Advanced electronic magnetic resonance (EMR) as well as nuclear magnetic resonance (NMR) methods have been used to examine properties of coals, chars, and molecular species related to constituents of coal. During the span of this grant, progress was made on construction and applications to coals and chars of two high frequency EMR systems particularly appropriate for such studies -48 GHz and 95 GHz electron magnetic resonance spectrometer, on new low-frequency dynamic nuclear polarization (DNP) experiments to examine the interaction between water and the surfaces of suspended char particulates in slurries, and on a variety of proton nuclear magnetic resonance (NMR) techniques to measure characteristics of the water directly in contact with the surfaces and pore spaces of carbonaceous particulates.
EXECUTIVE SUMMARYThe main advanced magnetic resonance methods employed over the period of this project were (1) W-band (100 GHz) electronic magnetic resonance (EMR) spectroscopy to provide an analytical tool to discriminate among very similar chemical species that are constituents of coals and closely related materials such as chars, (2) construction of a U-band (50 GHz) EMR spectrometer to aid such analysis by filling the wide gap between W-band and the lower available frequencies, (3) very low frequency pulsed dynamic nuclear polarization (DNP) spectroscopy for study of the interfaces between coal-like particles and the water medium in which they are suspended, and (4) a variety of proton nuclear magnetic resonance (NMR) techniques to measure characteristics of the water in contact with particle surfaces and pore spaces.This project was carried out over a forty-two month period. Six individual project reports to the DOE described the instrumentation, techniques, theory, and typical results.1-6 Sixteen peerreviewed articles 7-22 contain details and discussions of parts of this work. These reports describe the first observations of solid-liquid electron spin density transfer, showing a transient chemical interaction between water molecules and particulate surfaces in an aqueous slurry of carbonaceous char particles by a proton pulsed Dynamic Nuclear Polarization (DNP) technique at low magnetic field. In a second study, by use of Fourier Transform PulsedField-Gradient spin-echo NMR spectroscopy several self-diffusion coefficients were obtained in aqueous char suspensions corresponding to different mobilities of water molecules in the porous structures. It was concluded that the short-range nuclear-electronic interactions in pore space have the dominant effect on DNP enhancement in char suspensions. In another study, a strong particle size influence on NMR transverse proton relaxation in aqueous suspensions of these newly synthesized chars was found.Multifrequency EMR spectroscopy can be a powerful tool in understanding details of the chemical species present in native and processed coals, coal constituents, and synthetic carbonaceous materials like chars. High frequency EMR is especially informative because of...