The water solubility of salts is ordinarily dictated by lattice energy and ion solvation. However, in the case of low melting salts also known as ionic liquids, lattice energy is immaterial and differences in hydrophobicity largely account for differences in their water solubility. In this contribution, the activity coefficients of ionic liquids in water are split into cation and anion contributions by regression against cation hydrophobicity parameters that are experimentally determined by reversed phase liquid chromatography. In this way, anion hydrophobicity parameters are derived, as well as an equation to estimate water solubilities for cation-anion combinations for which the water solubility has not been measured. Thus, a new pathway to the quantification of aqueous ion solvation is shown, making use of the relative weakness of interactions between ionic liquid ions as compared to their hydrophobicities.
We demonstrate a simple route to fabricate hierarchical structures by combining the electrospinning technique and the wetting of porous templates. Poly(methyl methacrylate) (PMMA) fibers are first prepared by electrospinning and are collected on a glass substrate. The PMMA fibers are then brought into contact with an anodic aluminum oxide template. Upon thermal annealing above the glass transition temperature of PMMA, wetting of the polymer chains into the nanopores occurs. After the removal of the AAO template, ordered arrays of nanorods on polymer fibers are obtained. This approach is also applied to polystyrene (PS), and similar structures are obtained. This work provides a promising approach to fabricate hierarchical polymer structures with sizes that can be controlled over the nanoscopic and microscopic length scales.
Electrospinning has been widely used to prepare polymer fibers with diameters ranging from a few nanometers to micrometers. While most studies focus on controlling the sizes and morphologies of electrospun polymer fibers by changing electrospinning conditions, the effect of post-treatments such as thermal annealing on the properties of electrospun polymer fibers has been less studied. Here, we investigate the effect of thermal annealing on the morphology changes of electrospun polystyrene (PS) fibers on substrates. Different from annealing the fibers in a uniform environment, annealing the fibers on substrates results in a substrate-dependent morphology transformation. When the electrospun PS fibers are annealed on a glass substrate, wetting of the fibers on the glass substrate occurs. When the electrospun PS fibers are annealed on a poly(methyl methacrylate) (PMMA)-coated substrate, a Rayleigh-instability-driven morphology transformation is observed. The polymer fibers transform into hemispherical polymer particles caused by the lower surface tension of PS than that of PMMA and the interfacial tension between PS and PMMA. This transformation process is influenced by the annealing time and temperature. The characteristic time of the transformation process is shorter when the sample is annealed at a higher temperature because of the lower polymer viscosity. The size of the polymer particles fits well with the theoretical prediction, which is dependent on the initial fiber diameter and is independent of the annealing temperature.
Electrospinning is a simple and convenient technique to produce polymer fibers with diameters ranging from several nanometers to a few micrometers. Different types of polymer fibers have been prepared by electrospinning for various applications. Among different post-treatment methods of electrospun polymer fibers, the annealing process plays a critical role in controlling the fiber properties. The morphology changes of electrospun polymer fibers under annealing, however, have been little studied. Here we investigate the annealing effect of electrospun poly(methyl methacrylate) (PMMA) fibers and their transformation into PMMA microspheres. PMMA fibers with an average size of 2.39 μm are first prepared by electrospinning a 35 wt% PMMA solution in dimethylformamide. After the electrospun fibers are thermally annealed in ethylene glycol, a non-solvent for PMMA, the surfaces of the fibers undulate and transform into microspheres driven by the Rayleigh instability. The driving force of the transformation process is the minimization of the interfacial energy between the polymer fibers and ethylene glycol. The sizes of the microspheres fit well with the theoretical predictions. Longer annealing times are found to be required at lower temperatures to obtain the microspheres.
We study the thermal annealing effect of poly(methyl methacrylate) (PMMA) nanofibers made from anodic aluminum oxide (AAO) templates and their transformation to PMMA nanospheres. The PMMA nanofibers are prepared by wetting an AAO template with a 30 wt % PMMA solution, followed by the evaporation of the solvent. After the AAO template is removed by a weak base, the PMMA nanofibers are thermally annealed in ethylene glycol, a nonsolvent for PMMA. The surfaces of the nanofibers undulate and transform into nanospheres, driven by the Rayleigh instability. The driving force for the transformation process is the minimization of the interfacial energy between PMMA nanofibers and ethylene glycol. The transformation times at higher annealing temperatures are shorter than those at lower annealing temperatures. This study provides a facile route to prepare polymer nanospheres which are not accessible by other traditional methods.
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