Pratyush Dayal

Porous Fiber Formation in Polymer-Solvent System Undergoing Solvent Evaporation

Temporal evolution of the fiber morphology during dry spinning has been investigated in the framework of Cahn-Hilliard equation [J. Chem. Phys. 28, 258 (1958)] pertaining to the concentration order parameter or volume fraction given by the Flory-Huggins free energy of mixing [P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, NY, 1953), p. 672] in conjunction with the solvent evaporation rate. To guide the solvent evaporation induced phase separation, equilibrium phase diagram of the starting polymer solution was established on the basis of the Flory-Huggins free energy of mixing. The quasi-steady-state approximation has been adopted to account for the nonconserved nature of the concentration field caused by the solvent loss. The process of solvent evaporation across the fiber skin-air interface was treated in accordance with the classical Fick’s law [R. B. Bird et al., Transport Phenomena (J. Wiley, New York, 1960), p. 780]. The simulated morphologies include gradient type, h...

Crystalline-amorphous interaction in relation to the phase diagrams of binary polymer blends containing a crystalline constituent.

The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.

Dynamics and morphology development in electrospun fibers driven by concentration sweeps

The present article describes the modeling and simulation of the dynamics of the electrospinning process coupled with the spatio-temporal evolution of fiber morphology driven by concentration sweeps. The electrospinning process has been modeled based on an array of beads connected by Maxwell’s elements in a cylindrical shell to describe the force balance between Coulombic and viscoelastic forces at the surface of the jet. The phase separation dynamics has been calculated in the framework of the Cahn-Hilliard time-evolution equation by incorporating Flory-Huggins free energy for liquid-liquid demixing in conjunction with solvent evaporation through the fiber surface. The simulations based on the coupling of these two processes have revealed in situ morphology development registering all structural forming processes such as polymer droplets, interconnected spinodal structure, and the porous structure along the spinline. The simulated porous fiber shows a striking resemblance to the experimental finding.

Modeling Chemoresponsive Polymer Gels

Stimuli-responsive gels are vital components in the next generation of smart devices, which can sense and dynamically respond to changes in the local environment and thereby exhibit more autonomous functionality. We describe recently developed computational methods for simulating the properties of such stimuli-responsive gels in the presence of optical, chemical, and thermal gradients. Using these models, we determine how to harness light to drive shape changes and directed motion in spirobenzopyran-containing gels. Focusing on oscillating gels undergoing the Belousov-Zhabotinksy reaction, we demonstrate that these materials can spontaneously form self-rotating assemblies, or pinwheels. Finally, we model temperature-sensitive gels that encompass chemically reactive filaments to optimize the performance of this system as a homeostatic device for regulating temperature. These studies could facilitate the development of soft robots that autonomously interconvert chemical and mechanical energy and thus perform vital functions without the continuous need of external power sources.

Crystal-liquid crystal binary phase diagrams

We propose a new theoretical scheme for the binary phase diagrams of crystal-liquid crystal mixtures by a combination of a phase field model of solidification, the Flory-Huggins theory for liquid-liquid mixing and Maier-Saupe-McMillan (FH-MSM) model for nematic and smectic liquid crystal orderings. The phase field theory describes the crystal phase transition of anisotropic organic crystal and/or side chain liquid crystalline polymer crystals while the FH-MSM model explains isotropic, nematic and smectic-A phase transitions. Self-consistent calculations reveal several possible phase diagram topologies of the binary crystal-liquid crystal mixtures. The calculated phase diagrams were found to accord well to the reported experimental results.

Using a single mask to create multiple patterns in three-component, photoreactive blends.

Via simulations, we demonstrate a simple route for forming defect-free patterns in a photosensitive, immiscible ABC blend. The first pattern is established by irradiating the sample through a mask, which serves to pin the C regions and thereby promotes the self-assembly of A and B into ordered domains. When the mask is removed, the photoactivity of the AB blend leads to different periodic patterns. Thus, the use of one mask permits the creation of multiple ordered morphologies, which can be locked into the film by quenching the system at the appropriate time.

CHAPTER 4:Modeling the Interaction of Active Cilia with Species in Solution: From Chemical Reagents to Microscopic Particles

Biological cilia can sense minute chemical variations or the presence of particulates in their environment, transmit this information to their neighbors, and thereby produce a global response to a local change. Using computational modeling, we demonstrate two distinct examples of analogous sensing and communicating behavior performed by artificial cilia. In the first example, cilia formed from chemo‐responsive gels undergo the oscillatory Belousov–Zhabotinsky (BZ) reaction. The activator for the reaction, u, is generated within these BZ cilia and diffuses between the neighboring gels. By varying the spatial arrangement of the BZ cilia, we not only alter the directionality of the traveling waves within the array, but also uncover a distinctive form of chemotaxis, where the tethered gels bend towards higher concentrations of u and, hence, towards each other. We also show that the cilial oscillations can be controlled remotely and non‐invasively by light. In our second example, we model the transport of a microscopic particle via a regular array of beating elastic cilia, whose tips experience an adhesive interaction with the particle’s surface. By varying the cilia–particle adhesion strength and the cilia stiffness, we pinpoint the parameters where the particle can be ‘released’, ‘propelled’ or ‘trapped’ by the cilial layer.