Dispersion stability and aggregation behavior of TEMPO-oxidized cellulose nanofibrils in water as a function of salt addition

• Published in: Cellulose (London) Vol. 21; no. 3; pp. 1553 - 1559
• Main Authors: Fukuzumi, Hayaka, Tanaka, Reina, Saito, Tsuguyuki, Isogai, Akira
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer-Verlag 2014; Springer Netherlands; Springer Nature B.V
• Subjects: Agglomeration; aggregation behavior; Bioorganic Chemistry; Calcium chloride; Cellulose; Ceramics; Chemistry; Chemistry and Materials Science; Composites; Dispersions; Electrolytes; Empirical analysis; energy; gels; Glass; Light transmittance; Magnesium chloride; Natural Materials; Organic Chemistry; Original Paper; Physical Chemistry; Polymer Sciences; Potential energy; salt concentration; Shear flow; sodium chloride; Stability; Sustainable Development; transmittance; viscosity; TEMPO-oxidized cellulose nanofibril; Critical aggregation concentration; Schulz–Hardy rule; DLVO theory
• ISSN: 0969-0239; 1572-882X
• DOI: 10.1007/s10570-014-0180-z

Dispersion stability of TEMPO-oxidized cellulose nanofibrils (TOCNs) in water was investigated through both experimental and theoretical analyses to elucidate the critical aggregation concentration of different salts. The 0.1 wt% TOCN/water dispersions with various NaCl concentrations were evaluated by measuring light transmittance, viscosity under steady-shear flow, and the weight fraction of TOCN that had aggregated. Homogeneous TOCN/water dispersion turned to gel as the NaCl concentration increased. The TOCN dispersion maintained its homogeneous state up to 50 mM NaCl, but aggregated gel particles were formed at 100 mM NaCl. The mixture became separated into two phases (gel and supernatant) at ≥200 mM NaCl. Theoretical analysis using ζ-potentials of TOCN elements in the dispersions revealed that the aggregation behavior upon NaCl addition could be explained well in terms of the interaction potential energy between two cylindrical rods based on the Derjaguin–Landau–Verwey–Overbeek theory. The experiments were extended to analyze critical aggregation concentrations of MgCl₂ and CaCl₂ for the 0.1 wt% TOCN dispersion. In the case of divalent electrolytes, TOCN elements began to form aggregated gel particles at salt concentrations of 2–4 mM, corresponding to the critical aggregation concentration predicted by the empirical Schultz-Hardy rule.