ABSTRACT
Responsive hollow microgels are a fascinating class of soft model systems at the crossover between polymer capsules and microgels. The presence of the cavity makes them promising materials for encapsulation and controlled release applications but also confers them an additional softness that is reflected by their peculiar behaviour in bulk and at interfaces. Their responsivity to external stimuli, such as temperature, pH, and ionic strength, can be designed from their synthesis conditions and the choice of functional moieties. So far most studies have focused on "small" hollow microgels that were mostly studied with scattering or atomic force microscopy techniques. In our previous study, we have shown that large fluorescent hollow poly(N-isopropylacrylamide) (PNIPAM) microgels could be synthesized using micrometer-sized silica particles as sacrificial templates allowing their investigation in situ via confocal microscopy. In this work, we extend this approach to charged large hollow microgels based on poly(N-isopropylacrylamide-co-itaconic acid) (P(NIPAM-co-IA)). Hereby, we compare the structure and responsivity of "neutral" (PNIPAM) and "charged" (P(NIPAM-co-IA)) hollow microgel systems synthesized under similar conditions with the same sacrificial template using confocal and atomic force microscopy and light scattering techniques. In particular, we could demonstrate the extremely soft character of the swollen charged hollow microgels and their responsivity to pH, ionic strength, and temperature. To conclude this study, the buckling behavior of the different capsules was investigated illustrating the potential of such systems to change its conformation by varying the osmotic pressure and pH conditions.
ABSTRACT
HYPOTHESIS: While the mechanical disruption of microscopic structures in complex fluids by large shear flows has been studied extensively, the effects of applied strains on the dielectric properties of macromolecular aggregates have received far less attention. Simultaneous rheology and dielectric experiments can be employed to study the dynamics of sheared colloidal suspensions over spatiotemporal scales spanning several decades. EXPERIMENTS: Using a precision impedance analyzer, we study the dielectric behavior of strongly sheared aqueous suspensions of thermoreversible hydrogel poly(N-isopropylacrylamide) (PNIPAM) particles at different temperatures. We also perform stress relaxation experiments to uncover the influence of large deformations on the bulk mechanical moduli of these suspensions. FINDINGS: All the sheared PNIPAM suspensions exhibit distinct dielectric relaxation processes in the low and high frequency regimes. At a temperature below the lower consolute solution temperature (LCST), the complex permittivities of highly dense PNIPAM suspensions decrease with increase in applied oscillatory strain amplitudes. Simultaneously, we note a counter-intuitive slowdown of the dielectric relaxation dynamics. Contrary to our rheo-dielectric findings, our bulk rheology experiments, performed under identical conditions, reveal shear-thinning dynamics with increasing strain amplitudes. We propose the shear-induced rupture of fragile clusters of swollen PNIPAM particles to explain our observations. Our work illustrates that rheo-dielectric studies have enormous potential for providing deep insights into the length scale-dependent dynamical properties of complex systems such as dense suspensions and soft glasses.
Subject(s)
Hydrogels , Water , Suspensions , Rheology , Temperature , Water/chemistryABSTRACT
Physical aging in colloidal dispersions manifests as a reduction in kinetic freedom of the colloids. In aqueous dispersions of charged clay colloids, the role of interparticle electrostatic interactions in determining the aging dynamics has been evaluated extensively. Despite water being the dispersion medium, the influence of water structure on the physicochemical properties of aging clay dispersions has, however, not been considered before. In this work, we use LAPONITE®, a model hectorite clay mineral that acquires surface charges when dispersed in water, to study the relative contributions of dispersion medium structure and interparticle electrostatic interactions on the physicochemical properties of aging hectorite clay dispersions. The structure of the dispersion medium is modified either by incorporating dissociating/non-dissociating kosmotropic (structure-inducing) or chaotropic (structure-disrupting) molecules or by changing dispersion temperature. Photon correlation spectroscopy, rheological measurements and particle-scale imaging are employed to evaluate the physicochemical properties of the dispersions. Our experiments involving incorporation of external additives demonstrate a strong influence of dispersion medium structure on the dispersion properties when the interparticle electrostatic interactions are weak. We introduce a new temperature dependent measurement protocol, wherein the temperature of the medium is fixed before adding the clay particles, to manipulate the hydrogen bonds in the aqueous medium in the absence of external additives. Accelerated aging, observed upon raising the temperature regardless of the experimental thermal histories, is attributed to increased interparticle electrostatic interactions as in the room temperature experiments with ionic additives. Our study identifies that in the presence of weak interparticle electrostatic interactions, changes in the physicochemical properties of charged clay dispersions can be driven by manipulating hydrogen bond populations in aqueous medium.
