The role of local-geometrical-orders on the growth of dynamic-length-scales in glass-forming liquids.

The precise nature of complex structural relaxation as well as an explanation for the precipitous growth of relaxation time in cooling glass-forming liquids are essential to the understanding of vitrification of liquids. The dramatic increase of relaxation time is believed to be caused by the growth of one or more correlation lengths, which has received much attention recently. Here, we report a direct link between the growth of a specific local-geometrical-order and an increase of dynamic-length-scale as the atomic dynamics in metallic glass-forming liquids slow down. Although several types of local geometrical-orders are present in these metallic liquids, the growth of icosahedral ordering is found to be directly related to the increase of the dynamic-length-scale. This finding suggests an intriguing scenario that the transient icosahedral connectivity could be the origin of the dynamic-length-scale in metallic glass-forming liquids.

The logarithmic relaxation process and the critical temperature of liquids in nano-confined states.

The logarithmic relaxation process is the slowest of all relaxation processes and is exhibited by only a few molecular liquids and proteins. Bulk salol, which is a glass-forming liquid, is known to exhibit logarithmic decay of intermediate scattering function for the ß-relaxation process. In this article, we report the influence of nanoscale confinements on the logarithmic relaxation process and changes in the microscopic glass-transition temperature of salol in the carbon and silica nanopores. The generalized vibrational density-of-states of the confined salol indicates that the interaction of salol with ordered nanoporous carbon is hydrophilic in nature whereas the interaction with silica surfaces is more hydrophobic. The mode-coupling theory critical temperature derived from the QENS data shows that the dynamic transition occurs at much lower temperature in the carbon pores than in silica pores. The results of this study indicate that, under nano-confinements, liquids that display logarithmic ß-relaxation phenomenon undergo a unique glass transition process.

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes.

While most supercapacitors are limited in their performance by the stability of the electrolyte, using neat ionic liquids (ILs) as the electrolyte can expand the voltage window and temperature range of operation. In this study, ILs with bis(trifluoromethylsulfonyl)imide (Tf2N) as the anion were investigated as the electrolyte in onion-like carbon-based electrochemical capacitors. To probe the influence of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests was performed using cyclic voltammetry (CV), galvanostatic cycling and electrochemical impedance spectroscopy (EIS). Diffusion coefficients were measured using EIS and correlated with quasielastic neutron scattering and molecular dynamics simulation. These three techniques were used in parallel to confirm a consistent trend between the three ILs. It was found that the IL with the smaller sized cation had a larger diffusion coefficient, leading to a higher capacitance at faster charge-discharge rates. Furthermore, the IL electrolyte performance was correlated with increasing temperature, which limited the voltage stability window and led to the formation of a solid electrolyte interphase on the carbon electrode surface, evident in both the CV and EIS experiments.

Dynamics of phenanthrenequinone on carbon nano-onion surfaces probed by quasielastic neutron scattering.

We used quasielastic neutron scattering (QENS) to study the dynamics of phenanthrenequinone (PQ) on the surface of onion-like carbon (OLC), or so-called carbon onions, as a function of surface coverage and temperature. For both the high- and low-coverage samples, we observed two diffusion processes; a faster process and nearly an order of magnitude slower process. On the high-coverage surface, the slow diffusion process is of long-range translational character, whereas the fast diffusion process is spatially localized on the length scale of ∼4.7 Å. On the low-coverage surface, both diffusion processes are spatially localized; on the same length scale of ∼4.7 Å for the fast diffusion and a somewhat larger length scale for the slow diffusion. Arrhenius temperature dependence is observed except for the long-range diffusion on the high-coverage surface. We attribute the fast diffusion process to the generic localized in-cage dynamics of PQ molecules, and the slow diffusion process to the long-range translational dynamics of PQ molecules, which, depending on the coverage, may be either spatially restricted or long-range. On the low-coverage surface, uniform surface coverage is not attained, and the PQ molecules experience the effect of spatial constraints on their long-range translational dynamics. Unexpectedly, the dynamics of PQ molecules on OLC as a function of temperature and surface coverage bears qualitative resemblance to the dynamics of water molecules on oxide surfaces, including practically temperature-independent residence times for the low-coverage surface. The dynamics features that we observed may be universal across different classes of surface adsorbates.