The effect of liquid ammonia on cotton fabric was studied using x‐ray diffraction (XRD) and electron microscopy. A phase diagram is presented describing the relationship between disordered cellulose, cellulose I, and cellulose III. The transition from cellulose I to III proceeds through the liquid ammonia. Cellulose III is obtained upon drying the ammonia‐cellulose without the presence of water. Treatment of the cellulose III or of the ammonia‐cellulose with water brings about the formation of cellulose I. The degree of crystalline order achieved in water is enhanced by heating, which is consistent with a glass transition temperature between room temperature and 100°C. The cellulose III crystallites obtained are much smaller than those of cellulose I,16‐23Åas against 50‐80Å
The interaction of ammonia with cotton cellulose is faster than with other swelling agents, such as ethylamine. The penetration of ammonia into the secondary wall of the cotton fiber is not only along the concentrical rings, as is the case with water, but also radially across the rings.
Prolonged soaking in water increases the crystallite size with simultaneous rejection of swelling water.