The reorganization of cellulose fibers by swelling treatments in alkali solutions results in numerous changes to fiber structure, causing changes of chemical reactivity in the fiber‐solution heterogeneous system. An important part of the change in chemical reactivity is the change of fiber accessibility because it results in exclusion of chemicals such as reagents or catalysts from the fiber. In the second of a two‐part series of papers, we examine the influence of changes in fiber accessibility and/or reactivity due to treatment in swelling solutions on the performance or behavior of substrates during and after chemical finishing treatments. Changes in fiber accessibility due to alkali treatments are visualized with fluorescence microscopy. The effect of alkali treatments on enzymatic hydrolysis and pad‐dry‐cure crosslinking treatments of cellulose substrates are discussed as representative examples to demonstrate the effects of swelling processes on fiber reactivity and accessibility. Model calculations indicate that a considerable redistribution of chemicals in substrates occurs during dry‐cure operations resulting from molecule‐specific exclusion effects. Pilling tests on lyocell knit‐fabrics show the impact of preceding alkali processes on the final physical performance of textile fabric highlighting the importance of correct selection of alkali processes to achieve desired behavior.
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