Confinement-induced self-assembly of a diblock copolymer within a non-uniform cylindrical nanopore.

The self-assembly of a diblock copolymer melt confined within a non-uniform cylindrical nanopore is studied using the self-consistent field theory. The non-uniformity manifests in the form of a converging-diverging cylindrical nanopore. The axial variation in pore diameter presents a range of curvatures within the same confinement pore as opposed to a single curvature in a uniform-diameter cylindrical pore. The introduction of multiple curvatures leads to the formation of novel microstructures not accessible in uniform cylindrical confinement. The well-known equilibrium structures like a single helix, double helices, and concentric lamella under cylindrical confinement transition into new morphologies such as hyperboloidal phases, microstructures containing rings with a bead, rings with spheres, and a squeezed helical phase as the pore diameter varies axially. The converging-diverging geometry of the confining pore renders the helical phases seen in the cylindrical pore less favorable. A phase diagram in the parametric space of the block fraction and the ratio of the smallest and largest pore radii has been constructed to depict the order-order transition of various microstructures. The ratio of radii, a measure of the non-uniformity of the pore, along with the pore length brings out some interesting morphologies. The mechanism of these structural transitions is understood as the interplay between the variation in pore curvature attributed to the non-uniformity, the spontaneous curvature of the block copolymer interface, and the enthalpic interaction between the segregated blocks.

Self-organization of a 4-miktoarm star block copolymer induced by cylindrical confinement.

Self-consistent field calculations have been carried out to reveal the self-assembly behavior of a melt of the ABCD star tetrablock copolymer confined within a cylindrical nanopore. The miktoarm star block copolymer exhibits a rich self-assembly behavior with a myriad of interesting three-dimensional ordered phases with the potential to produce advanced nanomaterials. The broad array of ordered mesophases includes helical microstructures, stack of rings/doughnuts, honeycomb structure, and perforated lamella with beads, depending on the individual block fractions and the size of the cylindrical nanopore. Such chiral motifs generated from achiral polymeric molecules are fascinating due to their superior performance in sophisticated opto-electronic devices. The study also demonstrates an interesting morphology, viz. a honeycomb structure, obtained from the self-organization of ABCD star block copolymer molecules with equal block fractions. The system exhibits order-order phase transition covering a range of ordered morphologies by changing either the block fraction or the nanopore radius. A representative phase diagram in terms of block fractions is constructed. These novel ordered microstructures, arising mainly out of structural frustration and confinement-induced entropy loss, can serve as structural scaffolds to host the spatial distribution of nanoparticles resulting into novel nanocomposites with significantly enhanced as well as controllable properties.

Diblock copolymer templated self-assembly of grafted nanoparticles under circular pore confinement.

Geometrical confinement plays an important role in generating novel molecular organization arising out of structural frustration and confinement-induced entropy loss. In the present study, we perform self-consistent mean-field theoretical calculations to examine a mixture of a diblock copolymer and polymer grafted nanoparticles confined in a cylindrical nanopore. The two-dimensional analysis is aimed at constructing the equilibrium nanostructures decorated with particles in an ordered manner. The rich variety of ordered mesophases of the diblock copolymer under confinement provide a template to achieve the self-assembly of nanoparticles in a selective domain. The localization behavior of nanoparticles under confinement is found to be qualitatively different from that in a bulk system. In particular, for the concentric lamellar phase the particles tend to localize predominantly in the region of greater curvature within the curved lamella. The incorporation of grafted nanoparticles also results in a transition in ordered phases. Various equilibrium morphologies are observed depending upon the degree of confinement, particle loading, density of grafted segments and selectivity of the particle core to the polymeric species. The ordering of particles and the ensuing equilibrium nanostructures are analyzed. The comprehensive understanding of the self-assembly behavior of particles enables one to design novel nanomaterials with desirable material properties.

Self-assembly of grafted nanoparticles in the lamellar mesophase of a symmetric triblock copolymer.

The self-assembly behavior of brush-grafted nanoparticles in the ordered mesophase of a symmetric triblock copolymer is studied using the self-consistent field theory. The emphasis is on the templated localization of nanoparticles in a two-dimensional lamellar microstructure formed by an ABA triblock copolymer. While particles grafted with either A-type or B-type polymeric chains preferentially localize in the respective micro-domain, the spatial distribution of particles within the selective domain is of great interest in controlling the properties of the nano-ordered morphologies. As the mid-block of an ABA triblock copolymer is entropically constrained, the localization behavior of B-grafted nanoparticles is found to be qualitatively different from that of A-grafted particles. The absence of free ends and the bridge conformation of the mid-block tend to reduce the spatial segregation of B-grafted particles at the center of the B-domain, a behavior in contrast to an AB diblock copolymer. Under similar conditions, while A-grafted particles self-assemble at the center of the A-domain, the B-grafted particles with a non-selective core segregate predominantly at the interface of A and B domains, especially when the particle size is large or grafting is weak. Upon increasing the grafting density, the morphology transitions from interface to center localization. The spatial localization of particles, governed by the interplay of enthalpic and entropic contributions to the free energy, is found to be strongly influenced by particle size, selectivity, volume fraction, and number and size of grafted chains. Controlling the self-assembly behavior of particles by tuning these parameters will be immensely helpful in designing advanced nanostructured materials with desired physical properties.

Stability analysis of a thinning electrified jet under nonisothermal conditions.

The linear stability of a jet propagating under an electric field is analyzed under nonisothermal conditions. The electrified jet of a Newtonian fluid is modeled as a slender filament, and the leaky dielectric model is used to account for the Maxwell stresses within the fluid. The convective heat transfer from high-temperature jet to the surroundings results in formation of thicker fibers owing to increased viscosity upon cooling. The jet exhibiting substantial thinning under the action of tangential electric field is examined for stability toward axisymmetric nonperiodic disturbances. This is in contrast to most prior studies which analyzed the stability of a cylindrical jet of uniform radius without thinning under extensional flow by examining only periodic disturbances. Two case studies of reference fluids differing in viscosity and electrical properties are examined. The spectrum of discrete growth rates for axisymmetric disturbances reveal qualitatively distinct instabilities for the two fluids. For a fluid with high electrical conductivity, the conducting mode driven by the coupling of surface charges and an external electric field is found to be the dominant mode of instability. On the contrary, for low conductivity materials, the surface-tension-driven capillary mode is found to be the most critical mode. Heat transfer from the jet to the surroundings tends to stabilize both types of instability mode. Under sufficiently strong heat transfer, the axisymmetric instability, which is believed to be responsible for producing nanofibers with diametric oscillations in electrospinning process, is suppressed. The stabilization is attributed to the enhancement of viscous stress in the thinning jet upon cooling. It is observed that the stabilization effect is relatively more pronounced in a thinning jet compared to the cylindrical jet of uniform radius. The effects of various material and process parameters on the stability behavior is also examined.

Self-Assembly of Polymer Grafted Nanoparticles within Spherically Confined Diblock Copolymers.

Geometric confinement plays an important role in the generation of interesting microstructures on account of structural frustration and confinement-induced entropy loss. In the present study, self-consistent field calculations have been performed to examine the self-assembly behavior of a mixture of diblock copolymers and polymer grafted nanoparticles within a spherical confinement. The analysis is aimed at obtaining the equilibrium distribution of nanoparticles with a high degree of order. The ordered mesophases of diblock copolymers provide useful templates to achieve ordering of nanoparticles in a selective domain. Self-assembly of nanoparticles within frustrated diblock copolymers is found to be very different from the bulk. A rich variety of equilibrium morphologies are observed depending on the degree of confinement and the extent of particle loading. In addition, the role of particle size and selectivity along with the length and the number of polymer chains grafted onto the surface of nanoparticles are analyzed to understand the self-assembly behavior. The specific interest is to obtain the chiral structures out of achiral block copolymers subjected to spherical confinement. The realization of various captivating microstructures, such as chiral ordering of nanoparticles, is highly essential to produce advanced nanomaterials with superior physical properties.

Weakly nonlinear analysis of viscous instability in flow past a neo-Hookean surface.

We analyze the stability of the plane Couette flow of a Newtonian fluid past an incompressible deformable solid in the creeping flow limit where the viscous stresses in the fluid (of the order eta_{f}VR ) are comparable with the elastic stresses in the solid (of the order G ). Here, eta_{f} is the fluid viscosity, V is the top-plate velocity, R is the channel width, and G is the shear modulus of the elastic solid. For (eta_{f}VGR)=O(1) , the flexible solid undergoes finite deformations and is, therefore, appropriately modeled as a neo-Hookean solid of finite thickness which is grafted to a rigid plate at the bottom. Both linear as well as weakly nonlinear stability analyses are carried out to investigate the viscous instability and the effect of nonlinear rheology of solid on the instability. Previous linear stability studies have predicted an instability as the dimensionless shear rate Gamma=(eta_{f}VGR) is increased beyond the critical value Gamma_{c} . The role of viscous dissipation in the solid medium on the stability behavior is examined. The effect of solid-to-fluid viscosity ratio eta_{r} on the critical shear rate Gamma_{c} for the neo-Hookean model is very different from that for the linear viscoelastic model. Whereas the linear elastic model predicts that there is no instability for H

Axisymmetric instability in a thinning electrified jet.

The axisymmetric stability of an electrified jet is analyzed under electrospinning conditions using the linear stability theory. The fluid is considered Newtonian with a finite electrical conductivity, modeled as a leaky dielectric medium. While the previous studies impose axisymmetric disturbances on a cylindrical jet of uniform radius, referred to as the base state, in the present study the actual thinning jet profile, obtained as the steady-state solution of the one-dimensional slender filament model, is treated as the base state. The analysis takes into account the role of variation in the jet variables like radius, velocity, electric field, and surface charge density along the thinning jet in the stability behavior. The eigenspectrum of the axisymmetric disturbance growth rate is constructed from the linearized disturbance equations discretized using the Chebyshev collocation method. The most unstable growth rate for the thinning jet is significantly different from that for the uniform radius jet. For the same electrospinning conditions, while the uniform radius jet is predicted to be highly unstable, the thinning jet profile is found to be unstable but with a relatively very low growth rate. The stabilizing role of the thinning jet is attributed to the variation in the surface charge density as well as the extensional deformation rate in the fluid ignored in the uniform radius jet analysis. The dominant mode for the thinning jet is an oscillatory conducting mode driven by the field-charge coupling. The disturbance energy balance finds the electric force to be the dominant force responsible for the disturbance growth, potentially leading to bead formation along the fiber. The role of various material and process parameters in the stability behavior is also investigated.

Wall-mode instability in plane shear flow of viscoelastic fluid over a deformable solid.

The linear stability analysis of a plane Couette flow of an Oldroyd-B viscoelastic fluid past a flexible solid medium is carried out to investigate the role of polymer addition in the stability behavior. The system consists of a viscoelastic fluid layer of thickness R, density ρ, viscosity η, relaxation time λ, and retardation time ßλ flowing past a linear elastic solid medium of thickness HR, density ρ, and shear modulus G. The emphasis is on the high-Reynolds-number wall-mode instability, which has recently been shown in experiments to destabilize the laminar flow of Newtonian fluids in soft-walled tubes and channels at a significantly lower Reynolds number than that for flows in rigid conduits. For Newtonian fluids, the linear stability studies have shown that the wall modes become unstable when flow Reynolds number exceeds a certain critical value Re(c) which scales as Σ(3/4), where Reynolds number Re=ρVR/η,V is the top-plate velocity, and dimensionless parameter Σ=ρGR(2)/η(2) characterizes the fluid-solid system. For high-Reynolds-number flow, the addition of polymer tends to decrease the critical Reynolds number in comparison to that for the Newtonian fluid, indicating a destabilizing role for fluid viscoelasticity. Numerical calculations show that the critical Reynolds number could be decreased by up to a factor of 10 by the addition of small amount of polymer. The critical Reynolds number follows the same scaling Re(c)∼Σ(3/4) as the wall modes for a Newtonian fluid for very high Reynolds number. However, for moderate Reynolds number, there exists a narrow region in ß-H parametric space, corresponding to very dilute polymer solution (0.9≲ß<1) and thin solids (H≲1.1), in which the addition of polymer tends to increase the critical Reynolds number in comparison to the Newtonian fluid. Thus, Reynolds number and polymer properties can be tailored to either increase or decrease the critical Reynolds number for unstable modes, thus providing an additional degree of control over the laminar-turbulent transition.