The different melting temperatures of N-methyl morpholine N-oxide (NMMO) hydrates in the cellulos-NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose-NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60-70degreesC, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose-NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8degreesC (n = 0.83), 70.2degreesC (n = 0.97), and 69.7degreesC (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose-NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose-NMMO products of granules or slurry obtained by high-speed mixing, which is a new preparation method, they still retained the original cellulose I structure. (C) 2004 Wiley Periodicals, Inc.