to estimate the apparent viscosity (ηa). During the penetrations, ηa was decreased very rapidly, approximately four orders of the magnitude by a temperature increase of 20 K, suggesting that the coal extracts-NMP mixtures undergoes a gel to sol transition. The heats of dissociation of crosslinks (ΔHm) were estimated by applying Eldridge–Ferry equation. The ΔHm of coal extracts-NMP mixtures was relatively small, i.e. approximately 10 kJ/mol, whereas the ΔHm of polyvinyl alcohol-NMP gel in which the hydrogen bonds contribute the formation of the physical network structures, was about 65 kJ/mol. Not the specific interaction such as hydrogen bonds, but weak interactions such as van der Waals force were likely to contribute the formation of the coal extracts-NMP gel.