An official website of the United States government
The thinning of a cylinder of a polymer solution in a volatile solvent is argued to be controlled by solvent diffusion through a dense polymer layer at the cylinder surface. This naturally leads to the exponential time dependence of cylinder radius that is observed in experiments using a fast camera, such as capillary breakup extensional rheometry (CaBER). The relaxation time is controlled by the thickness of the dense (and often glassy) polymer layer and the diffusion coefficient of solvent through that layer. If correct, this means that while CaBER is very useful for understanding fiber spinning, the relaxation time does not yield a measure of the extensional viscosity of polymer solutions in volatile solvents.
more »
« less
Effect of thermal treatment on the structure and gas transport properties of a triptycene-based polybenzoxazole exhibiting configurational free volume
The effect of thermal treatment at 220 °C for 10 days on the structure and transport properties of a triptycene-based polybenzoxazole (TPBO) was investigated experimentally and theoretically. Gas and water vapor sorption in TPBO is virtually unaffected by thermal treatment, while diffusion and permeability coefficients decrease by just 20%. Remarkably, the CO2/CH4 selectivity exhibit a negligible change. Fluorescence spectroscopy, WAXD and FTIR analysis indicate that, in sharp contrast with typical behavior of glassy polymers, TPBO does not experience accelerated physical aging, and rule out formation of intermolecular charge transfer complexes upon thermal treatment. According with this physical picture, the diffusion coefficient of penetrant molecules sorbed in the Langmuir's mode, DH, does not change after treatment. Small molecule diffusivity and permeability decline is caused by a decrease in polymer chain mobility, which makes more difficult opening gaps to allow penetrant diffusion jumps. According to this picture, the Henry's mode diffusion coefficient, DD, substantially decreases upon thermal treatment. The higher stability exhibited by TPBO relative to other high Tg glassy polymers is ascribed to the presence of configurational free volume, which is not related to the non-equilibrium transient conformation, but to the molecular configuration and, as such, it is not relaxed upon protracted exposure to high temperatures.
more »
« less
- Award ID(s):
- 1926868
- PAR ID:
- 10158001
- Date Published:
- Journal Name:
- Journal of membrane science
- Volume:
- 597
- Issue:
- 1
- ISSN:
- 0376-7388
- Page Range / eLocation ID:
- 117759
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Rotational–translational decoupling in systems near T g , in which translational diffusion is apparently enhanced relative to rotation, has been observed in ensemble and single molecule experiments and has been linked to dynamic heterogeneity. Here, simulations of single molecules experiencing homogeneous diffusion and static and dynamic heterogeneous diffusion are performed to clarify the contributions of heterogeneity to such enhanced translational diffusion. Results show that time-limited trajectories broaden the distribution of diffusion coefficients in the presence of homogeneous diffusion but not when physically reasonable degrees of static heterogeneity are present. When dynamic heterogeneity is introduced, measured diffusion coefficients uniformly increase relative to input diffusion coefficients, and the widths of output distributions decrease, providing support for the idea that dynamic heterogeneity can drive apparent translational enhancement. Among simulations with dynamic heterogeneity, when the frequency of dynamic exchange is correlated with the initial diffusion coefficient, the measured diffusion coefficient behavior as a function of observation time matches that seen experimentally, the only set of simulations explored in which this occurs. Taken together with experimental results, this suggests that enhanced translational diffusion in glassy systems occurs through dynamic exchange consistent with wide underlying distributions of diffusion coefficients and exchange coupled to local spatiotemporal dynamics.more » « less
-
X-ray scattering has been used to characterize the columnar packing and the π stacking in a glass-forming discotic liquid crystal. In the equilibrium liquid state, the intensities of the scattering peaks for π stacking and columnar packing are proportional to each other, indicating concurrent development of the two orders. Upon cooling into the glassy state, the π–π distance shows a kinetic arrest with a change in the thermal expansion coefficient (TEC) from 321 to 109 ppm/K, while the intercolumnar spacing exhibits a constant TEC of 113 ppm/K. By changing the cooling rate, it is possible to prepare glasses with a wide range of columnar and π stacking orders, including zero order. For each glass, the columnar order and the π stacking order correspond to a much hotter liquid than its enthalpy and π–π distance, with the difference between the two internal (fictive) temperatures exceeding 100 K. By comparison with the relaxation map obtained by dielectric spectroscopy, we find that the δ mode (disk tumbling within a column) controls the columnar order and the π stacking order trapped in the glass, while the α mode (disk spinning about its axis) controls the enthalpy and the π–π spacing. Our finding is relevant for controlling the different structural features of a molecular glass to optimize its properties.more » « less
-
Porous nanoscale carbonaceous materials are widely employed for catalysis, separations, and electrochemical devices where device performance often relies upon specific and well-defined regular feature sizes. The use of block polymers as templates has enabled affordable and scalable production of diverse porous carbons. However, popular carbon preparations use equilibrating micelles which can change dimensions in response to the processing environment. Thus, polymer methods have not yet demonstrated carbon nanomaterials with constant average template diameter and tailored wall thickness. In contrast, persistent micelle templates (PMTs) use kinetic control to preserve constant micelle template diameters, and thus PMT has enabled constant pore diameter metrics. With PMT, the wall thickness is independently adjustable via the amount of material precursor added to the micelle templates. Previous PMT demonstrations relied upon thermodynamic barriers to inhibit chain exchange while in solution, followed by rapid evaporation and cross-linking of material precursors to mitigate micelle reorganization once the solvent evaporated. It is shown here that this approach, however, fails to deliver kinetic micelle control when used with slowly cross-linking material precursors such as those for porous carbons. A new modality for kinetic control over micelle templates, glassy-PMTs, is shown using an immobilized glassy micelle core composed of polystyrene (PS). Although PS based polymers have been used to template carbon materials before, all prior reports included plasticizers that prevented kinetic micelle control. Here the key synthetic conditions for carbon materials with glassy-PMT control are enumerated, including dependencies upon polymer block selection, block molecular mass, solvent selection, and micelle processing timeline. The use of glassy-PMTs also enables the direct observation of micelle cores by TEM which are shown to be commensurate with template dimensions. Glassy-PMTs are thus robust and insensitive to material processing kinetics, broadly enabling tailored nanomaterials with diverse chemistries.more » « less
-
Graft polymers are gaining increasing interest because of their unique architectural characteristics. We recently reported a novel type of depolymerizable graft polymer based on poly(trans-cyclobutane fused cyclooctene), in an effort to address the trade-off between depolymerizability and controlled grafting-through polymerization. In this work, we examine the thermal, mechanical, and morphological properties of a graft copolymer thermoplastic material prepared by copolymerizing poly(L-lactide) and margaric acid-based macromonomers. A copolymerization kinetics study reveals that the two macromonomers are incorporated almost randomly and that the domain spacing measured from small-angle X-ray scattering is consistent with the random distribution. An investigation of the crystallization behavior suggests that proper thermal treatment is required to maximize, or to even observe crystallinity. The physical states of the soft and hard domains, whether melt, glassy, or semicrystalline, significantly impact the tensile properties of the resulting copolymer materials. Finally, the rheological properties and morphological features are discussed.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/https://doi.org/10.1016/j.memsci.2019.117759
