Tatiana Budtova

Rheological Properties of Cellulose/Ionic Liquid Solutions: From Dilute to Concentrated States

Steady state shear flow of different types of cellulose (microcrystalline, spruce sulfite and bacterial) dissolved in 1-ethyl-3-methylimidazolium acetate was studied in a large range of concentrations (0-15%) and temperatures (0-100 degrees C). Newtonian flow was recorded for all experimental conditions; these viscosity values were used for detailed viscosity-concentration and viscosity-temperature analysis. The exponent in the viscosity-concentration power law was found to be around 4 for temperatures from 0 to 40 degrees C, which is comparable with cellulose dissolved in other solvents, and around 2.5-3 for 60-100 degrees C. Intrinsic viscosities of all celluloses decreased with temperature, indicating a drop in solvent thermodynamic quality with heating. The data obtained can be reduced to a master plot of viscosity versus (concentration x intrinsic viscosity) for all celluloses studied in the whole temperature range. Mark-Houwink exponents were determined: they were lower than that for cellulose dissolved in LiCl/N,N-dimethylacetamide at 30 degrees C and close to theta-value. Viscosity-inverse temperature plots showed a concave shape that is dictated by solvent temperature dependence. The values of the activation energies calculated within Arrhenius approximation are in-line with those obtained for cellulose of comparable molecular weights in other solvents.

Viscosity of cellulose-imidazolium-based ionic liquid solutions.

The viscosities of microcrystalline cellulose dissolved in 1-ethyl-3-methylimidazolium acetate (EMIMAc) and in 1-butyl-3-methylimidazolium chloride (BMIMCl) were studied in detail as a function of polymer concentration and temperature. The goal was to compare the flow of solutions, macromolecule hydrodynamic properties in each solvent, and the activation energies of viscous flow. Intrinsic viscosities were determined using the truncated form of the general Huggins equation. In both solvents cellulose intrinsic viscosity decreases with increasing temperature, indicating the decrease of solvent thermodynamic quality. The activation energies for both types of cellulose solutions were calculated. For cellulose-EMIMAc the Arrhenius plot showed a concave shape, and thus the Vogel-Tamman-Fulcher (VTF) approach was used. We suggest an improved method of data analysis for the determination of VTF constants and demonstrate that cellulose-EMIMAc solution viscosity obeys VTF formalism. Once the dependences of Arrhenius activation energy and VTF pseudo-activation energy were obtained for the whole range of concentrations studied, they were all shown to be described by a simple power-law function of polymer concentration.

Macroscopic and microscopic study of 1-ethyl-3-methyl-imidazolium acetate-water mixtures.

Mixtures of 1-ethyl-3-methyl-imidazolium acetate ([C2mim][OAc]) and water across the entire composition range, from pure [C2mim][OAc] to pure water, have been investigated using density, viscosity, and NMR spectroscopy, relaxometry, and diffusion measurements. These results have been compared to ideal mixing laws for the microscopic data obtained from the NMR results and macroscopic data through the viscosity and density. It was also found that the mixing of the two fluids is exothermal. The proton spectra indicate though that [C2mim][OAc] and water are interacting without the formation of new compounds. The maximal deviations of experimental data from theoretical mixing rules were all found to occur within the range 0.74 ± 0.06 mol fraction of water, corresponding to approximately three water molecules per [C2mim][OAc] molecule.

Aeropectin: Fully Biomass-Based Mechanically Strong and Thermal Superinsulating Aerogel

Monolithic pectin aerogels, aeropectins, were prepared via dissolution-gelation-coagulation and subsequent drying with supercritical CO2. Aeropectin had pore sizes that varied from mesopores to small macropores and compression moduli in the range from 4 to 18 MPa. Aeropectins show plastic deformation up to 60% strain before the pore walls collapse. Pectin aerogels have a thermal conductivity below that of air in ambient conditions, making them new thermal superinsulating fully biomass-based materials. The contribution of gas and solid conduction plus radiative heat transfer were determined and discussed.

Cellulose–silica aerogels

Aerogels based on interpenetrated cellulose-silica networks were prepared and characterised. Wet coagulated cellulose was impregnated with silica phase, polyethoxydisiloxane, using two methods: (i) molecular diffusion and (ii) forced flow induced by pressure difference. The latter allowed an enormous decrease in the impregnation times, by almost three orders of magnitude, for a sample with the same geometry. In both cases, nanostructured silica gel was in situ formed inside cellulose matrix. Nitrogen adsorption analysis revealed an almost threefold increase in pores specific surface area, from cellulose aerogel alone to organic-inorganic composite. Morphology, thermal conductivity and mechanical properties under uniaxial compression were investigated. Thermal conductivity of composite aerogels was lower than that of cellulose aerogel due to the formation of superinsulating mesoporous silica inside cellulose pores. Furthermore, composite aerogels were stiffer than each of reference aerogels.

Cellulose in NaOH–water based solvents: a review

The article is a critical review of all aspects of the dissolution of cellulose in NaOH-based aqueous solutions: from the background properties of the solvent itself, to the mechanisms of cellulose fibre swelling and dissolution, solution structure and properties and influence of additives and, finally, to the properties of various materials (fibres, films, aerogels, composites and interpenetrated networks) prepared from these solutions. A historical evolution of the research on this topic is presented. The pros and cons of NaOH-based aqueous solvent for cellulose are summarised and some prospects are suggested.

Dissolution of unmodified waxy starch in ionic liquid and solution rheological properties

Dissolution of waxy corn starch in 1-ethyl-3-methylimidazolium acetate (EMIMAc) was qualitatively studied and compared with gelatinisation process in water. The rheological properties of starch-EMIMAc solutions were investigated in dilute and semi-dilute regions, from 0.1 to 10 wt% over temperature range from 20 °C to 100 °C. The values of zero shear viscosity were obtained by applying Carreau-Yasuda model to shear-thinning flow curves and plotted vs. polymer concentration. Power law exponents in viscosity-concentration dependence in semi-dilute region were compared with the ones reported previously for microcrystalline cellulose. Intrinsic viscosity was obtained as a function of temperature and compared with the one of microcrystalline cellulose; starch was found to be much less temperature sensitive than cellulose. Amylopectin overlap concentration in EMIMAc was compared with the one in water and 0.5 M NaOH-water. Based on these comparisons it was suggested that starch conformation in EMIMAc is similar to the one in water (compact ellipsoid). The activation energy was calculated for starch-EMIMAc solutions and demonstrated to obey power-law concentration dependence.

Phase diagram, solubility limit and hydrodynamic properties of cellulose in binary solvents with ionic liquid.

Cellulose solubility phase diagrams in two binary solvents based on 1-ethyl-3-methylimidazolium acetate (EmimAc) mixed with water and with dimethylsulfoxide (DMSO) were built. The minimal amount of EmimAc molecules needed to dissolve cellulose is 2.5-3moles per anhydroglucose unit. This proportion allows calculation of the maximal cellulose concentration soluble in EmimAc-DMSO at any composition; in EmimAc it is around 25-27wt%. Water forms hydrogen bonds with EmimAc and thus competes with cellulose for ionic liquid; the solubility of cellulose in EmimAc-water is much lower than that in EmimAc-DMSO. Hydrodynamic properties of cellulose in two solvent systems were compared. In EmimAc-DMSO cellulose intrinsic viscosity practically does not depend on DMSO content as predicted by the phase diagram. The intrinsic viscosity in EmimAc-water first increases with water content due to cellulose self-aggregation and then abruptly decreases due to coagulation.

Interpolymer complexation between polyacrylic acid and cellulose ethers: Formation and properties

The interaction between polyacrylic acid and two water-soluble cellulose ethers (methylcellulose and hydroxyethylcellulose) was studied. Viscometry, velocity sedimentation, small-angle neutron scattering, and potentiometric titration methods show the formation of stable water-soluble interpolymer complexes due to hydrogen bonding between nondissociated groups of polyacrylic acid and proton-acceptor groups of the cellulose ether. Both complexes exhibit polyelectrolyte properties and keep the conformation of the semirigid chain component. The hydrophobic groups in the methylcellulose macromolecule are responsible for the absence of complexes at temperatures greater than 60 °C.

Swelling kinetics of a polyelectrolyte gel in water and salt solutions. coexistence of swollen and collapsed phases

The swelling of polyelectrolyte gels in water and salt solutions is associated with the presence of up to three coexisting phases: a dry phase, a swollen phase, and a collapsed one due to the binding of metal ions to polyions. Swelling in pure water proceeds in two ways: a transition from the dry to swollen state, whose kinetics scales with the square of the initial gel size, and a further swelling that scales linearly with the initial gel size. We show that there exist various swelling paths depending on the gel interaction with metal ions and their concentration.