Influence of molecular weight and rheological behavior on electrospinning cellulose nanofibers from ionic liquids

Dissolving pulp was depolymerized with 2.5M HCl into cellulose fractions with decreasing molecular weight relative to acid treatment time. The cellulose fractions were dissolved at various concentrations in the ionic liquid 1-ethyl-3-methylimidazolium acetate (EmimAc) with co-solvent DMSO at ratio 1 : 1 (w/w) and electrospun. Size exclusion chromatography was used to evaluate the molecular weight distributions and the rheological properties were characterized with a cone-and-plate rheometer. Scanning electron microscope was used to evaluate the fiber morphology, and thereby spinnability. Zero shear viscosity as a function of cellulose concentration show that all the solutions in this study are in the entangled semi-dilute regime; where the polymer concentration is large enough for significant overlap necessary for chain entanglement. However, within the intervals studied, neither cellulose concentration nor molecular weight seems to be decisive for if a solution can be electrospun into fibers or not. It is rather the viscosity of the solution that is decisive for electrospinnability, even though the solution is in the entangled semi-dilute regime.

[1]  W. Graessley,et al.  Effects of polydispersity on linear viscoelasticity in entangled polymer melts , 1992 .

[2]  D. Klemm,et al.  Cellulose: fascinating biopolymer and sustainable raw material. , 2005, Angewandte Chemie.

[3]  W. Graessley Viscosity of Entangling Polydisperse Polymers , 1967 .

[4]  R. Colby Structure and linear viscoelasticity of flexible polymer solutions: comparison of polyelectrolyte and neutral polymer solutions , 2010 .

[5]  F. Morehead,et al.  Level-Off Degree of Polymerization , 1956 .

[6]  Timothy E. Long,et al.  Correlations of solution rheology with electrospun fiber formation of linear and branched polyesters , 2004 .

[7]  Paul Gatenholm,et al.  Electrospinning of cellulose nanofibers from ionic liquids: The effect of different cosolvents , 2012 .

[8]  Rute A. S. Ferreira,et al.  Electrospun nanosized cellulose fibers using ionic liquids at room temperature , 2011 .

[9]  Y. Y. Lee,et al.  Heterogeneous aspects of acid hydrolysis of α-cellulose , 2003 .

[10]  Gary E. Wnek,et al.  Role of chain entanglements on fiber formation during electrospinning of polymer solutions: Good solvent, non-specific polymer-polymer interaction limit , 2005 .

[11]  Yung-Ho Chang,et al.  Degradation of cotton cellulose treated with hydrochloric acid either in water or in ethanol , 2009 .

[12]  In-Joo Chin,et al.  Characterization of cellulose fibers electrospun using ionic liquid , 2010 .

[13]  Huaping Wang,et al.  Rheology of Concentrated Cellulose Solutions in 1-Butyl-3-methylimidazolium Chloride , 2009 .

[14]  A. Isogai,et al.  Degrees of polymerization (DP) and DP distribution of dilute acid-hydrolyzed products of alkali-treated native and regenerated celluloses , 2008 .

[15]  Shanshan Xu,et al.  Electrospinning of native cellulose from nonvolatile solvent system , 2008 .

[16]  Zhi-Gang Wang,et al.  Celluloses in an ionic liquid: the rheological properties of the solutions spanning the dilute and semidilute regimes. , 2008, The journal of physical chemistry. B.

[17]  T. Budtova,et al.  Rheological properties of cellulose/ionic liquid solutions: from dilute to concentrated states. , 2009, Biomacromolecules.

[18]  W. Cox,et al.  Correlation of dynamic and steady flow viscosities , 1958 .

[19]  A. C. O'sullivan Cellulose: the structure slowly unravels , 1997, Cellulose.

[20]  T. Budtova,et al.  Viscosity of cellulose-imidazolium-based ionic liquid solutions. , 2010, The journal of physical chemistry. B.

[21]  Christoph Michels,et al.  Dissolution and forming of cellulose with ionic liquids , 2008 .

[22]  Eric Uerdingen,et al.  New Developments in Dissolving and Processing of Cellulose in Ionic Liquids , 2008 .

[23]  Sang Hyun Lee,et al.  Effect of co-solvent on the spinnability and properties of electrospun cellulose nanofiber. , 2012, Carbohydrate polymers.

[24]  Robin D. Rogers,et al.  Dissolution of Cellose with Ionic Liquids , 2002 .

[25]  G. McKinley,et al.  Shear and extensional rheology of cellulose/ionic liquid solutions. , 2012, Biomacromolecules.

[26]  P. Ajayan,et al.  Preparation of biopolymer fibers by electrospinning from room temperature ionic liquids. , 2006, Biomacromolecules.