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Liquid-liquid phase separation, whereby two liquids spontaneously demix, is ubiquitous in industrial, environmental, and biological processes. While isotropic fluids are known to condense into spherical droplets in the binodal region, these dynamics are poorly understood for structured fluids. Here, we report the novel observation of condensate networks, which spontaneously assemble during the demixing of a mesogen from a solvent. Condensing mesogens form rapidly-elongating filaments, rather than spheres, to relieve distortion of a simultaneously-forming internal smectic mesophase. As filaments densify, they collapse into bulged discs, lowering the elastic free energy. Additional distortion is relieved by retraction of filaments into the bulged discs, which are straightened under tension to form a ramified network. Understanding and controlling these dynamics may provide new avenues to direct pattern formation or template materials.

Microcapsules are commonly used in applications ranging from therapeutics to personal care products due to their ability to deliver encapsulated species through their porous shells. Here, we demonstrate a simple and scalable approach to fabricate microcapsules with porous shells by interfacial complexation of cellulose nanofibrils and oleylamine, and investigate the rheological properties of suspensions of the resulting microcapsules. The suspensions of neat capsules are viscous liquids whose viscosity increases with volume fraction according to a modified Kreiger-Dougherty relation with a maximum packing fraction of 0.73 and an intrinsic viscosity of 4. When polyacrylic acid (PAA) is added to the internal phase of the microcapsule, however, the suspensions become elastic and display yield stresses with power-law dependencies on capsule volume fraction and PAA concentration. The elasticity appears to originate from associative interactions between microcapsules induced by PAA that resides within the microcapsule shells. These results demonstrate that it is possible to tune the rheological properties of microcapsule suspensions by changing only the composition of the internal phase, thereby providing a novel method to tailor complex fluid rheology.

The yielding of disordered materials is a complex transition involving significant changes of the material's microstructure and dynamics. After yielding, many soft materials recover their quiescent properties over time as they age. There remains, however, a lack of understanding of the nature of this recovery. Here, we elucidate the mechanisms by which fibrillar networks restore their ability to support stress after yielding. Crucially, we observe that the aging response bifurcates around a critical stress $\sigma_\mathrm{c}$, which is equivalent to the material yield stress. After an initial yielding event, fibrillar networks subsequently yield faster and at lower magnitudes of stress. For stresses $\sigma<\sigma_\mathrm{c}$, the time to yielding increases with waiting time $t_\mathrm{w}$ and diverges once the network has restored sufficient entanglement density to support the stress. When $\sigma > \sigma_\mathrm{c}$, the yield time instead plateaus at a finite value because the developed network density is insufficient to support the applied stress. We quantitatively relate the yielding and aging behavior of the network to the competition between stress-induced disentanglement and dynamic fluctuations of the fibrils rebuilding the network. The bifurcation in the material response around $\sigma_c$ provides a new possibility to more rigorously localize the yield stress in disordered materials with time-dependent behavior.

The rheological properties of emulsions are of considerable importance in a diverse range of scenarios. Here we describe a superposition of the effects of droplet elasticity and volume fraction on the dynamics of emulsions. The superposition is governed by physical interactions between droplets, and provides a new mechanism for modifying the flow behavior of emulsions, by controlling the elasticity of the dispersed phase. We investigate the properties of suspensions of emulsified wormlike micelles (WLM). Dense suspensions of the emulsified WLM droplets exhibit thermally responsive properties in which the viscoelastic moduli decrease by an order of magnitude over a temperature range of 0 $^\circ$C to 25 $^\circ$C. Surprisingly, the fragility (i.e. the volume-fraction dependence of the modulus) of the emulsions does not change with temperature. Instead, the emulsion modulus scales as a power-law with volume fraction with a constant exponent across all temperatures even as the droplet properties change from elastic to viscous. Nevertheless, the underlying droplet dynamics depend strongly on temperature. From stress relaxation experiments, we quantify droplet dynamics across the cage breaking time scale below which the droplets are locally caged by neighbors and above which the droplets escape their cages to fully relax. For elastic droplets and high volume fractions, droplets relax less stress through cage rattling and the terminal relaxations are slower than for viscous droplets and lower volume fractions. The cage rattling and cage breaking dynamics are highly correlated for variations in both temperature and emulsion concentration, suggesting that thermal and volume fraction effects represent independent parameters to control emulsion properties., Comment: 6 figures

Recent experiments have highlighted the intrinsic magnetic anisotropy in coil-coil diblock copolymers, specifically in poly(styrene-b-4-vinylpyridine) (PS-b-P4VP), that enables magnetic field alignment at field strengths of a few tesla. We consider here the alignment response of two low molecular weight (MW) lamallae-forming PS-b-P4VP systems. Cooling across the disorder-order transition temperature ($\mathrm{T_{odt}}$) results in strong alignment for the higher MW sample (5.5K), whereas little alignment is discernible for the lower MW system (3.6K). This disparity under otherwise identical conditions of field strength and cooling rate suggests that different average grain sizes are produced during slow cooling of these materials, with larger grains formed in the higher MW material. Blending the block copolymers results in homogeneous samples which display $\mathrm{T_{odt}}$, d-spacings and grain sizes that are intermediate between the two neat diblocks. Similarly, the alignment quality displays a smooth variation with the concentration of the higher MW diblock in the blends and the size of grains likewise interpolates between limits set by the neat diblocks, with a factor of 3.5X difference in the grain size observed in high vs low MW neat diblocks. These results highlight the importance of grain growth kinetics in dictating the field response in block copolymers and suggests an unconventional route for the manipulation of such kinetics., Comment: 14 pages, 11 figures

We elucidate the roles of the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) transitions in magnetic field directed self-assembly of a liquid crystalline block copolymer (BCP), using \textit{in situ} x-ray scattering. Cooling into the nematic from the disordered melt yields poorly ordered and weakly aligned BCP microdomains. Continued cooling into the SmA however results in an abrupt increase in BCP orientational order with microdomain alignment tightly coupled to the translational order parameter of the smectic layers. These results underscore the significance of the N-SmA transition in generating highly aligned states under magnetic fields in these hierarchically ordered materials.

We examine the role of intrinsic chain susceptibility anisotropy in magnetic field directed self-assembly of a block copolymer using \textit{in situ} X-ray scattering. Alignment of a lamellar mesophase is observed on cooling across the disorder-order transition with the resulting orientational order inversely proportional to the cooling rate. We discuss the origin of the susceptibility anisotropy, $\Delta\chi$, that drives alignment, and calculate its magnitude using coarse-grained molecular dynamics to sample conformations of surface-tethered chains, finding $\Delta\chi\approx 2\times10^{-8}$. From field-dependent scattering data we estimate grains of $\approx1.2$ $\mu$m are present during alignment. These results demonstrate that intrinsic anisotropy is sufficient to support strong field-induced mesophase alignment and suggest a versatile strategy for field control of orientational order in block copolymers.

A bulk metallic glass forming alloy is subjected to shear flow in its supercooled state by compression of a short rod to produce a flat disc. The resulting material exhibits enhanced crystallization kinetics during isothermal annealing as reflected in the decrease of the crystallization time relative to the non-deformed case. The transition from quiescent to shear-accelerated crystallization is linked to strain accumulated during shear flow above a critical shear rate $\dot\gamma_c\approx 0.3$ s$^{-1}$ which corresponds to P\'{e}clet number, $Pe\sim\mathcal{O}(1)$. The observation of shear accelerated crystallization in an atomic system at modest shear rates is uncommon. It is made possible here by the substantial viscosity of the supercooled liquid which increases strongly with temperature in the approach to the glass transition. We may therefore anticipate the encounter of non-trivial shear-related effects during thermoplastic deformation of similar systems., Comment: 7 pages, 7 figures. To appear in Phys. Rev. E

We consider gelation of colloidal particles in suspension after cessation of shear flow. Particle aggregation is driven by a temperature-tunable attractive potential which controls the growth of clusters under isothermal conditions. A series of frequency resolved time sweeps is used to systematically reconstruct the frequency dependent dynamic moduli as a function of time and temperature or attraction strength. The data display typical hallmarks of gelation with an abrupt transition from a fluid state into a dynamically arrested gel state after a characteristic gelation time $t_g$ that varies exponentially with temperature and serves to collapse the evolution of the system onto a universal curve. We observe the viscoelastic properties of the critical gel where we find that $G'(\omega)\approxeq G''(\omega)\sim \omega^{n_c}$ where $n_c=0.5$ in a narrow time window across all attraction strengths. We measure a dynamic critical exponent of $\kappa=0.25$ which is similar to that observed in crosslinked polymer gels. The approach to the critical gel is therefore governed by $\eta_0\sim-\epsilon^{-s}$ and $G_e\sim\epsilon^z$ with $s=z=2$ where $\epsilon=p/p_c-1$ is the distance to the gel point. Remarkably, the relaxation moduli of the near-critical gels are identical across the temperatures considered, with $G(t)\approx0.33t^{-0.5}$. This suggests an underlying strong similarity in gel structure in the regime of attraction strengths considered, despite the differences in aggregation kinetics. We contrast these findings with the behavior of a colloidal glass undergoing dynamical arrest where no critical state is observed and where the arrest time of the system displays a marked frequency dependence. These findings highlight the underlying structural differences between colloidal gels and glasses which are manifest in their dynamic properties in the vicinity of the liquid-to-solid transition., Comment: 34 pages, 14 figures

We present results of temperature resolved scattering studies of a liquid crystalline block copolymer undergoing an order-disorder transition (ODT) in the presence of magnetic fields and time-resolved measurements during isothermal field annealing at sub-ODT temperatures. In each case, field interactions produced strongly textured mesophases with the cylindrical microdomains aligned parallel to the field. We find there is no measurable field-induced shift in the ODT temperature ($T_{ODT}$) which suggests that selective melting does not play a role in mesophase alignment during isothermal experiments. Our data indicate instead that sub-ODT alignment occurs by slow, large scale grain rotation whereas alignment during cooling from the disordered melt is rapid and driven by the nucleation of weakly ordered but preferentially aligned material. We identify an optimum sub-cooling that maximizes alignment during isothermal field annealing. This is corroborated by a simple model incorporating the competing effects of an exponentially decreasing mobility and divergent, increasing magnetic anisotropy on cooling below $T_{ODT}$. The absence of measurable field-effects on $T_{ODT}$ is consistent with rough estimates derived from the relative magnitudes of the free energy due to field interaction and the enthalpy of the isotropic-LC transition., Comment: 5 figures; To appear in Physical Review Letters

Dilute Laponite suspensions in water at low salt concentration form repulsive colloidal glasses which display physical aging. This phenomenon is still not completely understood and in particular, little is known about the connection between the flow history, as a determinant of the initial state of the system, and the subsequent aging dynamics. Using a stress controlled rheometer, we perform stress jump experiments to observe the elastic component of the flow stress that remains on cessation of flow or flow quenching. We investigate the connection between the dynamics of these residual stresses and the rate of physical aging upon quenching from different points on the steady state flow curve. Quenching from high rates produces a fluid state, G">G', with small, fast relaxing residual stresses and rapid, sigmoidal aging of the complex modulus. Conversely, quenching from lower shear rates produces increasingly jammed states featuring slowly relaxing stresses and a slow increase of the complex modulus with system age. Flow cessation from a fixed shear rate with varying quench durations shows that slower quenches produce smaller residual stresses at short times which relax at long times by smaller extents, by comparison with faster quenches. These smaller stresses are correlated with a higher modulus but slower physical aging of the system. The characteristic time for the residual stress relaxation scales inversely with the quench rate. This implies a frustrated approach to any ideal stress-free state that succinctly reflects the frustrated nature of these glassy systems., Comment: 21 pages, 14 figures; Submitted to Journal of Rheology

Evolution of the energy landscape during physical aging of glassy materials can be understood from the frequency and strain dependence of the shear modulus but the non-stationary nature of these systems frustrates investigation of their instantaneous underlying properties. Using a series of time dependent measurements we systematically reconstruct the frequency and strain dependence as a function of age for a repulsive colloidal glass undergoing structural arrest. In this manner, we are able to unambiguously observe the structural relaxation time, which increases exponentially with sample age at short times. The yield stress varies logarithmically with time in the arrested state, consistent with recent simulation results, whereas the yield strain is nearly constant in this regime. Strikingly, the frequency dependence at fixed times can be rescaled onto a master curve, implying a simple connection between the aging of the system and the change in the frequency dependent modulus., Comment: To appear in Phys. Rev. E.; 5 pages, 5 figures

We employ parallel superposition rheology to study the dynamics of an aging colloidal glass in the presence of a mean field stress. Over a range of intermediate stresses, the loss modulus exceeds the storage modulus at short times but develops a maximum concomitant with a crossover between the two as the system ages. This is attended by a narrowing of the loss peak on increasing stress. We show that this feature is characteristic of the structural arrest in these materials, which is made observable on reasonable timescales by the activating influence of the stress. The arrest time displays an exponential dependence on inverse stress. These results provide experimental validation of the role of stress as an effective temperature in soft glassy systems as has been advanced in recent theoretical frameworks., Comment: 5 pages, 5 figures

We monitor the relaxation of internal stresses in a fractal colloidal gel on cessation of flow and find a weak power law decay, $\sigma_i \sim t^{-\alpha}$ over 5 decades of time where $\alpha \approx 0.07$. The system exhibits physical aging of the elastic modulus, $G' \sim t^{\beta}$, with $\beta \approx \alpha$. Imposition of zero stress after waiting time $t_w$ results in strain recovery as the system relaxes without constraint. Remarkably, recoveries at different $t_w$ can be shifted to construct a master curve where data are scaled vertically by $1/\sigma_i(t_w)$ and plotted horizontally as $(t-t_w)/t_w^{\mu}$ where $\mu\approx 1.25$, indicative of a super-aging response., Comment: 4 pages, 5 figures

Vorticity aligned cylindrical flocs of carbon black particles are coincident with a primary shear thickening transition in steady flow and also appear as transient structures in the flow response of gels produced by a secondary shear thickening at high shear rates., Comment: 6 pages, 7 figures v2: Added normal stress data; Added optical micrograph of structures under steady shear Published in Soft Matter

Dilute oil dispersions of fractal carbon black particles with attractive Van der Waals interactions display continuous shear thickening followed by shear thinning at high shear rates. The shear thickening transition occurs at $\dot\gamma_{c}\approx 10^{2}-10^{3}s^{-1}$ and is driven by hydrodynamic breakup of clusters. Pre-shearing dispersions at shear rates $\dot\gamma>\dot\gamma_{c}$ produces enhanced-modulus gels where $G' \sim \sigma_{pre-shear}^{1.5-2}$ and is directly proportional to the residual stress in the gel measured at a fixed sample age. The observed data can be accounted for using a simple scaling model for the breakup of fractal clusters under shear stress., Comment: 5 pages, 5 figures; v2: treating low shear rate date separately; edited title; reworked figures