Daniel L. Blair

Robust Organogels from Nitrogen-Containing Derivatives of (R)-12-Hydroxystearic Acid as Gelators: Comparisons with Gels from Stearic Acid Derivatives†

Thirteen members of a new class of low molecular-mass organogelators (LMOGs), amides, and amines based on (R)-12-hydroxystearic acid (HSA; i.e., (R)-12-hydroxyoctadecanoic acid) and the properties of their gels have been investigated by a variety of structural and thermal techniques. The abilities of these LMOGs, molecules with primary and secondary amide and amine groups and the ammonium carbamate salt of 1-aminooctadecan-12-ol, to gelate a wide range of organic liquids have been ascertained. Their gelating efficiencies are compared with those of HSA and the corresponding nitrogen-containing molecules derived from stearic acid (i.e., HSA that lacks a 12-hydroxyl group). Several of the HSA-derived molecules are exceedingly efficient LMOGs, with much less than 1 wt % being necessary to gelate several organic liquids at room temperature. Generally, the self-assembled fibrillar networks of the gels consist of spherulitic objects whose dimensions depend on the protocol employed to cool the precursor sol phases. X-ray studies indicate that the LMOG molecules are packed in lamellae within the fibers that constitute the spherulites. In addition, some of the organogels exhibit unusual thixotropic properties: they recover a large part of their viscoelasticity within seconds of being destroyed by excessive strain shearing. This recovery is at least an order of magnitude faster than for any other organogel with a crystalline fibrillar network reported to date. Correlations of these LMOG structures (as well as with those that lack a hydroxyl group along the n-alkyl chain, a headgroup at its end, or both) with the properties of their gels, coupled with the unusual theological properties of these systems, point to new directions for designing LMOGs and organogels.

Cyclic hardening in bundled actin networks

Nonlinear deformations can irreversibly alter the mechanical properties of materials. Most soft materials, such as rubber and living tissues, display pronounced softening when cyclically deformed. Here we show that, in contrast, reconstituted networks of crosslinked, bundled actin filaments harden when subject to cyclical shear. As a consequence, they exhibit a mechano-memory where a significant stress barrier is generated at the maximum of the cyclic shear strain. This unique response is crucially determined by the network architecture: at lower crosslinker concentrations networks do not harden, but soften showing the classic Mullins effect known from rubber-like materials. By simultaneously performing macrorheology and confocal microscopy, we show that cyclic shearing results in structural reorganization of the network constituents such that the maximum applied strain is encoded into the network architecture.

Geometry of Crumpled Paper

We measure the geometry of a crumpled sheet of paper with laser-aided topography and discuss its statistical properties. The curvature of an elastoplastic fold scales linearly with applied force. The curvature distribution follows an exponential form with regions of high curvature localized along ridges. The measured ridge length distribution is consistent with a hierarchical model for ridge breaking during crumpling. A large fraction of the ridges are observed to terminate without bifurcating, and the ridge network connectedness is not as complete as anticipated. The self-affinity of the surface is characterized by a Hurst exponent of 0.71+/-0.01 in contrast with previous results.

Size-Dependent Rheology of Type-I Collagen Networks

We investigate the system size-dependent rheological response of branched type I collagen gels. When subjected to a shear strain, the highly interconnected mesh dynamically reorients, resulting in overall stiffening of the network. When a continuous shear strain is applied to a collagen network, we observe that the local apparent modulus, in the strain-stiffening regime, is strongly dependent on the gel thickness. In addition, we demonstrate that the overall network failure is determined by the ratio of the gel thickness to the mesh size. These findings have broad implications for cell-matrix interactions, the interpretation of rheological tissue data, and the engineering of biomimetic scaffolds.

Vortices in vibrated granular rods.

We report the experimental observation of vortex patterns in vertically vibrated granular rods. Above a critical packing fraction, moving ordered domains of nearly vertical rods spontaneously form and coexist with horizontal rods. The domains of vertical rods coarsen in time to form large vortices. We investigate the conditions under which the vortices occur by varying the number of rods, vibration amplitude, and frequency. The size of the vortices increases with the number of rods. We characterize the growth of the ordered domains by measuring the area fraction of the ordered regions as a function of time. A void-filling model is presented to describe the nucleation and growth of the vertical domains. We track the ends of the vertical rods and obtain the velocity fields of the vortices. The rotation speed of the rods is observed to depend on the vibration velocity of the container and on the packing. To investigate the impact of the direction of driving on the observed phenomena, we performed experiments with the container vibrated horizontally. Although vertical domains form, vortices are not observed. We therefore argue that the motion is generated due to the interaction of the inclination of the rods with the bottom of a vertically vibrated container. We also perform simple experiments with a single row of rods in an annulus. These experiments directly demonstrate that the rod motion is generated when the rods are inclined from the vertical, and is always in the direction of the inclination.

Rheology and microrheology of a microstructured fluid: The gellan gum case

Particle tracking microrheology is used to study the effect of a constant applied shear during gelation of aqueous gellan gum with a monovalent salt. Shear modifies the gellan gum hydrogel microstructure and the bulk rheological properties of the system, depending on whether shear is applied during gelation or afterwards. The microstructure determines the linear elastic response of the gel, as well as the critical strain and stress above which the response becomes nonlinear. Bulk oscillatory rheology is used to study microstructured gellan gum hydrogels at different polymer and salt concentrations. The similarity between our system and concentrated microgel particle suspensions can be explained by considering the microstructured gellan system to be composed of microgel particles whose size is set by the applied shear stress magnitude during gelation. Polymer concentration and ionic strength control the individual microgel particles’ elastic properties. We also find the gellan system exhibits an isoenerget...

Electrostatically driven granular media: phase transitions and coarsening

We report the experimental and theoretical study of electrostatically driven granular material. We show that the charged granular medium undergoes a hysteretic phase transition from the immobile condensed state (granular solid) to a fluidized dilated state (granular gas) with a changing applied electric field. In addition we observe a spontaneous precipitation of dense clusters from the gas phase and subsequent coarsening-coagulation of these clusters. Molecular dynamics simulations show qualitative agreement with experimental results.

A rheological signature of frictional interactions in shear thickening suspensions

Colloidal shear thickening presents a significant challenge because the macroscopic rheology becomes increasingly controlled by the microscopic details of short ranged particle interactions in the shear thickening regime. Our measurements here of the first normal stress difference over a wide range of particle volume fractions elucidate the relative contributions from hydrodynamic lubrication and frictional contact forces, which have been debated. At moderate volume fractions we find N_{1}<0, consistent with hydrodynamic models; however, at higher volume fractions and shear stresses these models break down and we instead observe dilation (N_{1}>0), indicating frictional contact networks. Remarkably, there is no signature of this transition in the viscosity; instead, this change in the sign of N_{1} occurs while the shear thickening remains continuous. These results suggest a scenario where shear thickening is driven primarily by the formation of frictional contacts, with hydrodynamic forces playing a supporting role at lower concentrations. Motivated by this picture, we introduce a simple model that combines these frictional and hydrodynamic contributions and accurately fits the measured viscosity over a wide range of particle volume fractions and shear stress.

Collision statistics of driven granular materials.

We present an experimental investigation of the statistical properties of spherical granular particles on an inclined plane that are excited by an oscillating side wall. The data is obtained by high-speed imaging and particle tracking techniques. We identify all particles in the system and link their positions to form trajectories over long times. Thus, we identify particle collisions to measure the effective coefficient of restitution and find a broad distribution of values for the same impact angles. We find that the energy inelasticity can take on values greater than one, which implies that the rotational degrees of freedom play an important role in energy transfer. We also measure the distance and the time between collision events in order to directly determine the distribution of path lengths and the free times. These distributions are shown to deviate from expected theoretical forms for elastic spheres, demonstrating the inherent clustering in this system. We describe the data with a two-parameter fitting function and use it to calculate the mean free path and collision time. We find that the ratio of these values is consistent with the average velocity. The velocity distributions are observed to be strongly non-Gaussian and do not demonstrate any apparent universal behavior. We report the scaling of the second moment, which corresponds to the granular temperature, and higher order moments as a function of distance from the driving wall. Additionally, we measure long-time correlation functions in both space and in the velocities to probe diffusion in a dissipative gas.

Velocity correlations in dense granular gases.

We report the statistical properties of spherical steel particles rolling on an inclined surface being driven by an oscillating wall. Strong dissipation occurs due to collisions between the particles and can be tuned by changing the number density. The velocities of the particles are observed to be correlated over large distances comparable to the system size. The distribution of velocities deviates strongly from a Gaussian. The degree of the deviation, as measured by the kurtosis of the distribution, is observed to be as much as four times the value corresponding to a Gaussian, signaling a significant breakdown of the assumption of negligible velocity correlations in a granular system.