The dynamics of unentangled polymers during capillary rise infiltration into a nanoparticle packing.

Although highly packed polymer nanocomposites (PNCs) are important for a wide array of applications, preparing them remains difficult because of the poor dispersion of NPs at high loading fractions. One method to successfully prepare PNCs with high loadings is through capillary rise infiltration, as previously shown by Huang et al., although the mechanism of polymer infiltration remains largely unknown. We use molecular dynamics simulations to directly simulate the process of capillary rise infiltration, and we show that the polymers follow Lucas-Washburn dynamics. We observe a wetting front that precedes bulk infiltration, and chains belonging to this front are highly adsorbed to NPs. We also investigate the viscosity of the model polymers both globally and locally in supported and free-standing films, and we find reduced viscosity near the surface of the films and increased viscosity near the supporting substrate, similar to the results of local relaxation times. The reduction in the viscosity at the free surface for short, oligomeric polymers is smaller than for higher molecular weight polymers, and the ratio of the surface viscosities is most consistent with the predictions of the Lucas-Washburn equation. Our results introduce the mechanism by which polymers infiltrate a highly packed NP film, which may shed light on better ways to prepare these materials for energy storage applications and protective coatings.

Physical aging, the local dynamics of glass-forming polymers under nanoscale confinement.

The glass transition temperature marks a point below which a material's properties change significantly, and it is well-established that confinement to the nanoscale modifies the properties of glass-forming materials. We use molecular dynamics simulations to investigate the dynamics and aging behavior of model glass-forming polymers near and below the glass transition temperature of bulk and confined films. We show that both relaxation times and physical age rates vary similarly throughout a free-standing polymer film at temperatures close to the bulk glass transition temperature, where the surfaces have both lower relaxation times and physical age rates. Moreover, we provide evidence suggesting that string lengths in the bulk control dynamic length scales in the film. This realization, combined with the similarity between aging behavior and dynamic profiles, has implications for design rationale in the microelectronics industry.

Strain localization in glassy polymers under cylindrical confinement.

Although the origin of ductility in crystalline materials is well understood through the motion of dislocations and defects, a similar framework for understanding deformation in amorphous materials remains elusive. In particular, the difference in the mechanical response for small-molecule amorphous solids, such as organic glasses that are typically brittle, and polymer glasses, which are frequently very tough, has not been systematically explored. Here, we employ molecular dynamics simulations to investigate the mechanical response of model glassy polymers confined to a nanoscopic pillar under tensile deformation. We vary the chain length, cooling rate for forming the glass, and the deformation rate and investigate the changes in the mechanical response. We find that samples that are cooled at a slower rate and deformed at a slower rate are more prone to localization of the strain response, or shear banding. Interestingly, this effect is independent of chain length over the range of parameters we have investigated so far, and we believe this is the first direct observation of shear banding in deformed polymer glasses under cylindrical confinement. Finally, by using the isoconfigurational ensemble approach, we provide evidence that the location where the shear band forms is due to structural features that are frozen in place during sample preparation.

Evolution of collective motion in a model glass-forming liquid during physical aging.

At temperatures moderately below their glass transition temperature, the properties of many glass-forming materials can evolve slowly with time in a process known as physical aging whereby the thermodynamic, mechanical, and dynamic properties all drift towards their equilibrium values. In this work, we study the evolution of the thermodynamic and dynamic properties during physical aging for a model polymer glass. Specifically, we test the relationship between an estimate of the size of the cooperative rearrangements taking the form of strings and the effective structural relaxation time predicted by the Adam-Gibbs relationship for both an equilibrium supercooled liquid and the same fluid undergoing physical aging towards equilibrium after a series of temperature jumps. We find that there is apparently a close correlation between a structural feature of the fluid, the size of the string-like rearrangements, and the structural relaxation time, although the relationship for the aging fluid appears to be distinct from that of the fluid at equilibrium.

Mixed alkylsilane functionalized surfaces for simultaneous wetting and homeotropic anchoring of liquid crystals.

Surfaces functionalized with a self-assembled monolayer (SAM) formed from a mixture of two alkylsilanes with different chain lengths have been designed to simultaneously improve the liquid crystal (LC) wettability and promote homeotropic anchoring of the LC. Most chemically functionalized surfaces (e.g., long alkyl chain SAMs) that promote homeotropic alignment of LC possess low surface energy and result in poor LC wettability, inhibiting LC infiltration into microstructured surfaces and sometimes resulting in LC dewetting from the surface. However, a surface modified with a mixed SAM of octadecyltriethoxysilane (C18) and ethyltriethoxysilane (C2) exhibited very low LC contact angle while providing homeotropic anchoring. Ellipsometry was used to correlate the bulk concentration of C18 in the deposition solution to the surface coverage of C18 in the mixed monolayer; these bulk and surface concentrations were found to be equal within experimental uncertainty. The LC contact angle was found to depend nonmonotically with the surface coverage density, with a minimum (14.4 ± 0.1°) at a C18 surface coverage of 0.26 ± 0.08. Homeotropic LC anchoring was achieved at a C18 surface coverage of ≥0.11 ± 0.04, in the regime where a minimum in the LC contact angle was observed. The practical application of this approach to surface modification was demonstrated using a micropillar array sensor substrate. When the array was functionalized with a conventional C18 SAM, the LC did not infiltrate the array and exhibited a contact angle of 47.4 ± 0.5°. However, the LC material successfully infiltrated and wetted the same microstructured substrate when functionalized with a C18/C2 mixed SAM, while still exhibiting the desired homeotropic anchoring.