Lars Nordstierna

Dissolution and Gelation of Cellulose in TBAF/DMSO Solutions: The Roles of Fluoride Ions and Water

Solutions of cellulose in a mixture of tetrabutylammonium fluoride and dimethyl sulfoxide (TBAF/DMSO) containing small and varying amounts of water were studied by nuclear magnetic resonance (NMR). By measuring the composition dependences of (19)F NMR and (1)H NMR chemical shifts and line widths, details on the dissolution and gelation mechanisms for cellulose in TBAF/DMSO were elucidated. Our results suggest that the strongly electronegative fluoride ions act as hydrogen bond acceptors to cellulose hydroxyl groups, thus dissolving the polymer by breaking the cellulose-cellulose hydrogen bonds and by rendering the chains an effective negative charge. It was found that the fluoride ions also interact strongly with water. Small amounts of water remove the fluoride ions from the cellulose chains and allow reformation of the cellulose-cellulose hydrogen bonds, which leads to formation of highly viscous solutions or gels even at low cellulose concentrations.

Effect of water on the transport properties of protic and aprotic imidazolium ionic liquids – an analysis of self-diffusivity, conductivity, and proton exchange mechanism

In this paper we report on the transport properties of protic and aprotic ionic liquids of the imidazolium cation (C2C1Im(+) or C2HIm(+)) and the TFSI(-) or TfO(-) anion as a function of added water. We observe that the self-diffusion coefficient of the ionic species increases upon addition of water, and that the cation diffuses faster than the anion in the entire water concentration range investigated. We also observe that the overall increase of anionic and cationic diffusion coefficients is significant for C2HImTfO while it is rather weak for C2C1ImTFSI, the former being more hydrophilic. Moreover, the difference between cationic and anionic self-diffusivity specifically depends on the structure of the ionic liquids ions. The degree of ion-ion association has been investigated by comparing the molar conductivity obtained by impedance measurements with the molar conductivity calculated from NMR data using the Nernst-Einstein equation. Our data indicate that the ions are partly dissociated (Λimp/ΛNMR in the range 0.45-0.75) but also that the degree of association decreases in the order C2HImTfO > C2HImTFSI ≈ C2C1ImTfO > C2C1ImTFSI. From these results, it seems that water finds different sites of interaction in the protic and aprotic ionic liquids, with a strong preference for hydrogen bonding to the -NH group (when available) and a stronger affinity to the TfO anion as compared to the TFSI. For the protic ionic liquids, the analysis of (1)H NMR chemical shifts (upon addition of H2O and D2O, respectively) indicates a water-cation interaction of hydrogen bonding nature. In addition, we could probe proton exchange between the -NH group and deuterated water for the protic cation, which occurs at a significantly faster rate if associated with the TfO anion as compared to the TFSI.

Towards novel wood-based materials: Chemical bonds between lignin-like model molecules and poly(furfuryl alcohol) studied by NMR

Abstract Wood modification with furfuryl alcohol is a non-toxic alternative to conventional preservation treatments. A process in which furfuryl alcohol polymerises in situ was previously proposed for chemical modification of wood. In the present work, liquid model systems were investigated using compounds that resemble repeating units of lignin to verify whether chemical bonds form between the furfuryl alcohol polymer and wood. Using different NMR spectroscopic techniques we confirmed that these model compounds do form covalent bonds with the polymerising polymer. The results indicate that the furan polymer grafts to lignin, supporting observations in similar studies performed with genuine wood materials.

Influence of water on swelling and dissolution of cellulose in 1-ethyl-3-methylimidazolium acetate

In this study the effect of residual coagulation medium (water) on cellulose dissolution in an ionic liquid is discussed. Solubility of dissolving grade pulp; HWP and SWP, and microcrystalline cellulose in binary solvents, mixtures of 1-ethyl-3-methyl-imidazolium acetate and water, was investigated by turbidity measurements, light microscopy, rheometry, and CP/MAS (13)C-NMR spectroscopy. The viscoelastic properties of the cellulose solutions imply that residual water affect the cellulose dissolution. However, it is not obvious that this always necessarily poses serious drawbacks for the solution properties or that the effects are as severe as previously believed. Turbidity measurements, viscosity data and crystallinity of the regenerated cellulose correlated well and an increased conversion to cellulose II was found at low water and cellulose contents with an apparent maximum of conversion at 2-5 wt% water. At high water content, above 10 wt%, dissolution and conversion was largely inhibited.

Use of microcapsules as controlled release devices for coatings

Biofouling of surfaces is a considerable problem in many industrial sectors and for the public community in general. The problem is usually approached by the use of functional coatings and most of such antifouling coatings rely on the effect of biocides. However, a substantial drawback is the poor control over the release of the biocide as well as its degradation in the paint. Encapsulation of the biocides in microcapsules is a promising approach that may overcome some of the problems associated with the more traditional ways of incorporating the antifouling agent into the formulation. In this review, we summarize more than a decade of microcapsule research from our lab as well as from other groups working on this topic. Focus will be on two coacervation-based encapsulation techniques; the internal phase separation method and the double emulsion method, which together enable the encapsulation of a broad spectrum of biocides with different physicochemical properties. The release of the biocide from core-shell particles and from encapsulated biocides in coatings is treated in detail. The release behaviour is interpreted in terms of the physicochemical properties of the core-shell particle and the coating matrix. In addition, special attention is given to the experimental release methodology and the implementation of proper diffusion models to describe the release. At the end of the review examples of antifouling properties of some coatings against common biofoulers are presented.

Modification of crystallinity and pore size distribution in coagulated cellulose films

In this study the effects of altering the coagulation medium during regeneration of cellulose dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate, were investigated using solid-state NMR spectroscopy and NMR cryoporometry. In addition, the influence of drying procedure on the structure of regenerated cellulose was studied. Complete conversion of the starting material into regenerated cellulose was seen regardless of the choice of coagulation medium. Coagulation in water predominantly formed cellulose II, whereas coagulation in alcohols mainly generated non-crystalline structures. Subsequent drying of the regenerated cellulose films, induced hornification effects in the form of irreversible aggregation. This was indicated by solid-state NMR as an increase in signal intensity originating from crystalline structures accompanied by a decrease of signal intensity originating from cellulose surfaces. This phenomenon was observed for all used coagulants in this study, but to various degrees with regard to the polarity of the coagulant. From NMR cryoporometry, it was concluded that drying induced hornification generates an increase of nano-sized pores. A bimodal pore size distribution with pore radius maxima of a few nanometers was observed, and this pattern increased as a function of drying. Additionally, cyclic drying and rewetting generated a narrow monomodal pore size pattern. This study implies that the porosity and crystallinity of regenerated cellulose can be manipulated by the choice of drying condition.

Nonideal Mixed Micelles of Fluorinated and Hydrogenous Surfactants in Aqueous Solution. NMR and SANS Studies of Anionic and Nonionic Systems

Contrast variation SANS and (19)F chemical shifts were measured for three mixed equimolar micelle systems: sodium perfluorooctanoate (SPFO) and sodiumdecylsulfate (SDeS) in 200 mM NaCl, lithium perfluorononanate (LiPFN) and lithium dodecylsulfate (LiDS) in 200 mM LiCl, and a nonionic system C(8)F(17)C(2)H(4)(OC(2)H(4))(9) and C(12)H(25)(OC(2)H(4))(8) in water, all at 25 degrees C. The chemical shift measurements allow the calculation of the average fraction of nearest neighbors of each kind around the reporter group (the trifluoromethyl group). A preference for like neighbors were found in all systems, smallest in the SDeS/SPFO system and largest in the nonionic system, but in all cases substantially smaller than expected at critical conditions. From the SANS measurements the width of the micelle composition distribution was obtained. For the ionic systems similar values were obtained, showing a broadening compared to ideal mixtures, but not broad enough for demixing or clearly bimodal distributions. In the nonionic system the width was estimated as sigma = 0.18 and 0.22 using two different evaluation methods. These values suggest that the system is close to critical conditions. The lower value refers to a direct modeling of the system, assuming an ellipsoidal shape and a Gaussian composition distribution. The modeling showed the nonionic mixed micelles to be prolate ellipsoids with axial ratio 2.2 and an aggregation number larger than 100, whereas the two ionic systems fitted best to oblate shapes (axial ratios 0.8 and 0.65 for SDeS/SPFO and LiDS/LiPFN, respectively) and aggregation numbers of 60 for both.

CP/MAS C-13 NMR study of pulp hornification using nanocrystalline cellulose as a model system

The hornification process of paper pulp was investigated using solid-state (13)C NMR spectroscopy. Nanocrystalline cellulose was used to serve as a model system of the crystalline parts of the fibrils in pulp fibers. Characterization of the nanocrystalline cellulose dimensions was carried out using scanning electron microscopy. The samples were treated by drying and wetting cycles prior to NMR analysis where the hornification phenomenon was recorded by spectral changes of the cellulose C-4 carbon signals. An increase of the crystalline signal and a decrease of the signals corresponding to the accessible amorphous domains were found for both paper pulp and nanocrystalline cellulose. These spectral changes grew stronger with repeating drying and wetting cycles. The results show that cellulose co-crystallization contribute to hornification. Another conclusion is that the surfaces of higher hydrophobicity in cellulose fibrils have an increased preference for aggregation.

Charged microcapsules for controlled release of hydrophobic actives. Part III: the effect of polyelectrolyte brush- and multilayers on sustained release.

Poly(methyl methacrylate) microspheres have been prepared by the internal phase separation method using either of the three conventional dispersants poly(vinyl alcohol) (PVA), poly(methacrylic acid) (PMAA), or the amphiphilic block copolymer poly(methyl methacrylate)-block-poly(sodium methacrylate). The block copolymer based microsphere, which has a polyelectrolyte brush on the surface, was surface modified with up to two poly(diallyldimethylammonium chloride)-poly(sodium methacrylate) bilayers. The microspheres were loaded with the hydrophobic dye 2-(4-(2-chloro-4-nitrophenylazo)-N-ethylphenylamino)ethanol (Disperse Red 13) and its release from aqueous dispersions of microspheres with the different surface compositions was measured by spectrophotometry. The burst fraction, burst rate and the diffusion constant were determined from a model combining burst and diffusive release. Out of the three dispersants, the block copolymer gave the slowest release of the dye, with respect to both burst release and diffusive release. A very pronounced further reduction of the diffusion constant was obtained by applying polyelectrolyte multilayers on top of the microspheres. However, the diffusion constant was very weakly dependent on further polyelectrolyte adsorption and one polyelectrolyte bilayer appeared to suffice.

Hydrophilic and hydrophobic modifications of colloidal silica particles for Pickering emulsions

Colloidal silica particles, functionalized with hydrophilic and hydrophobic groups, have been studied for utilization in particle-stabilized emulsions, so called Pickering emulsions. The amounts of attached groups have been characterized using NMR spectroscopy and elemental analysis. A range of particles were prepared, with sizes from around 13 to 70nm in diameter. Hydrophilic functionalization of the silica sols was achieved by attaching methyl poly(ethylene glycol) (mPEG) silane to the silica particle surface. This provides a reduction of surface charge density, a pH dependent and controllable flocculation behavior and surface activity. The hydrophobic functionalization of the silica sols was accomplished by attaching organosilanes containing mainly propyl and methyl groups. The emulsification abilities were evaluated by preparing Pickering emulsions using particles, with varying degrees and combinations of surface functionalization, as stabilizers and comparing the obtained emulsion droplet size distributions. It was found that colloidal silica functionalized with hydrophobic groups produced emulsions with smaller droplets compared to using unmodified silica. The emulsification performance was further improved by the combination of both hydrophilic and hydrophobic groups. All particles having this heterogeneous modification were found to generate emulsions with high stability towards coalescence (from five weeks to 1.5 years).