Universal Polymeric-to-Colloidal Transition in Melts of Hairy Nanoparticles.

Two different classes of hairy self-suspended nanoparticles in the melt state, polymer-grafted nanoparticles (GNPs) and star polymers, are shown to display universal dynamic behavior across a broad range of parameter space. Linear viscoelastic measurements on well-characterized silica-poly(methyl acrylate) GNPs with a fixed core radius (Rcore) and grafting density (or number of arms f) but varying arm degree of polymerization (Narm) show two distinctly different regimes of response. The colloidal Regime I with a small Narm (large core volume fraction) is characterized by predominant low-frequency solidlike colloidal plateau and ultraslow relaxation, while the polymeric Regime II with a large Narm (small core volume fractions) has a response dominated by the starlike relaxation of partially interpenetrated arms. The transition between the two regimes is marked by a crossover where both polymeric and colloidal modes are discerned albeit without a distinct colloidal plateau. Similarly, polybutadiene multiarm stars also exhibit the colloidal response of Regime I at very large f and small Narm. The star arm retraction model and a simple scaling model of nanoparticle escape from the cage of neighbors by overcoming a hopping potential barrier due to their elastic deformation quantitatively describe the linear response of the polymeric and colloidal regimes, respectively, in all these cases. The dynamic behavior of hairy nanoparticles of different chemistry and molecular characteristics, investigated here and reported in the literature, can be mapped onto a universal dynamic diagram of f/[Rcore3/ν0)1/4] as a function of (Narmν0f)/(Rcore3), where ν0 is the monomeric volume. In this diagram, the two regimes are separated by a line where the hopping potential ΔUhop is equal to the thermal energy, kBT. ΔUhop can be expressed as a function of the overcrowding parameter x (i.e., the ratio of f to the maximum number of unperturbed chains with Narm that can fill the volume occupied by the polymeric corona); hence, this crossing is shown to occur when x = 1. For x > 1, we have colloidal Regime I with an overcrowded volume, stretched arms, and ΔUhop > kBT, while polymeric Regime II is linked to x < 1. This single-material parameter x can provide the needed design principle to tailor the dynamics of this class of soft materials across a wide range of applications from membranes for gas separation to energy storage.

Glassy states in adsorbing surfactant-microgel soft nanocomposites.

Mixtures of polymer-colloid hybrids such as star polymers and microgels with non-adsorbing polymeric additives have received a lot of attention. In these materials, the interplay between entropic forces and softness is responsible for a wealth of phenomena. By contrast, binary mixtures where one component can adsorb onto the other one have been far less studied. Yet real formulations in applications often contain low molecular weight additives that can adsorb onto soft colloids. Here we study the microstructure and rheology of soft nanocomposites made of surfactants and microgels using linear and nonlinear rheology, SAXS experiments, and cryo-TEM techniques. The results are used to build a dynamical state diagram encompassing various liquid, glassy, jammed, metastable, and reentrant liquid states, which results from a subtle interplay between enthalpic, entropic, and kinetic effects. We rationalize the rheological properties of the nanocomposites in each domain of the state diagram, thus providing exquisite solutions for designing new rheology modifiers at will.

Nonmonotonic Stress Relaxation after Cessation of Steady Shear Flow in Supramolecular Assemblies.

Stress relaxation upon cessation of shear flow is known to be described by single-mode or multimode monotonic exponential decays. This is considered to be ubiquitous in nature. However, we found that, in some cases, the relaxation becomes anomalous in that an increase in the relaxing stress is observed. Those observations were made for physicochemically very different systems, having in common, however, the presence of self-associating units generating structures at large length scales. The nonmonotonic stress relaxation can be described phenomenologically by a generic model based on a redistribution of energy after the flow has stopped. When broken bonds are reestablished after flow cessation, the released energy is partly used to locally increase the elastic energy by the formation of deformed domains. If shear has induced order such that these elastic domains are partly aligned, the reestablishing of bonds gives rise to an increase of the overall stress.

Rheological Behavior and in Situ Confocal Imaging of Bijels Made by Mixing.

Bijels (bicontinuous interfacially jammed emulsion gels) have the potential to be useful in many different applications due to their internal connectivity and the possibility of efficient mass transport through the channels. Recently, new methods of making the bijel have been proposed, which simplify the fabrication process, making commercial application more realistic. Here, we study the flow properties of bijels prepared by mixing alone using oscillatory rheology combined with confocal microscopy and also squeezing flow experiments. We found that the bijel undergoes a two-step yielding process where the first step corresponds to the fluidizing of the interface, allowing the motion of the structure, and the second step corresponds to the breaking of the structure. In the squeeze flow experiments, the yield stress of the bijel is observed to show a power law dependence on squeezing speed. However, when stress in excess of yield stress is plotted against shear rate, all the different squeeze flow data show a superposition.

On the universality of the flow properties of soft-particle glasses.

We identify the minimal interparticle interactions necessary for a particle dynamics simulation to predict the structure and flow behaviour of soft particle glasses (SPGs). Generally, two kinds of forces between the particles must be accounted for in simulations of SPGs: viscous or frictional drag forces and elastic contact forces. Far field drag forces are required to dissipate energy in the simulations and capture the effect of the rheology of the suspending fluid. Elastic forces are found to be dominant compared to near-field drag or other forms of friction forces and are the most important component to compute the rheology. The shear stress, the first and second normal stress differences for different interparticle force laws collapse onto universal master curves of the Herschel-Bulkley form by non-dimensionalizing the stress with the yield stress and the shear rate with the viscosity of the suspending fluid divided by the low-frequency shear modulus. The Herschel-Bulkley exponents are close to 0.5 with a slight dependence on the repulsive pairwise elastic forces.

Versatile Encapsulation Technology Based on Tailored pH-Responsive Amphiphilic Polymers: Emulsion Gels and Capsules.

We present a multipurpose technology to encapsulate hydrophobic substances in micron-sized emulsion droplets and capsules. The encapsulating agent is a comblike stimuli-responsive copolymer comprising side-chain surfactants attached to a methacrylic acid/ethyl acrylate polyelectrolyte backbone. The composition and structure of the hydrophobic moieties of the side chains are customized to tune the particle morphology and the processing conditions. The technology exploits the synergy of properties provided by the copolymer: interfacial activity, pH responsiveness, and viscoelasticity. A one-pot process produces emulsion gels or capsule dispersions consisting of a hydrophobic liquid core surrounded by a polymer shell. The dispersions resist high ionic strengths and exhibit long-term stability. The versatility of the method is demonstrated by encapsulating various hydrophobic substances covering a broad range of viscosities and polarities-conventional and technical oils, perfumes, and alkyd paints-with a high degree of morphological and rheological control.

Particle-wall tribology of slippery hydrogel particle suspensions.

Slip is an important phenomenon that occurs during the flow of yield stress fluids like soft materials and pastes. Densely packed suspensions of hydrogel microparticles are used to show that slip is governed by the tribological interactions occurring between the samples and shearing surfaces. Both attractive/repulsive interactions between the dispersed particles and surface, as well as the viscoelasticity of the suspension, are found to play key roles in slip occurring within rheometric flows. We specifically discover that for two completely different sets of microgels, the sliding stress at which slip occurs scales with both the modulus of the particles and the bulk suspension modulus. This suggests that hysteresis losses within the viscoelastic particles contribute to friction forces and thus slip at the particle-surface tribo-contact. It is also found that slip during large amplitude oscillatory shear and steady shear flows share the same generic features.

The glass and jamming transitions of soft polyelectrolyte microgel suspensions.

We explore the influence of particle softness on the state diagram of well characterized polyelectrolyte microgel suspensions using dynamic light scattering and rheology. Upon increasing the polymer concentration, we cross successively the well defined glass and jamming transitions which delimit four different states: dilute colloidal suspension, entropic glass, jammed glass, and dense glass. Each state has a specific dynamical fingerprint dictated by two key ingredients related to particle softness: elastic contact interactions, and osmotic or steric deswelling. Soft interactions control yielding and flow of the jammed glasses. The shrinkage of the microgels makes the glass transition look smoother than in hard sphere suspensions. We quantify the relationship between the polymer concentration and the volume fraction, and show that the glass transition behaviour of soft microgels can be mapped to that of hard sphere glasses once the volume fraction is used as the control parameter.

Dynamical role of slip heterogeneities in confined flows.

We demonstrate that flows in confined systems are controlled by slip heterogeneities below a certain size. To show this we image the motion of soft glassy suspensions in microchannels whose inner walls impose different slip velocities. As the channel height decreases, the flow ceases to have the symmetric shape expected for yield-stress fluids. A theoretical model accounts for the role of slip heterogeneities and captures the velocity profiles. We generalize these results by introducing a length scale, valid for all fluids, below which slip heterogeneities dominate the flow in confined systems. General implications of this notion, concerning the interplay between slip and confinement, are presented.

The viscosity of short polyelectrolyte solutions.

We consider the viscosity of solutions of highly charged short polyelectrolytes. Our system is a poly(styrene-maleic acid) copolymer solution (SMA) with various added salt concentrations in dilute and semidilute regimes. The SMA solutions show some particular features: (i) variations of the specific viscosity measured for different values of concentration and ionic strength can be rescaled on two universal curves when plotted as a function of the effective volume fraction; (ii) the reduced viscosity is proportional to the Debye length. In order to describe the viscosity of such a system we model the motion of the charged rods considering a simpler system: we replace each charged rod and its corresponding charge cloud by an effective neutral rod. This modified system is yet below the concentrated regime and, at most, steric interactions are left. In the semidilute regime, we model the rescaled rods moving under a mean field potential and obtain a dynamical equation for the orientational tensor, considered small, and the viscosity is derived from it. Within our mean field approach, the effects due to the rod Brownian motion and due to the potential cancel each other and the behavior of the viscosity is explained in terms of the effective volume fraction only. Our predictions are in good qualitative agreement with the experimental results over a wide range of parameters, and suggest a method for obtaining the rotational diffusion constant in the semidilute regime.

Microscopic origin of internal stresses in jammed soft particle suspensions.

The long time persistence of mechanical stresses is a generic property of glassy materials. Here we identify the microscopic mechanisms that control internal stresses in highly concentrated suspensions of soft particles brought to rest from steady flow. The persistence of the asymmetric angular distortions which characterize the pair distribution function during flow is at the origin of the internal stresses. Their long time evolution is driven by in-cage rearrangements of the elastic contacts between particles. The trapped macroscopic stress is related to the solvent viscosity, particle elasticity and volume fraction through a universal scaling derived from simulations and experiments.

Order-disorder transition in supramolecular polymers.

In supramolecular polymers, directional interactions control the constituting units connectivity, but dispersion forces may conspire to make complex organizations. Here we report on the long-range order and order-disorder transition (ODT) of main-chain supramolecular polymers based on poly(propylene oxide) (PPO) spacers functionalized on both ends with thymine. Below the ODT temperature (T(ODT)), these compounds are semicrystalline with a lamellar structure, showing nanophase separation between crystallized thymine planes and amorphous PPO layers. Above T(ODT), they are amorphous and homogeneous even though their X-ray scattering spectrum reveals a peak. This peak is due to correlation hole effect resulting from contrast between end-functional groups and spacer. Macroscopically, the transition is accompanied by dramatic flow and mechanical properties changes.

A micromechanical model to predict the flow of soft particle glasses.

Soft particle glasses form a broad family of materials made of deformable particles, as diverse as microgels, emulsion droplets, star polymers, block copolymer micelles and proteins, which are jammed at volume fractions where they are in contact and interact via soft elastic repulsions. Despite a great variety of particle elasticity, soft glasses have many generic features in common. They behave like weak elastic solids at rest but flow very much like liquids above the yield stress. This unique feature is exploited to process high-performance coatings, solid inks, ceramic pastes, textured food and personal care products. Much of the understanding of these materials at volume fractions relevant in applications is empirical, and a theory connecting macroscopic flow behaviour to microstructure and particle properties remains a formidable challenge. Here we propose a micromechanical three-dimensional model that quantitatively predicts the nonlinear rheology of soft particle glasses. The shear stress and the normal stress differences depend on both the dynamic pair distribution function and the solvent-mediated EHD interactions among the deformed particles. The predictions, which have no adjustable parameters, are successfully validated with experiments on concentrated emulsions and polyelectrolyte microgel pastes, highlighting the universality of the flow properties of soft glasses. These results provide a framework for designing new soft additives with a desired rheological response.

Unique slow dynamics and aging phenomena in soft glassy suspensions of multiarm star polymers.

We use time-resolved rheology to elucidate the slow dynamics and aging in highly concentrated suspensions of multiarm star polymers. The linear and nonlinear rheological properties exhibit a terminal regime corresponding to a well-defined maximal relaxation time. Terminal relaxation is driven by arm relaxation which speeds up the escape of stars from their cages. The fact that the system fully relaxes and flows at long times has important consequences. The yield stress only exists in the limited range of frequencies or shear rates where solid-like behavior is observed. Aging is controlled by the total time elapsed after flow cessation and not by the time elapsed from flow cessation to the beginning of the measurement as in other glassy materials. Our results, which demonstrate the importance of particle architecture with respect to glassy dynamics, should be generic for long hairy particles.

Doubly responsive polymer-microgel composites: rheology and structure.

Mixtures of alkali swellable microgels and linear PNIPAm chains exhibit doubly responsive properties both with pH and temperature. Below the lower critical solution temperature (LCST), the linear chains of PNIPAm are soluble and increase the osmotic pressure outside the microgels, which causes them to deswell. Above the LCST, the PNIPAm chains become insoluble and form spherical colloidal particles confined between the microgels that subsequently reswell. The swelling and deswelling of the microgels change the rheological properties of the composites, providing a unique way to tune the elasticity of the composites with temperature. The structure of the composites above the LCST is studied using multiple light scattering and fluorescence confocal microscopy. The phase separation of PNIPAm above the LCST is strongly affected by the confinement of the PNIPAm chains between the microgels.

Colloidal phase separation of concentrated PNIPAm solutions.

In the concentration range of 1-6 wt %, solutions of a thermosensitive polymer (poly-N-isopropylacrylamide (PNIPAm), Mw = 1.4 x 10(5) g.mol(-1)) are shown to phase separate in the form of dense stable colloids of nearly pure polymer. Diffuse wave spectroscopy and small-angle neutron scattering both provide consistent measurements of the colloidal size as a function of temperature. Results are in agreement with a Cahn regime of spinodal decomposition blocked at an early stage, prior to a growth that would lead to a macroscopic phase separation. [Early results of this work were presented at the 231st American Chemical Society National Meeting, Symposium on Amphiphilic Polymers, Atlanta, GA, 2006, March 26-30.].

Control of the chemical cross-linking of gelatin by a thermosensitive polymer: example of switchable reactivity.

Chemical cross-linking of gelatin is achieved using a thermosensitive reactive copolymer based on N-isopropylacrylamide (NIPAM). The copolymer bears 5 mol % acrylic acid units which form amide bonds with the amino groups of gelatin in the presence of a water-soluble carbodiimide. The cross-linking reaction occurs only below the LCST congruent with 34 degrees C (lower critical solution temperature), i.e., when the copolymer is in the coil conformation. Above the LCST the copolymer adopts a globule conformation and its ability to react with gelatin is drastically reduced. By setting the temperature above or below the LCST it is possible to switch off or on the reactivity of the system and control the gelation process. The switch temperature can be set at the desired value by adjusting the composition of the thermosensitive copolymer.

Slip and flow in soft particle pastes.

Concentrated dispersions of soft particles are shown to exhibit a generic slip behavior near smooth surfaces. Slip results from a balance between osmotic forces and noncontact elastohydrodynamic interaction between the squeezed particles and the wall. A model is presented that predicts the slip properties and provides insight into the behavior of the bulk paste.

Glassy dynamics and flow properties of soft colloidal pastes.

The local dynamics and the nonlinear rheology of soft colloidal pastes are shown to exhibit a remarkable universal behavior in terms of a unique microscopic time scale. This variable is associated with structural relaxation under the combined action of local frictional forces and elastic driving forces. These results establish a link between the local dynamics of pastes and their nonlinear flow behavior and provide a unified description of paste rheology.

Static and dynamic properties of highly turbid media determined by spatially resolved diffusive-wave spectroscopy.

We show that spatially resolved backscattering can be used for simultaneous measurements of static and dynamic properties of highly turbid media. The spatial variation of the backscattered intensity gives access to the transport men free path. The decay of the temporal intensity-intensity correlation function depends on the point of observation. This property can be used to probe complex dynamics with several time scales. The implementation of the method and the data analysis are tested on concentrated suspensions of polystyrene spheres.