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General procedure for determining cellulose nanocrystal sulfate half-ester content by conductometric titration

Beck, Stephanie, Méthot, Myriam, Bouchard, Jean
Cellulose 2015 v.22 no.1 pp. 101-116
acid hydrolysis, cellulose, crystal structure, feedstocks, instrumentation, nanocrystals, neutralization, optical properties, rheological properties, sodium hydroxide, sulfur, sulfuric acid, titration, wood pulp
Charged groups on the surface of cellulose nanocrystals (CNCs) control the colloidal stability and electrostatic and rheological properties of aqueous CNC suspensions, as well as their ability to self-assemble into liquid crystalline structures with unique optical properties. CNCs extracted from wood pulp by sulfuric acid hydrolysis typically contain 200–300 mmol/kg of anionic sulfate half-esters introduced at some of the hydroxyl sites. Two analysis methods to determine CNC surface charge are presented in the published literature: total sulfur content determination by elemental analysis and protonated sulfate half-ester group determination by conductometric titration with sodium hydroxide. The main drawbacks to elemental analysis are the expensive and complicated instrumentation and sample preparation procedures it requires. Conductometric titration is a much simpler method, but requires complete protonation of the CNC samples in order to obtain an accurate value. Unfortunately, significant discrepancies between the sulfate half-ester contents measured with the two techniques are often observed in the literature, particularly with neutralized Na-CNCs. There are specific assumptions and pitfalls inherent to both analysis methods which must be taken into account and reconciled if comparable results are to be achieved by titration and elemental analysis. In particular, sample preparation is crucial to obtaining accurate determinations of sulfate half-ester content by conductometric titration; however, methods differ widely among laboratories and are often not specified in detail, rendering published results meaningless. We have developed a rapid sample preparation protocol which allows quantitative and accurate determination of the sulfate half-ester content of CNCs from various cellulosic feedstocks (for H- and Na-CNCs, in both never-dried and redispersed dried forms) by conductometric titration, yielding results in good agreement with the total sulfur content determined by elemental analysis.