Controlling the elasticity of polyacrylonitrile fibers via ionic liquids containing cyano-based anions.

As the predominant precursor for high-performance carbon fiber manufacturing, the fabrication of polyacrylonitrile (PAN)-based composite fibers attracts great interest. Ionic liquids (ILs) have recently been investigated for melt-spinning of ultrafine PAN fibers. The plasticizing properties of ILs are significantly affected by the structure of ILs and can be influenced by electronegativity, steric effects, etc. Herein, we report a facile strategy to control the elasticity of the PAN/ILs fibers by tuning the anion structure of ILs. Particularly, the ILs containing nitrile-rich groups exhibited enhanced plasticizing effect and nucleating ability on dissolving PAN components, achieving highly stretchable PAN/ILs fibers.

Effect of the Ionic Liquid Structure on the Melt Processability of Polyacrylonitrile Fibers.

The production of high-strength carbon fibers is an energy-intensive process, where a significant cost involves the wet or dry-spinning of polyacrylonitrile (PAN) fiber precursors. Melt-spinning PAN fibers would allow for significant reduction in the production cost and production hazards. Ionic liquids (ILs) are an attractive fiber-processing medium because of their negligible vapor pressure and low toxicity. In addition, they are carbon-forming precursors; upon carbonization, residual ILs can enhance the carbon yield, although primarily useful for plasticized melt-spinning of PAN precursor fibers. In this research, we investigated the influence of the molecular structure of ILs and the control of plasticizing interactions with PAN during melt-spinning. The structural, thermal, and mechanical properties of the melt-spun PAN fibers were obtained by a combination of various characterization methods, such as differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and mechanical testing. These results demonstrated that the IL structure and counteranions influence the PAN fiber formation. More specifically, ILs containing bromide counteranions produced PAN precursor fibers with increased mechanical properties compared to ILs containing chloride anions. Our research can provide a foundation to understand the influence of ILs on melt-spinning of PAN fibers and provides us the guidelines for a higher cost-/energy-efficient production of PAN-based carbon fibers.

Dialing in Direct Air Capture of CO2 by Crystal Engineering of Bisiminoguanidines.

Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO2 concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis(iminoguanidine) (BIG) carbonate salts. Their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO2, and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.

Tunable synthetic control of soft polymeric nanoparticle morphology.

With a growing variety of nanoparticles available, research probing the influence of particle deformability, morphology, and topology on the behavior of all polymer nanocomposites is also increasing. In particular, the behavior of soft polymeric nanoparticles in polymer nanocomposites has displayed unique behavior, but their precise performance depends intimately on the internal structure and morphology of the nanoparticle. With the goal of providing guidelines to control the structure and morphology of soft polymeric nanoparticles, we have examined monomer starved semi-batch nano-emulsion polymerizations that form organic, soft nanoparticles, to correlate the precise structure of the nanoparticle to the rate of monomer addition and crosslinking density. The synthesis method produces 5-20 nm radii polystyrene nanoparticles with tunable morphologies. We report small angle neutron scattering (SANS) results that correlate synthetic conditions to the structural characteristics of soft polystyrene nanoparticles. These results show that the measured molecular weight of the nanoparticles is controlled by the monomer addition rate, the total nanoparticle radius is controlled by the excess surfactant concentration, and the crosslinking density has a direct effect on the topology of each nanoparticle. These studies thus provide pathways to control these 3 structural characteristics of the nanoparticle. This research, therefore provides a conduit to thoroughly investigate the effect of structural features of soft nanoparticles on their individual properties and those of their polymer nanocomposites.