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Register a new userPhase Behavior of Poly(N-isopropylacrylamide) Nanogel dispersions: Temperature Dependent Particle Size and Interactions
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Added by
Butchi V. R. Tata Dr.
Publication date
2008
fields
Physics
and research's language is
English
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The phase behavior of poly (N-isopropylacrylamide) nanoparticles dispersed in aqueous medium is investigated as a function of temperature using static and dynamic light scattering techniques. The diameter, d of the particles, as determined by dynamic light scattering measurements on dilute dispersion showed a decrease in size from 273 nm at 25C to 114 nm at 40C as function of temperature with a sudden collapse of particle volume (volume phase transition) at 32.4C. Further this nanoparticle dispersion is found to turn turbid beyond volume phase transition. Static light scattering measurements on samples with intermediate concentration and high concentration showed liquid-like order and crystalline order respectively. The intensity of the Bragg peak of the crystallized sample when monitored as a function of temperature showed crystal to liquid transition at 26.2C and a fluid to fluid transition at 31C. The occurrence of melting at a volume fraction of 0.85 and the absence of change in number density across the fluid-to-fluid transition suggest that interparticle interaction is repulsive soft-sphere below the volume phase transition. The reported results on the phase behavior of poly(N-isopropylacrylamide) nanogel suspensions are discussed in the light of the present results.
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Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of different sizes are synthesized by varying the concentration of sodium dodecyl sulphate (SDS) in a one-pot method. The sizes, size polydispersities and the thermoresponsivity of the PNIPAM particles are characterized by using dynamic light scattering and scanning electron microscopy. It is observed that the sizes of these particles decrease with increase in SDS concentration. Swelling ratios of PNIPAM particles measured from the thermoresponsive curves are observed to increase with decrease in particle size. This observation is understood by minimizing the Helmholtz free energy of the system with respect to the swelling ratio of the particles. Finally, the dynamics of these particles in jammed aqueous suspensions are investigated by performing rheological measurements.
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.
A high-resolution calorimetric spectroscopy study has been performed on pure glycerol and colloidal dispersions of an aerosil in glycerol covering a wide range of temperatures from 300 K to 380 K, deep in the liquid phase of glycerol. The colloidal glycerol+aerosil samples with 0.05, 0.10, and 0.20 mass fraction of aerosil reveal glassy, activated dynamics at temperatures well above the $T_g$ of the pure glycerol. The onset of glass-like behavior appears to be due to the structural frustration imposed by the silica gel on the glycerol liquid. The aerosil gel increases the net viscosity of the mixture, placing the sample effectively at a lower temperature thus inducing a glassy state. Given the onset of this behavior at relatively low aerosil density (large mean-void length compared to the size of a glycerol molecule), this induced glassy behavior is likely due to a collective mode of glycerol molecules. The study of frustrated glass-forming systems may be a unique avenue for illuminating the physics of glasses.
When systems that can undergo phase separation between two coexisting phases in the bulk are confined in thin film geometry between parallel walls, the phase behavior can be profoundly modified. These phenomena shall be described and exemplified by computer simulations of the Asakura-Oosawa model for colloid-polymer mixtures, but applications to other soft matter systems (e.g. confined polymer blends) will also be mentioned. Typically a wall will prefer one of the phases, and hence the composition of the system in the direction perpendicular to the walls will not be homogeneous. If both walls are of the same kind, this effect leads to a distortion of the phase diagram of the system in thin film geometry, in comparison with the bulk, analogous to the phenomenon of capillary condensation of simple fluids in thin capillaries. In the case of competing walls, where both walls prefer different phases of the two phases coexisting in the bulk, a state with an interface parallel to the walls gets stabilized. The transition from the disordered phase to this soft mode phase is rounded by the finite thickness of the film and not a sharp phase transition. However, a sharp transition can occur where this interface gets localized at (one of) the walls. The relation of this interface localization transition to wetting phenomena is discussed. Finally, an outlook to related phenomena is given, such as the effects of confinement in cylindrical pores on the phase behavior, and more complicated ordering phenomena (lamellar mesophases of block copolymers or nematic phases of liquid crystals under confinement).
Auger recombination (AR) of the ground biexciton state in quantum-confined lead salt nanowires (NWs) with a strong coupling between the conduction and the valence bands is shown to be strongly suppressed, and only excited biexciton states contribute to Auger decay. The AR rate is predicted to be greatly reduced when temperature or the NW radius are decreased, and the effect is explained by decrease in both the population of excited biexciton states and overlap of phonon-broadened single- and biexciton states. Suppression of AR of multiexciton states exhibiting strong radiative decay makes obviously lead salt NWs a subject of special interest for numerous lasing applications.
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