Biomedical subjects

Nitash P Balsara

Publications and source records attributed to Nitash P Balsara.

8 recordsLinked to original sources

PubMed2006

Electrochemically controlled self-assembly of an organometallic block copolymer.

A new means of controlling the order-disorder transition of block copolymers is presented. By applying small electrical potentials (2 V/cm) to disordered solutions of an organometallic block copolymer, oriented ordered grains were obtained near the positive electrode. After reversing the electrical bias on the system, the ordered grains disappeared, and new, oriented, ordered regions were formed at the opposite electrode. Our work establishes the concept of electrochemical self-assembly for controlling order formation in block copolymers.

Journal Article↗

PubMed2006

Diblock copolymer surfactant transport across the interface between two homopolymers.

Dynamics of adsorption and desorption of a diblock copolymer to an interface between two homopolymers was measured using dynamic secondary-ion mass spectrometry (SIMS). Thin films were constructed consisting of a layer of saturated polybutadiene with 90% 1,2-addition (sPB90), followed by a layer of saturated polybutadiene with 63% 1,2-addition (sPB63), and finally by another layer of the sPB90 homopolymer. A sPB90-sPB63 diblock copolymer was initially included only in the top sPB90 layer of the film at a volume fraction of 0.05. The thin films were annealed at ambient temperature for times ranging between 0.2 and 108 h, and the concentration profiles of the diblock copolymer through the films were measured using SIMS. The dynamics of adsorption and desorption of the diblock copolymer at the two sPB90-sPB63 interfaces was gauged by comparing the different transient concentration profiles. The sorption process was modeled as diffusion in an external field, generated from self-consistent field theory (SCFT). All parameters for the model were determined independently. Although the model neglects the dynamics of conformational change, experimental results matched theory very well.

Polymers↗

PubMed2006

Relationship between macroscopic and microscopic models of surfactant adsorption dynamics at fluid interfaces.

In a companion preceding paper, we presented an experimental investigation into the adsorption dynamics of a diblock copolymer surfactant to a polymer/polymer interface and found them to be well-described by a microscopic model of diffusion in a potential generated using self-consistent field theory. We compare the predictions of the microscopic approach with a macroscopic (adsorption-diffusion) model and demonstrate the equivalence of the two models when the free-energy well underlying surfactant adsorption is flanked by barriers that are significantly larger than thermal energy (kT). However, when the energy barriers are nonexistent, as is the case for the experimental system of interest, a finite interfacial width must be introduced into the classical model to obtain physically meaningful results (i.e., nonnegative desorption rates). Surprisingly, we find that the predictions of the macroscopic finite interfacial width model with no adjustable parameters are in excellent agreement with experimental data presented in the companion paper even though the latter was obtained with molecular resolution. This agreement provides insight into aspects of the free-energy landscape that determine surfactant transport.

Adsorption↗

PubMed2006

Relationship between structural and stress relaxation in a block-copolymer melt.

The relationship between structural relaxation on molecular length scales and macroscopic stress relaxation was explored in a disordered block-copolymer melt. Experiments show that the structural relaxation time, measured by x-ray photon correlation spectroscopy is larger than the terminal stress relaxation time, measured by rheology, by factors as large as 100. We demonstrate that the structural relaxation data are dominated by the diffusion of intact micelles while the stress relaxation data are dominated by contributions due to disordered concentration fluctuations.

Journal Article↗

PubMed2006

Neutron scattering and monte carlo determination of the variation of the critical nucleus size with quench depth.

We have used a combination of neutron scattering experiments and Monte Carlo simulations to study the initial stages of first-order phase transitions. We focus on quenches wherein the nascent phase is formed by homogeneous nucleation, and we approach the spinodal, i.e., the quench depth at which the original phase becomes unstable. In this regime, we show how critical nuclei sizes are determined from neutron scattering structure factors. Prevailing thought is that the size of the critical nucleus should increase with increasing quench depth and diverge at the spinodal. To the contrary, our experiments and simulations indicate that the critical nucleus size decreases monotonically as quench depth is increased and is finite at the spinodal.

Journal Article↗

PubMed2005

Does coarsening begin during the initial stages of spinodal decomposition?

The initial stages of spinodal decomposition were studied by subjecting a critical blend of model polyolefins to a pressure quench and monitoring the evolution by time-resolved small angle neutron scattering. Contrary to the predictions of the widely accepted Cahn-Hilliard-Cook theory, we demonstrate that coarsening of the phase-separated structure begins immediately after the quench and occurs throughout the initial stages of spinodal decomposition.

Journal Article↗

PubMed2004

Effect of chemical oxidation on the self-assembly of organometallic block copolymers.

The thermodynamic interactions in poly(styrene-block-ferrocenyldimethylsilane) and poly(isoprene-block-ferrocenyldimethylsilane) copolymers were systematically tuned by oxidation of the ferrocene moieties with silver nitrate. Small-angle X-ray scattering experiments show that oxidizing 8% of the ferrocene moieties lowers the order-disorder transition temperature of the copolymers by as much as 40 degrees C.

Butadienes↗

PubMed2003

Responsive solids from cross-linked block copolymers.

Novel responsive solids were prepared by randomly cross-linking the polyisoprene chains of a disordered polystyrene-polyisoprene block copolymer. Our experiments show that block copolymer chains, composed of hundreds of repeat units, can undergo reversible order-disorder transitions despite the quenched randomness that arises due to the attachment of one of the blocks to a cross-linked network. The structure, properties, and phase behavior of these materials are determined by a delicate interplay between the density of cross-links and the nature of the ordered state.

Journal Article↗