Matthew E. Helgeson

Rheology and spatially resolved structure of cetyltrimethylammonium bromide wormlike micelles through the shear banding transition

We present the first combined study of spatially resolved structure and shear rheology for a model shear banding fluid comprised of cetyltrimethylammonium bromide wormlike micelles. Combining conventional rheometry, velocimetry, flow birefringence, and flow-small angle neutron scattering (flow-SANS) in the 1–2 (flow-gradient) plane of shear completely characterizes shear banding in the system and enables comparison of local flow kinematics to local segmental orientation and alignment within the bands. The Giesekus constitutive equation with stress diffusion is shown to successfully model the viscoelasticity, steady shear viscosity, and shear banding kinematics. Flow-SANS measurements in the 1–2 plane exhibit a critical alignment and orientation required for shear banding, followed by a first order orientational transition to a paranematic state in the high-shear band. Master curves of the segmental orientation and alignment are constructed by comparing the local structural features to the locally observed...

Mesoporous organohydrogels from thermogelling photocrosslinkable nanoemulsions

We report the formation of mesoporous organohydrogels from oil-in-water nanoemulsions containing an end-functionalized oligomeric gelator in the aqueous phase. The nanoemulsions exhibit an abrupt thermoreversible transition from a low-viscosity liquid to a fractal-like colloidal gel of droplets with mesoscale porosity and solid-like viscoelasticity with moduli approaching 100 kPa, possibly the highest reported for an emulsion-based system. We hypothesize that gelation is brought about by temperature-induced interdroplet bridging of the gelator, as shown by its dependence on the gelator chemistry. The use of photocrosslinkable gelators enables the freezing of the nanoemulsions microstructure into a soft hydrogel nanocomposite containing a large fraction of dispersed liquid hydrophobic compartments, and we show its use in the encapsulation and release of lipophilic biomolecules. The tunable structural, mechanical and optical properties of these organohydrogels make them a robust material platform suitable for a wide range of applications.

Gel-Induced Selective Crystallization of Polymorphs

Although nanoporous materials have been explored for controlling crystallization of polymorphs in recent years, polymorphism in confined environments is still poorly understood, particularly from a kinetic perspective, and the role of the local structure of the substrate has largely been neglected. Herein, we report the use of a novel material, polymer microgels with tunable microstructure, for controlling polymorph crystallization from solution and for investigating systematically the effects of nanoconfinement and interfacial interactions on polymorphic outcomes. We show that the polymer microgels can improve polymorph selectivity significantly. The polymorphic outcomes correlate strongly with the gel-induced nucleation kinetics and are very sensitive to both the polymer microstructure and the chemical composition. Further mechanistic investigations suggest that the nucleation-templating effect and the spatial confinement imposed by the polymer network may be central to achieving polymorph selectivity. We demonstrate polymer microgels as promising materials for controlling crystal polymorphism. Moreover, our results help advance the fundamental understanding of polymorph crystallization at complex interfaces, particularly in confined environments.

Viscoelasticity and shear melting of colloidal star polymer glasses

Dispersions of multiarm star polymers in an athermal solvent are studied as a model system to explore the effects of soft colloidal interactions on the dynamics of colloidal glasses. Linear viscoelastic measurements in the glassy state are congruent with Mode Coupling Theory predictions for hard sphere glasses at moderate frequencies, indicating similarities in the relaxation processes of hard and soft colloidal glasses near equilibrium. On the other hand, distinct features of the star relaxation (related to arm disengagement) are observed to affect the nonlinear behavior associated with shear melting of the glass, which exhibits transitions previously unreported for hard sphere systems. Whereas a single maximum in G″(γ) is evident under large amplitude oscillatory shear at frequencies near the beta relaxation, secondary transitions between yielding and the onset of macroscopic flow are observed at higher and lower frequencies. The latter are annealed out upon complete fluidization of the star polymer sus...

Controlled Nucleation from Solution Using Polymer Microgels

Despite its widespread occurrence in nature and broad application in industrial practice, nucleation of crystalline materials remains largely unpredictable and therefore difficult to control. In this work, we demonstrate a new method to control nucleation with polymer microgels by tuning their microstructure to vary systematically the degree of nanoscopic confinement and its effects on nucleation. We find that the polymer microstructure has a significant impact on nucleation kinetics. Moreover, there exists an optimum polymer mesh size at which the rate of nucleation is dramatically enhanced, the degree to which depends on the extent of polymer-solute interactions. With easily tunable microstructure and chemistry, polymer microgels offer a promising approach for the rational design of materials for controlling nucleation from solution.

Relating shear banding, structure, and phase behavior in wormlike micellar solutions

The rheological behavior of concentrated cationic wormlike micellar surfactant solutions (cetyltrimethylammonium bromide) near the isotropic–nematic (I–N) transition is studied as a function of composition and temperature to determine the relationship between shear banding, fluid microstructure and underlying equilibrium phase behavior. The combination of conventional rheometry, velocimetry, and spatially-resolved flow-small angle neutron scattering allows detailed exploration of the differences between shear banding and non-shear banding solutions. The shear rheology of isotropic WLM solutions are shown to be well-described by the Giesekus constitutive model, which provides a quantitative discrimination between banding and non-banding wormlike micellar fluids through the drag anisotropy coupling parameter. This anisotropy parameter is shown to correlate with the order parameter describing the relative distance to the equilibrium I–N transition. Combining this information with measurements of the critical shear rates for shear banding allows the construction of a non-equilibrium state diagram for the shear banding fluid in terms of the Weissenberg number and the compositional order parameter.

A systematic study of equilibrium structure, thermodynamics, and rheology of aqueous CTAB/NaNO3 wormlike micelles

We present a systematic study of the self-assembly of wormlike micelles (WLMs) comprised of cetyltrimethylammonium bromide (CTAB) and sodium nitrate (NaNO(3)) in aqueous solution as a function of CTAB concentration, NaNO(3) concentration, and temperature throughout the dilute and semi-dilute regions of the phase diagram where linear micelles are observed. Combining measurements using isothermal titration calorimetry, rheometry, flow-birefringence, cryo-transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS) enables complete characterization of the structure, thermodynamics, and rheology of CTAB/NaNO(3) micelles. The addition of NaNO(3) is found to increase the micellization enthalpy as well as the micellar scission energy, resulting in the elongation and growth of WLMs. We find quantitative agreement between the scission energy determined from rheology and the enthalpy of micellization determined from ITC, as well as for contour lengths extracted from rheology and SANS. At fixed molar ratio of NaNO(3) and CTAB, the solution rheology exhibits scaling consistent with dilute, semi-dilute overlapping, and semi-dilute entangled regimes typically found in polymer solutions, as confirmed by cryo-TEM and SANS. The transition between these scaling regimes coincides with the structural transitions identified by SANS. The results validate the relationship between structural parameters and rheological behavior underlying theories for ionic WLMs.

Microstructure and shear rheology of entangled wormlike micelles in solution

The shear rheology of a model wormlike micellar solution exhibits moderate shear thinning and curved flow velocity profiles without discontinuity (nonbanding case). The shear rheology and the flow kinematics are analyzed within the framework of the Giesekus constitutive equation. Macroscopically, the steady state flow curve of the solution exhibits shear thinning with a shear exponent <1 without hysteresis, indicative of a sample that does not shear band. The microstructure of the micellar network is probed by the combination of dynamic rheology, rheo-optics, and SANS. Flow kinematics in a Couette geometry are measured by particle tracking velocimetry and found to be consistent with predictions of the Giesekus constitutive equation fit to the bulk shear rheology. 1-2 plane SANS measurements of the segmental alignment under shear are also found to be in agreement with predictions of the constitutive equation, providing a coherent picture of the mechanisms by which wormlike micelles flow and shear thin. The...

Nanoemulsion Composite Microgels for Orthogonal Encapsulation and Release

Polymer hydrogels and microgels have been widely exploited for the controlled storage, delivery and detection of active compounds, including small molecules and biologics. [ 1 , 2 ] However, due to their intrinsically hydrated microenvironment, the development of hydrogels for encapsulation and/or release of poorly water-soluble cargos remains a persistent challenge. [ 3 ] As such, the development of novel hydrogels with well-controlled hydrophobic compartments remains important to a number of delivery applications including pharmaceuticals, [ 3 , 4 ] cosmetics, [ 5 ]

Microstructure and nonlinear signatures of yielding in a heterogeneous colloidal gel under large amplitude oscillatory shear

We investigate yielding in a colloidal gel that forms a heterogeneous structure, consisting of a two-phase bicontinuous network of colloid-rich domains of fractal clusters and colloid-poor domains. Combining large amplitude oscillatory shear measurements with simultaneous small and ultra-small angle neutron scattering (rheo-SANS/USANS), we characterize both the nonlinear mechanical processes and strain amplitude-dependent microstructure underlying yielding. We observe a broad, three-stage yielding process that evolves over an order of magnitude in strain amplitude between the onset of nonlinearity and flow. Analyzing the intracycle response as a sequence of physical processes reveals a transition from elastic straining to elastoplastic thinning (which dominates in region I) and eventually yielding (which evolves through region II) and flow (which saturates in region III), and allows quantification of instantaneous nonlinear parameters associated with yielding. These measures exhibit significant strain rate amplitude dependence above a characteristic frequency, which we argue is governed by poroelastic effects. Correlating these results with time-averaged rheo-USANS measurements reveals that the material passes through a cascade of structural breakdown from large to progressively smaller length scales. In region I, compression of the fractal domains leads to the formation of large voids. In regions II and III, cluster-cluster correlations become increasingly homogeneous, suggesting breakage and eventually depercolation of intercluster bonds at the yield point. All significant structural changes occur on the micron-scale, suggesting that large-scale rearrangements of hundreds or thousands of particles, rather than the homogeneous rearrangement of particle-particle bonds, dominate the initial yielding of heterogeneous colloidal gels.