Phase-separation of cellulose from ionic liquid upon cooling: preparation of microsized particles

Cellulose - Cellulose is an historical polymer, for which its processing possibilities have been limited by the absence of a melting point and insolubility in all non-derivatizing molecular...     

Rheological Behavior of Poly(vinylpyrrolidone)/Fullerene C60 Complexes in Aqueous Medium

Aqueous solutions of complexes formed between poly(vinylpyrrolidone) (PVP), as a matrix polymer, and fullerene C₆₀ were investigated. The effect of the external hydrodynamic field on the supermolecular assemblies formed by the complexes was analyzed. Despite the low content in the complexes (1.5 mass%), fullerene significantly modified the viscosity of aqueous PVP. Thus, the dynamic viscosity of the PVP/C₆₀ complexes grew faster than that of the pure PVP upon increasing the PVP/C₆₀ concentration. The difference in viscosities is especially pronounced for semidilute solutions. As a possible explanation, it is assumed that fullerenes act as crosslinks, in addition to the physical entanglements of the PVP macromolecules, which appear in the vicinity of the crossover concentration. Shear flow corresponding to the high shear rates destroyed fullerene‐induced intermolecular crosslinks in PVP/C₆₀ solutions.     

Conformational changes of a polyelectrolyte in mixtures of water and acetone

Samples of a polyelectrolyte poly(methacryloylethyl trimethylammonium methylsulfate), PMETMMS, with molar masses M_w = 22−25 × 10⁶ were examined with viscosity, static light scattering, and conductivity measurements in a water–acetone solvent. Because acetone is a nonsolvent for this polymer the measurements were performed to determine the influence of the solvent composition, the polymer concentration, and the presence of added ions on the conformation of the polyelectrolyte in mixed solvents. The possible influence of a hydrodynamic field on the polymer conformation was also studied. The viscosity of the polymer solutions as a function of polymer concentration, as well as of the solvent composition, was studied using a broad range of shear rates. When the mass fraction of acetone in the solvent, γ, is below 0.5, the solutions show a usual polyelectrolyte behavior. When γ ≥ 0.80, the polymer adopts a compact conformation. This is observed as a decrease of the radius of gyration, R_g, second virial coefficient, A₂, the viscosity, and also as a change in the conductivity of the solution. The change in the polymer conformation may be induced also by dilution. When 0.60 ≤ γ < 0.80, a gradual decrease in the polymer concentration leads to a sudden decrease of the reduced viscosity, which indicates a decrease in the particle size. The values of M_w measured by static light scattering were constant in all experiments. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1107–1114, 1998     

Influence of Time-of-Flight Chromatic Aberration on the Dynamics of Propagation of Pulsed Electron Beam in Ultrafast Electron Microscopy: A New Strategy for Better Temporal Resolution

Journal of Experimental and Theoretical Physics - A common strategy aimed at achieving a high temporal resolution in ultrafast electron microscopy and diffraction is based on the use of strong...     

Ionization of fast rydberg atoms in longitudinal and transverse electric fields

The main properties of longitudinal and transverse electric field ionizers for fast Rydberg atoms n=21–40 have been investigated. The dispersion and the background due to collisional processes between fast atoms and residual gas molecules have been measured and calculated. The kinetic energy spread of ions formed by field ionization of Rydberg atoms and their trajectories have been calculated. The potassium beam energy was 3.9 keV.     

Aggregation and protein binding of sodium maleate copolymers with varying hydrophobicities

Copolymers of sodium maleate with methyl methacrylate, styrene, or vinyl acetate have been synthesized and studied in aqueous NaCl solutions of various ionic strengths. The polymers are polyelectrolytes with varying hydrophobicities, and their solution properties have been studied using static and dynamic light scattering. Copolymers containing methyl methacrylate or styrene were shown to aggregate in water upon increasing salt concentration. Copolymers of sodium maleate and vinyl acetate do not associate with increasing ionic strength. The binding of bovine serum albumin and cytochrome C to the sodium maleate copolymers was also investigated by light scattering. It was observed that cytochrome C forms complexes with the copolymers containing methyl methacrylate or vinyl acetate whereas albumin does not bind to any of the copolymers studied. Copyright © 2004 John Wiley & Sons, Ltd.     

Thermo-Reversible Cellulose Micro Phase-Separation in Mixtures of Methyltributylphosphonium Acetate and γ-Valerolactone or DMSO

We have identified cellulose solvents, comprised of binary mixtures of molecular solvents and ionic liquids that rapidly dissolve cellulose to high concentration and show upper-critical solution temperature (UCST)-like thermodynamic behaviour - upon cooling and micro phase-separation to roughly spherical microparticle particle-gel mixtures. This is a result of an entropy-dominant process, controllable by changing temperature, with an overall exothermic regeneration step. However, the initial dissolution of cellulose in this system, from the majority cellulose I allomorph upon increasing temperature, is also exothermic. The mixtures essentially act as ‘thermo-switchable’ gels. Upon initial dissolution and cooling, micro-scaled spherical particles are formed, the formation onset and size of which are dependent on the presence of traces of water. Wide-angle X-ray scattering (WAXS) and ¹³C cross-polarisation magic-angle spinning (CP-MAS) NMR spectroscopy have identified that the cellulose micro phase-separates with no remaining cellulose I allomorph and eventually forms a proportion of the cellulose II allomorph after water washing and drying. The rheological properties of these solutions demonstrate the possibility of a new type of cellulose processing, whereby morphology can be influenced by changing temperature.     

Few cycle dynamics of multiphoton double ionization

In intense field ionization, an electron removed from the atomic core oscillates in the combined fields of the laser and the parent ion. This oscillation forces repeated revivals of its spatial correlation with the bound electrons. The total probability of double ionization depends on the number of returns and therefore on the number of optical periods in the laser pulse. We observed the yield of Ne(2+) relative to Ne(+) with 12 fs pulses to be clearly less compared to 50 fs pulses in qualitative agreement with our theoretical model.     

Hollow-tip scanning photoelectron microscopy

A new type of microscopy based on scanning in vacuum by a beam of charged particles transmitted through a hollow probe has been implemented. This approach provides controllable motion of spatially localized ion, electron, molecular (atomic), and soft X-ray beams and investigation of the surface in the shear force mode. In the photoelectron mode, in which electrons are transmitted through a 2-μm quartz capillary, a surface profile of gadolinium irradiated by 400-nm femtosecond laser pulses has been visualized with a subwave spatial resolution. The new method of microscopy opens an opportunity of investigations in the field of nanometer local photodesorption of molecular ions (one of the last ideas of V.S. Letokhov).     

Vortex identification in the wake of a model wind turbine array

Vortex identification techniques are used to analyse the wake of a 4 × 3 array of model wind turbines. The Q-criterion, Δ-criterion, and λ₂-criterion are applied to particle image velocimetry data gathered fore and aft of the last row centerline turbine. The Q-criterion and λ₂-criterion provide a clear indication of regions where vortical activity exists, while the Δ-criterion is not successful. Galilean decomposition, Reynolds decomposition, vorticity, and swirling strength are used to further understand the location and behaviour of the vortices. The techniques identify and display the high-magnitude vortices in high-shear zones resulting from the blade tips. Using Galilean and Reynolds decomposition, swirling motions are shown encapsuling vortex regions in agreement with the identification criteria. The Galilean decompositions selected are 20% and 50% of a convective velocity of 7 m/s. As the vortices convect downstream, the strength of the vortices decreases in magnitude, particularly in the far wake of the array, to approximately 25% of those present in the near wake. A high level of vortex activity is visualised as a result of the top tip of the wind turbine blade -- the location where the highest vertical entrainment is present. Analysing the full frame set, the Q-criterion, λ₂-criterion, and swirling strength prove comparable, while the Δ-criterion under-performs in regions of high turbulence activity, namely in the back of the turbine. Entraining flow into the turbine canopy interacting with the turbine generates high-magnitude vortices concentrated at the blade tips. The count of vortices decreases when moving from the top tip down to the wall, as well as their strength for each Galilean technique when a non-zero threshold is applied. Vortex sizes in the near wake are found comparable to turbine blade, hub, and mast dimensions. In the far wake, the resulting size of the vortices is approximately 30% of those in the near wake. These vortices increase in velocity as they convect downstream, following the mean velocity behaviour. The lowest magnitude vortices reside at the hub height in the near-wake region, where they convect at nearly half the speed of those at the blade tips.