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Register a new userInfluence of particle size on the thermoresponsive and rheological properties of aqueous poly(N-isopropylacrylamide) colloidal suspensions
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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.
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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.
We fabricated thermoresponsive colloidal molecules of ca. 250 nm size. Electron- and scanning force microscopy reveal the dumbbell-shaped morphology. The temperature dependence of the size and aspect ratio (ca. 1.4 to 1.6) is analyzed by depolarized dynamic light scattering and found to be in good agreement with microscopic evidence.
Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of a nearly constant swelling ratio and with polydispersity indices (PDIs) varying over a wide range (7.4% - 48.9%) are synthesized to study the effects of polydispersity on the dynamics of suspensions of soft PNIPAM colloidal particles. The PNIPAM particles are characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). The zero shear viscosity ($eta_{0}$) data of these colloidal suspensions, estimated from rheometric experiments as a function of the effective volume fraction $phi_{eff}$ of the suspensions, increases with increase in $phi_{eff}$ and shows a dramatic increase at $phi_{eff}=phi_{0}$. The data for $eta_{0}$ as a function of $phi_{eff}$ fits well to the Vogel-Fulcher-Tammann (VFT) equation. It is observed that increasing PDIs results in increasingly fragile supercooled liquid-like behavior, with the parameter $phi_{0}$, extracted from the fits to the VFT equation, shifting towards higher $phi_{eff}$. The observed increase in fragility is attributed to the prevalence of dynamical heterogeneities (DHs) in these polydisperse suspensions, while the simultaneous shift in $phi_{0}$ is ascribed to the decoupling of the dynamics of the smallest and largest particles. Finally, it is observed that the intrinsic nonlinearity of these suspensions, estimated at the third harmonic near $phi_{0}$ in Fourier transform oscillatory rheological experiments, increases with increase in PDIs. Our results are in agreement with theoretical predictions and simulation results for polydisperse hard sphere colloidal glasses and clearly demonstrate that jammed suspensions of polydisperse colloidal particles can be effectively fluidized with increasing PDIs.
We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerably reduced as compared to the prediction based on the primitive model. When these forces are repulsive, the long-distance behaviour can be described by an effective Yukawa pair potential with a solvent-renormalized charge. As a function of colloidal volume fraction and added salt concentration, this solvent-renormalized charge behaves qualitatively similar to that obtained via the Poisson-Boltzmann cell model but there are quantitative differences. For divalent counterions and nano-sized colloids, on the other hand, the hydration may lead to overscreened colloids with mutual attraction while the primitive model yields repulsive forces. All these new effects can be accounted for through a solvent-averaged primitive model (SPM) which is obtained from the full model by integrating out the solvent degrees of freedom. The SPM was used to access larger colloidal particles without simulating the solvent explicitly.
Hypothesis: Aging in colloidal suspensions manifests as a reduction in kinetic freedom of the colloids. In aqueous suspensions of charged colloids, the role of inter-particle electrostatics interactions on the aging dynamics is well debated. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging colloids has never been considered before. Laponite, a model hectorite clay, could be used to evaluate the relative contributions of medium structure and electrostatics in determining the physicochemical properties of aging colloidal suspensions. Experiments: The structure of the dispersion medium is modified either by incorporating uncharged/charged kosmotropic (structure-inducing) or chaotropic (structure-disrupting) molecules or by changing suspension temperature. A new protocol, wherein the medium is heated before adding clay particles, is also introduced to evaluate the effects of hydrogen bond disruptions on suspension aging. Dynamic light scattering, rheological measurements and particle-scale imaging are employed to evaluate the physicochemical properties of the suspensions. Findings: A strong influence of medium structure is evident when inter-particle electrostatic interactions are weak. Enhancement and disruption of hydrogen bonds in the medium are, respectively, strongly correlated with acceleration and delay of suspension aging dynamics. The physicochemical properties of charged clay colloidal suspensions are therefore controlled by altering hydrogen bonding in the dispersion medium.
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