AbstractThe low temperature surface and bulk nitration of cellulose has been investigated by electron spectroscopy for chemical analysis (ESCA),13C‐NMR and X‐ray diffraction. Acid mix composition has been probed at room temperature and at low temperatures (0–20°C) by Raman spectroscopy. This multitechnique approach has been employed to elucidate the behavior of surface degree of substitution (DOS) with acid mix composition over a 40°C temperature range. The data obtained have prompted a reinterpretation of previously reported work. Surface “equilibrium DOS” is shown to be established within 1 s at all temperatures investigated. but, at lower temperatures (>5°C) the surface DOS as monitored by ESCA is observed to “dip” after immersion times oft<5 s. This change in DOS is correlated with major structural changes in the fiber as observed by SEM. At low temperatures, e.g., −15°C, nitration is shown to be complete throughout the cellulose fiber after 10 h nitration. Solution state13C‐NMR is used to compare the nitrate ester substitution distribution in cellulose nitrates prepared from acid mixes of the same composition at d
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