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Register a new userPhase behavior and dynamics of a micelle-forming triblock copolymer system
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Added by
Ranjini Bandyopadhyay
Publication date
2008
fields
Physics
and research's language is
English
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Synperonic F-108 (generic name, pluronic) is a micelle forming triblock copolymer of type ABA, where A is polyethylene oxide (PEO) and B is polypropylene oxide (PPO). At high temperatures, the hydrophobicity of the PPO chains increase, and the pluronic molecules, when dissolved in an aqueous medium, self-associate into spherical micelles with dense PPO cores and hydrated PEO coronas. At appropriately high concentrations, these micelles arrange in a face centred cubic lattice to show inverse crystallization, with the samples exhibiting high-temperature crystalline and low-temperature fluidlike phases. By studying the evolution of the elastic and viscous moduli as temperature is increased at a fixed rate, we construct the concentration-temperature phase diagram of Synperonic F-108. For a certain range of temperatures and at appropriate sample concentrations, we observe a predominantly elastic response. Oscillatory strain amplitude sweep measurements on these samples show pronounced peaks in the loss moduli, a typical feature of soft solids. The soft solid-like nature of these materials is further demonstrated by measuring their frequency dependent mechanical moduli. The storage moduli are significantly larger than the loss moduli and are almost independent of the applied angular frequency. Finally, we perform strain rate frequency superposition (SRFS) experiments to measure the slow relaxation dynamics of this soft solid.
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We examined the kinetics of the transformation from the lamellar (LAM) to the hexagonally packed cylinder (HEX) phase for the triblock copolymer, polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) in dibutyl phthalate (DBP), a selective solvent for polystyrene (PS), using time-resolved small angle x-ray scattering (SAXS). We observe the HEX phase with the EB block in the cores at a lower temperature than the LAM phase due to the solvent selectivity of DBP for the PS block. Analysis of the SAXS data for a deep temperature quench well below the LAM-HEX transition shows that the transformation occurs in a one-step process. We calculate the scattering using a geometric model of rippled layers with adjacent layers totally out of phase during the transformation. The agreement of the calculations with the data further supports the continuous transformation mechanism from the LAM to HEX for a deep quench. In contrast, for a shallow quench close to the OOT we find agreement with a two-step nucleation and growth mechanism.
Photon correlation spectroscopy and rheological measurements are performed to investigate the microscopic dynamics and mechanical responses of aqueous solutions of triblock copolymers and aqueous mixtures of triblock copolymers and anionic surfactants. Increasing the concentration of triblock copolymers results in a sharp increase in the magnitude of the complex moduli characterising the samples. This is understood in terms of the changes in the aggregation and packing behaviours of the copolymers and the constraints imposed upon their dynamics due to increased close packing. The addition of suitable quantities of an anionic surfactant to a strongly elastic copolymer solution results in a decrease in the complex moduli of the samples by several decades. It is argued that the shape anisotropy and size polydispersity of the micelles comprising mixtures cause dramatic changes in the packing behaviour, resulting in sample unjamming and the observed decrease in complex moduli. Finally, a phase diagram is constructed in the temperature-surfactant concentration plane to summarise the jamming-unjamming behaviour of aggregates constituting triblock copolymer-anionic surfactant mixtures.
Using dissipative particle dynamics (DPD) simulation method, we study the phase separation dynamics in block copolymer (BCP) melt in $d=3$, subjected to external stimuli such as light. An initial homogeneous BCP melt is rapidly quenched to a temperature $T < T_c$, where $T_c$ is the critical temperature. We then let the system go through alternate light on and off cycles. An on-cycle breaks the stimuli-sensitive bonds connecting both the blocks A and B in BCP melt, and during the off-cycle, broken bonds reconnect. By simulating the effect of light, we isolate scenarios where phase separation begins with the light off (set 1); the cooperative interactions within the system allow it to undergo microphase separation. When the phase separation starts with the light on (set 2), the system undergoes macrophase separation due to the bond breaking. Here, we report the role of alternate cycles on domain morphology by varying bond-breaking probability for both the sets 1 and 2, respectively. We observe that the scaling functions depend upon the conditions mentioned above that change the time scale of the evolving morphologies in various cycles. However, in all the cases, the average domain size respects the power-law growth: $R(t)sim t^{phi}$ at late times, here $phi$ is the dynamic growth exponent. After a short-lived diffusive growth ($phi sim 1/3$) at early times, $phi$ illustrates a crossover from the viscous hydrodynamic ($phi sim 1$) to the inertial hydrodynamic ($phi sim 2/3$) regimes at late times.
The adsorption of a single multi-block $AB$-copolymer on a solid planar substrate is investigated by means of computer simulations and scaling analysis. It is shown that the problem can be mapped onto an effective homopolymer adsorption problem. In particular we discuss how the critical adsorption energy and the fraction of adsorbed monomers depend on the block length $M$ of sticking monomers $A$, and on the total length $N$ of the polymer chains. Also the adsorption of the random copolymers is considered and found to be well described within the framework of the annealed approximation. For a better test of our theoretical prediction, two different Monte Carlo (MC) simulation methods were employed: a) off-lattice dynamic bead-spring model, based on the standard Metropolis algorithm (MA), and b) coarse-grained lattice model using the Pruned-enriched Rosenbluth method (PERM) which enables tests for very long chains. The findings of both methods are fully consistent and in good agreement with theoretical predictions.
We have used the Scheutjens-Fleer self-consistent field (SF-SCF) method to predict the self-assembly of triblock copolymers with a solvophilic middle block and sufficiently long solvophobic outer blocks. We model copolymers consisting of polyethylene oxide (PEO) as solvophilic block and poly(lactic-co-glycolic) acid (PLGA) or poly({ko}-caprolactone) (PCL) as solvophobic block. These copolymers form structurally quenched spherical micelles provided the solvophilic block is long enough. Predictions are calibrated on experimental data for micelles composed of PCL-PEO-PCL and PLGA-PEO-PLGA triblock copolymers prepared via the nanoprecipitation method. We establish effective interaction parameters that enable us to predict various micelle properties such as the hydrodynamic size, the aggregation number and the loading capacity of the micelles for hydrophobic species that are consistent with experimental finding.
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