Surface diffusion has been measured in the glass of an organic semiconductor, MTDATA, using the method of surface grating decay. The decay rate was measured as a function of temperature and grating wavelength, and the results indicate that the decay mechanism is viscous flow at high temperatures and surface diffusion at low temperatures. Surface diffusion in MTDATA is enhanced by 4 orders of magnitude relative to bulk diffusion when compared at the glass transition temperature T g . The result on MTDATA has been analyzed along with the results on other molecular glasses without extensive hydrogen bonds. In total, these systems cover a wide range of molecular geometries from rod-like to quasi-spherical to discotic and their surface diffusion coefficients vary by 9 orders of magnitude. We find that the variation is well explained by the existence of a steep surface mobility gradient and the anchoring of surface molecules at different depths. Quantitative analysis of these results supports a recently proposed double-exponential form for the mobility gradient: log D( T, z) = log D v ( T) + [log D 0 − log D v ( T)]exp(− z/ξ), where D( T, z) is the depth-dependent diffusion coefficient, D v ( T) is the bulk diffusion coefficient, D 0 ≈ 10 −8 m 2 /s, and ξ ≈ 1.5 nm. Assuming representative bulk diffusion coefficients for these fragile glass formers, the model reproduces the presently known surface diffusion rates within 0.6 decade. Our result provides a general way to predict the surface diffusion rates in molecular glasses.
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Surface diffusion in glasses of rod-like molecules posaconazole and itraconazole: effect of interfacial molecular alignment and bulk penetration
The method of surface grating decay has been used to measure surface diffusion in the glasses of two rod-like molecules posaconazole (POS) and itraconazole (ITZ). Although structurally similar antifungal medicines, ITZ forms liquid-crystalline phases while POS does not. Surface diffusion in these systems is significantly slower than in the glasses of quasi-spherical molecules of similar volume when compared at the glass transition temperature T g . Between the two systems, ITZ has slower surface diffusion. These results are explained on the basis of the near-vertical orientation of the rod-like molecules at the surface and their deep penetration into the bulk where mobility is low. For molecular glasses without extensive hydrogen bonds, we find that the surface diffusion coefficient at T g decreases smoothly with the penetration depth of surface molecules and the trend has the double-exponential form for the surface mobility gradient observed in simulations. This supports the view that these molecular glasses have a similar mobility vs. depth profile and their different surface diffusion rates arise simply from the different depths at which molecules are anchored. Our results also provide support for a previously observed correlation between the rate of surface diffusion and the fragility of the bulk liquid.
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- Award ID(s):
- 1720415
- NSF-PAR ID:
- 10213887
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 16
- Issue:
- 21
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 5062 to 5070
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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X-ray scattering has been used to characterize glassy itraconazole (ITZ) prepared by cooling at different rates. Faster cooling produces ITZ glasses with lower (or zero) smectic order with more sinusoidal density modulation, larger molecular spacing, and shorter lateral correlation between the rod-like molecules. We find that each glass is characterized by not one, but two fictive temperatures Tf(the temperature at which a chosen order parameter is frozen in the equilibrium liquid). The higher Tfis associated with the regularity of smectic layers and lateral packing, while the lower Tfwith the molecular spacings between and within smectic layers. This indicates that different structural features are frozen on different timescales. The two timescales for ITZ correspond to its two relaxation modes observed by dielectric spectroscopy: the slower δ mode (end-over-end rotation) is associated with the freezing of the regularity of molecular packing and the faster α mode (rotation about the long axis) with the freezing of the spacing between molecules. Our finding suggests a way to selectively control the structural features of glasses.
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The phase transition from subcritical to supercritical conditions, referred to as transcritical behavior, significantly impacts the evaporation and fuel–air mixing in high-pressure liquid-fuel propulsion systems. Transcritical behavior is characterized as a transition from classical two-phase evaporation to a single-phase gas-like diffusion regime as surface tension and latent heat of vaporization reduce. However, the interfacial behavior represented by the surface tension coefficient and evaporation rate during this transition which are crucial inputs for Computational Fluid Dynamics (CFD) simulations of practical transcritical fuel spray is still missing. This study aims at developing new evaporation rate and surface tension models for transcritical n-dodecane droplets using molecular dynamics (MD) simulations irrespective of the droplet size. As MD simulations are primarily limited to the nanoscale, the new models can bridge the gap between MD and continuum simulations and enable the direct application of these findings to microscopic droplets. A new characteristic timescale, i.e., “undroplet time,” is defined which marks the transition from classical two-phase evaporation to single-phase gas-like diffusion behavior. The undroplet time indicates the onset of droplet core disintegration and penetration of nitrogen molecules into the droplet, which occurs after the vanishment of the surface tension. By normalizing the time with respect to the undroplet time, the rate of surface tension decay, evaporation rate, and the rate of droplet mass depletion become independent of the droplet size. Calculation of pairwise correlation coefficients for the entire MD results shows that both surface tension coefficient and evaporation rate are strongly correlated with the background temperature, while pressure and droplet size play a less significant role past the critical point. Therefore, new models for surface tension coefficient and evaporation rate spanning from sub- to supercritical conditions are developed as a function of background pressure and temperature, which can be used in continuum simulations. The identified phase change behavior based on the undroplet time shows a good agreement with the phase change regime maps obtained using microscale experiments and nanoscale MD predictions.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sm00353k
