Insights into the assembly process and properties of regenerated cellulose beads prepared in alkali/urea aqueous solutions

Taking the perspective of cellulose molecular chain assembly via the “bottom-top” route, we delve into the influence of both the cellulose solution and the coagulation bath on the assembly process and structure of regenerated cellulose beads (RCBs). The results show that cellulose molecular weight, mass fraction, and the presence of surfactant have an impact on RCBs. Contrary to traditional views where the structures of material are determined by solvent-nonsolvent exchange rate, ion-cellulose binding capacity also affects RCBs. Overall, the influence of ions follows the Hofmeister sequence. Kosmotropes promote the assembly of cellulose chains and elementary fibers, leading to “salting out” effects, reduced pore size of RCBs, increased crystallinity, and enhanced mechanical properties. In contrast, chaotropes induce “salting in” effects, resulting in opposite outcomes. The average pore size of RCBs coagulated in NaSCN solution was approximately 15-folds larger than those prepared in sodium citrate solution. Anions have a greater impact than cations, and both “salting out” and “salting in” effects strengthen with concentration. Temperature variations primarily affect solvent and nonsolvent exchange speed during cellulose regeneration. These findings provide new insights into regulating RCBs, enabling tailored performance for different applications.