Michael Persson

Local coordination and dynamics of a protic ammonium based ionic liquid immobilized in nano-porous silica micro-particles probed by Raman and NMR spectroscopy

Room temperature ionic liquids confined in a solid material, for example, nano-porous silica, are particularly propitious for energy related applications. The aim of this study is to probe the molecular interactions established between the protic ionic liquid diethylmethylammonium methanesulfonate (DEMA-OMs) and silica, where the latter consists of nano-porous micro-particles with pores in the size range of 10 nm. The changes in the local coordination and transport properties induced by the nano-confinement of the ionic liquid are investigated by a combination of Raman and solid-state NMR spectroscopy. In particular, one-dimensional (1D) (1)H and (29)Si and two-dimensional (2D) (29)Si{(1)H} HETOCR solid-state NMR are combined to identify the sites of interaction at the silica-ionic liquid interface. Pulsed field gradient (PFG) NMR experiments are performed to estimate the self-diffusion of both bulk and nano-confined DEMA-OMs. Complementary information on the overall coordination and interaction scheme is achieved by Raman spectroscopy. All these advanced experimental techniques are revealed to be crucial to differentiate between ionic liquid molecules residing in the inter- or intra-particle domains.

Surface activity and flocculation behavior of polyethylene glycol-functionalized silica nanoparticles

Colloidal silica nanoparticles have been functionalized with methyl polyethylene glycol silane (mPEG silane) and the PEGylated particles have been characterized with focus on exploring their surface chemical properties. The degree of surface functionalization was quantified using NMR diffusometry, and the measurements showed that the silane binds covalently to the silica surface. Samples with surface coverages ranging from 0.068 to 0.315 μmol silane/m(2) have been analyzed. The functionalized particles proved to be surface active and showed a significant reduction in surface charge and zeta potential with increasing degree of PEG functionalization. All samples showed colloidal stability at neutral pH and above within the range studied. At lower pH, the samples with low surface coverage displayed a reversible flocculation behavior, while samples with a high surface coverage and samples without functionalization remained stable. This suggests that steric stabilization is effective at low pH when the surface coverage is high enough; electrostatic stabilization is effective for samples without functionalization; and that inter-particle PEG-silica interactions cause flocculation of particles with too low degrees of PEG functionalization.

Competitive adsorption of amylopectin and amylose on cationic nanoparticles: a study on the aggregation mechanism

In this study we investigate the interactions between cationic nanoparticles and anionic starch, where the starch was composed of 20 wt% of amylose, a linear polymer, and 80 wt% of amylopectin, a branched polymer. The mechanism of aggregation was investigated by scattering techniques. It was found that the cationic particles formed large aggregates with the starch as a result of selective adsorption of the amylopectin. Amylose did not participate significantly in the aggregate formation even when the charge ratio of starch to particles was <1. For starch to particle ratio >1 stabilization was recovered mostly due to the large hindrance brought about by the highly branched amylopectin. This results in a shift of the stabilization mechanism from electrostatic to electrosteric. The internal structure of the aggregates was composed of primary particles with starch coils adsorbed on the surface. This information supports the proposed aggregation mechanism, which is based on adsorption of the negatively charged starch in patches on the positively charged nanoparticles causing attractive interaction between the particles.

The influence of the molecular weight of the water-soluble polymer on phase-separated films for controlled release

Hydroxypropyl cellulose (HPC) and ethyl cellulose (EC) can be used for extended release coatings, where the water-soluble HPC may act as a pore former. The aim was to investigate the effect of the molecular weight of HPC on the microstructure and mass transport in phase-separated freestanding EC/HPC films with 30% w/w HPC. Four different HPC grades were used, with weight averaged molecular weights (Mw) of 30.0 (SSL), 55.0 (SL), 83.5 (L) and 365 (M) kg/mol. Results showed that the phase-separated structure changed from HPC-discontinuous to bicontinuous with increasing Mw of HPC. The film with the lowest Mw HPC (SSL) had unconnected oval-shaped HPC-rich domains, leaked almost no HPC and had the lowest water permeability. The remaining higher Mw films had connected complex-shaped pores, which resulted in higher permeabilities. The highest Mw film (M) had the smallest pores and very slow HPC leakage, which led to a slow increase in permeability. Films with grade L and SL released most of their HPC, yet the permeability of the L film was three times higher due to greater pore connectivity. It was concluded that the phase-separated microstructure, the level of pore percolation and the leakage rate of HPC will be affected by the choice of HPC Mw grade used in the film and this will in turn have strong impact on the film permeability.

On the potential of using nanocellulose for consolidation of painting canvases

Nanocellulose has been recently proposed as a novel consolidant for historical papers. Its use for painting canvas consolidation, however, remains unexplored. Here, we show for the first time how different nanocelluloses, namely mechanically isolated cellulose nanofibrils (CNF), carboxymethylated cellulose nanofibrils (CCNF) and cellulose nanocrystals (CNC), act as a bio-based alternative to synthetic resins and other conventional canvas consolidants. Importantly, we demonstrate that compared to some traditional consolidants, all tested nanocelluloses provided reinforcement in the adequate elongation regime. CCNF showed the best consolidation per added weight; however, it had to be handled at very low solids content compared to other nanocelluloses, exposing canvases to larger water volumes. CNC reinforced the least per added weight but could be used in more concentrated suspensions, giving the strongest consolidation after an equivalent number of coatings. CNF performed between CNC and CCNF. All nanocelluloses showed better consolidation than lining with synthetic adhesive (Beva 371) and linen canvas in the elongation region of interest.

A long-chain protic ionic liquid inside silica nanopores: Enhanced proton mobility due to efficient self-assembly and decoupled proton transport

We report enhanced protonic and ionic dynamics in an imidazole/protic ionic liquid mixture confined within the nanopores of silica particles. The ionic liquid is 1-octylimidazolium bis(trifluoromethanesulfonyl)imide ([HC8Im][TFSI]), while the silica particles are microsized and characterized by internal well connected nanopores. We demonstrate that the addition of imidazole is crucial to promote a proton motion decoupled from molecular diffusion, which occurs due to the establishment of new N-HN hydrogen bonds and fast proton exchange events in the ionic domains, as evidenced by both infrared and 1H NMR spectroscopy. An additional reason for the decoupled motion of protons is the nanosegregated structure adopted by the liquid imidazole/[HC8Im][TFSI] mixture, with segregated polar and non-polar nano-domains, as clearly shown by WAXS data. This arrangement, promoted by the length of the octyl group and thus by significant chain-chain interactions, reduces the mobility of molecules (Dmol) more than that of protons (DH), which is manifested by DH/Dmol ratios greater than three. Once included into the nanopores of hydrophobic silica microparticles, the nanostructure of the liquid mixture is preserved with slightly larger ionic domains, but effects on the non-polar ones are unclear. This results in a further enhancement of proton motion with localised paths of conduction. These findings demonstrate significant progress in the design of proton conducting materials via tailor-made molecular structures as well as by smart exploitation of confinement effects. Compared to other imidazole-based proton conducting materials that are crystalline up to 90 °C or above, the gel materials that we propose are useful for applications at room temperature, and can thus find applications in e.g. intermediate temperature proton exchange fuel cells.

Combined Nanocellulose/Nanosilica Approach for Multiscale Consolidation of Painting Canvases

The restoration of painting canvases is a complex problem that, because of the hierarchical nature of the canvas, requires intervention at several length scales. We propose an approach combining polyelectrolyte-treated silica nanoparticles (SNP) and cellulose nanofibrils (CNF) for canvas consolidation. The formulations, applied on model-degraded canvases, gave a total weight increase of <5 wt %. Scanning electron microscopy and micro-X-ray fluorescence measurements were used for determining the component distribution across the canvas depth, while tensile testing demonstrated the mechanical efficiency of the consolidation. CNF formed a film at the canvas surface that increased the ductility. SNP penetrated deeper and reinforced at the fiber scale, yielding higher stiffness. The two effects could be balanced by varying the SNP/CNF ratio to reach a suitable reinforcement. This approach offers an alternative to the conventional treatments based on, e.g., relining with a new canvas or application of synthetic...