Colloidal Glass Research Articles

Connectivity and free-surface effects in polymer glasses

The glass transition is one of the few unsolved problems in condensed matter physics: agreement on the cause of the slowing down of structural relaxation in glass-forming liquids is lacking. Glasses are amorphous solids, which do not possess the long-range crystalline order, yet display arrested dynamics and the shear elastic modulus characteristic of equilibrium elasticity. It has been suggested that due to the influence of intramolecular interactions and chain connectivity, the nature of the glass transition in polymers and in standard glass-formers is fundamentally different. Here, we discuss the role of connectivity in polymer glasses, demonstrating that although covalent bonding promotes glass formation, bonding sequentiality that defines a polymer chain is not critical in the bulk: glassy dynamics is purely a result of the number of connections per particle, independently of how these connections are formed, agreeing with the classical Phillips-Thorpe topological constraint theory. We show that bonding sequentiality does play an important role in the surface effects of the glass, highlighting a major difference between polymeric and colloidal glasses. Further, we identify the heterogenous dynamics of model coarse-grained polymer chains both in ‘bulk’ and near the free surface, and demonstrate characteristic domain patterns in local displacement and connectivity.

Visualizing flow-unit-mediated deformation in a simple glass

Flow unit (FU), as the fundamental carrier of plasticity, is central to the mechanical behaviors of amorphous solids. Despite its importance, however, the structural origin of itself has remained elusive. This has been due in part to the limitations of existing experimental evidence for FUs. Here, we used a simple colloidal glass as model to monitor the plastic behavior of amorphous solid on particle level. We directly visualized the FUs in real space. It is observed that the FUs initiate preferentially from liquid-like regions. More specifically, liquid-like particles possessing high dilatancy ability prefer to participate in the operation of FUs.

Emergence of Goldstone excitations in stress correlations of glass-forming colloidal dispersions

We compute the dynamic correlations of the nonlocal shear stress at the liquid to glass transition in colloidal dispersions. Whereas Eshelby's elastic pattern is recovered independently of the dynamics, the Goldstone modes of the colloidal glass are diffusive, , because the transverse momentum is not conserved —excluding propagating transverse sound. Precursors of both, the Goldstone modes and the long-ranged, anisotropic stress correlations, can be observed in the colloidal fluid. The slow diffusive mode dominates the dynamics in the supercooled liquid for wave numbers with a correlation length which grows like the square root of the relaxation time τ. Time- and space-dependent stress correlations are anisotropic, decaying like . These results are derived within a hydrodynamic theory, generalising Maxwell‘s model to finite wave numbers, after the dynamics has been decomposed into potentially slow modes, associated with the order parameter, and fast microscopic degrees of freedom. Alternatively, hydrodynamic equations, closed by constitutive laws, can be used to predict the linear response of stress to an applied shear flow.

Ion-Induced Formation of Nanocrystalline Cellulose Colloidal Glasses Containing Nematic Domains.

Controlling the assembly of colloids in dispersion is a fundamental approach toward the production of functional materials. Nanocrystalline cellulose (NCC) is a charged nanoparticle whose colloidal interactions can be modulated from repulsive to attractive by increasing ionic strength. Here, we combine polarized optical microscopy, rheology, and small-angle scattering techniques to investigate (i) the concentration-driven transition from isotropic dispersion to cholesteric liquid crystals and (ii) salt-induced NCC phase transitions. In particular, we report on the formation of NCC attractive glasses containing nematic domains. At increasing NCC concentration, a structure peak was observed in small-angle X-ray scattering (SAXS) patterns. The evolution of the structure peak demonstrates the decrease in NCC interparticle distance, favoring orientational order during the isotropic-cholesteric phase transition. Small amounts of salt reduce the cholesteric volume fraction and pitch by a decrease in excluded volume. Beyond a critical salt concentration, NCC forms attractive glasses due to particle caging and reduced motility. This results in a sharp increase in viscosity and formation of viscoelastic glasses. The presence of nematic domains is suggested by the appearance of interference colors and the Cox-Merz rule failure and was confirmed by an anisotropic SAXS scattering pattern at q ranges associated with the presence of nematic domains. Thus, salt addition allows the formation of NCC attractive glasses with mechanical properties similar to those of gels while remaining optically active owed to entrapped nematic domains.

Entropy-driven docosahedral short-range order in simple liquids and glasses.

The energetically favored icosahedral structure has been seen as the central figure for describing the local structure of simple liquids and glasses. Although regular icosahedral structures are rarely found, it is accepted that distorted icosahedral structures occur in simple liquids and glasses. However, which local structure dominates and why it is more frequent than the others remain unanswered questions. In this study, by using a recently developed structure descriptor, we show that docosahedral structures are the most favored not only in models of simple liquids and glasses but also in an experimental colloid glass. We also show that the the predominance of docosahedral structures is entropy-driven. Our findings represent a significant milestone towards comprehending mysterious phenomena such as supercooling, glass transition, and crystallization, where local structures play a key role.

Structural Coloration with Nonclose-Packed Array of Bidisperse Colloidal Particles.

Colloidal crystals and glasses have their own photonic effects. Colloidal crystals show high reflectivity at narrowband, whereas colloidal glasses show low reflectivity at broadband. To compromise the opposite optical properties, a simple means is suggested to control the colloidal arrangement between crystal and glass by employing two different sizes of silica particles with repulsive interparticle potential. Monodisperse silica particles with repulsive potential spontaneously form crystalline structure at volume fraction far below 0.74. When two different sizes of silica particles coexist, the arrangement of silica particles is significantly influenced by two parameters: size contrast and mixing ratio. When the size contrast is small, a long-range order is partially conserved in the entire mixing ratio, resulting in a pronounced reflectance peak and brilliant structural color. When the size contrast is large, the long-range order is rapidly reduced along with mixing ratio. Nevertheless, a short-range order survives, which causes low reflectivity at a broad wavelength, developing faint structural colors. These findings offer an insight into controlling the colloidal arrangements and provide a simple way to tune the optical property of colloidal arrays for structural coloration.

Identity crisis in alchemical space drives the entropic colloidal glass transition

A universally accepted explanation for why liquids sometimes vitrify rather than crystallize remains hotly pursued, despite the ubiquity of glass in our everyday lives, the utilization of the glass transition in innumerable modern technologies, and nearly a century of theoretical and experimental investigation. Among the most compelling hypothesized mechanisms underlying glass formation is the development in the fluid phase of local structures that somehow prevent crystallization. Here, we explore that mechanism in the case of hard particle glasses by examining the glass transition in an extended alchemical (here, shape) space; that is, a space where particle shape is treated as a thermodynamic variable. We investigate simple systems of hard polyhedra, with no interactions aside from volume exclusion, and show via Monte Carlo simulation that glass formation in these systems arises from a multiplicity of competing local motifs, each of which is prevalent in—and predictable from—nearby ordered structures in alchemical space.

Local elasticity in nonlinear rheology of interacting colloidal glasses revealed by neutron scattering and rheometry.

The flow of colloidal suspensions is ubiquitous in nature and industry. Colloidal suspensions exhibit a wide range of rheological behavior, which should be closely related to the microscopic structure of the systems. With in situ small-angle neutron scattering complemented by rheological measurements, we investigated the deformation behavior of a charge-stabilized colloidal glass at particle level undergoing steady shear. A short-lived, localized elastic response at particle level, termed as the transient elasticity zone (TEZ), was identified from the neutron spectra. The existence of the TEZ, which could be promoted by the electrostatic interparticle potential, is a signature of deformation heterogeneity: the body of fluids under shear behaves like an elastic solid within the spatial range of the TEZ but like fluid outside the TEZ. The size of the TEZ shrinks as the shear rate increases in the shear thinning region, which shows that the shear thinning is accompanied by a diminishing deformation heterogeneity. More interestingly, the TEZ is found to be the structural unit that provides the resistance to the imposed shear, as evidenced by the quantitative agreement between the local elastic stress sustained by the TEZ and the macroscopic stress from rheological measurements at low and moderate shear rates. Our findings provide an understanding on the nonlinear rheology of interacting colloidal glasses from a micro-mechanical view.

Physical aging and compressed exponential behaviors in a model soft colloidal system

Diffusing wave spectroscopy (DWS)-based micro-rheology has been used in different optical geometries (backscattering and transmission) as well as different sample thicknesses in order to probe system dynamics at different length scales [D. J. Pine, D. A. Weitz, J. X. Zhu, E. Herbolzheimer. J. Phys., 1990, 51(18), 2101-2127]. Previous study from this lab [Q. Li, X. Peng, G. B. McKenna. Soft Matter, 2017, 13(7), 1396-1404] indicates the DWS-based micro-rheology observes the system non-equilibrium behaviors differently from macro-rheology. The object of the present work was to further explore the non-equilibrium dynamics and to address the range of utility of DWS as a micro-rheological method. A thermo-sensitive core-shell colloidal system was investigated both during aging and subsequent to aging into a metastable equilibrium state using temperature-jump induced volume fraction-jump experiments. We find that in the non-equilibrium state, significant differences in the measured dynamics are observed for the different geometries and length scales. Compressed exponential relaxations for the autocorrelation function g2(t) were observed for large length scales. However, upon converting the g2(t) data to the mean square displacement (MSD), such differences with length scale diminished and the long-time MSD behavior was consistent with diffusive behavior. These observations in the non-equilibrium behaviors for different length scales leads to questioning of some interpretations in the current field of light scattering-based micro-rheology and provides a possibility to interrogate the aging mechanisms in colloidal glasses from a broader perspective than normally considered in measurements of g2(t) using DWS-based micro-rheology.

Precursors of fluidisation in the creep response of a soft glass.

Via extensive numerical simulations, we study the fluidisation process of dense amorphous materials subjected to an external shear stress, using a three-dimensional colloidal glass model. In order to disentangle possible boundary effects from finite size effects in the process of fluidisation, we implement a novel geometry-constrained protocol with periodic boundary conditions. We show that this protocol is well controlled and that the longtime fluidisation dynamics is, to a great extent, independent of the details of the protocol parameters. Our protocol, therefore, provides an ideal tool to investigate the bulk dynamics prior to yielding and to study finite size effects regarding the fluidisation process. Our study reveals the existence of precursors to fluidisation observed as a peak in the strain-rate fluctuations, that allows for a robust definition of a fluidisation time. Although the exponents in the power-law creep dynamics seem not to depend significantly on the system size, we reveal strong finite size effects for the onset of fluidisation.

Shear melting and recovery of crosslinkable cellulose nanocrystal-polymer gels.

Cellulose nanocrystals (CNC) are naturally-derived nanostructures of growing importance for the production of composites having attractive mechanical properties, and offer improved sustainability over purely petroleum-based alternatives. Fabrication of CNC composites typically involves extrusion of CNC suspensions and gels in a variety of solvents, in the presence of additives such as polymers and curing agents. Most studies so far have focused on aqueous CNC gels, yet the behavior of CNC-polymer gels in organic solvents is important to their wider processability. Here, we study the rheological behavior of composite polymer-CNC gels in dimethylformamide, which include additives for both UV and thermal crosslinking. Using rheometry coupled with in situ infrared spectroscopy, we show that under external shear, CNC-polymer gels display progressive and irreversible failure of the hydrogen bond network that is responsible for their pronounced elastic properties. In the absence of cross-linking additives, the polymer-CNC gels show an instantaneous but partial recovery of their viscoelasticity upon cessation of flow, whereas, the presence of additives allows the gels to recover over much longer timescale via van der Waals interactions. By exploring a broad range of shear history and CNC concentrations, we construct master curves for the temporal evolution of the viscoelastic properties of the polymer-CNC gels, illustrating universality of the observed dynamics with respect to gel composition and flow conditions. We find that polymer-CNC composite gels display a number of the distinctive features of colloidal glasses and, strikingly, that their response to the flow conditions encountered during processing can be tuned by chemical additives. These findings have implications for processing of dense CNC-polymer composites in solvent casting, 3D printing, and other manufacturing techniques.

Binary colloidal glasses: linear viscoelasticity and its link to the microscopic structure and dynamics.

We study the relation between the microscopic structure and dynamics and the macroscopic rheological response of glass-forming colloidal suspensions, namely binary colloidal hard-sphere mixtures with large size asymmetry (1 : 5) that span a large range of mixture compositions close to the glass transition. The dynamical shear moduli are measured by oscillatory rheology and the structure and dynamics on the single-particle level by confocal microscopy. The data are compared with Brownian Dynamics simulations and predictions from mode-coupling theory based on the Percus-Yevick approximation. Experiments, simulations and theory consistently observe a strong decrease of the intermediate-frequency mechanical moduli combined with faster dynamics at intermediate mixing ratios and hence a non-monotonic dependence of these parameters but a localization of the large particles which decreases monotonically as the fraction of small particles is increased. We find that the Generalized-Stokes Einstein relation applied to the mean square displacements of the two components leads to a reasonable estimate of the shear moduli of the mixtures and hence links the rheological response to the particle dynamics which in turn reflects the microscopic structure.

Vibrational Modes and Dynamic Heterogeneity in a Near-Equilibrium 2D Glass of Colloidal Kites.

Using video microscopy and particle-tracking techniques developed for dense Brownian systems of polygons, we study the structure-dynamics relationship in a near-equilibrium 2D glass consisting of anisotropic Penrose kite-shaped colloids. Detailed vibrational properties of kite glasses, both translational and rotational, are obtained using covariance matrix techniques. Different from other colloidal glasses of spheres and ellipsoids, the vibrational modes of kite glasses at low frequencies show a strong translational character with spatially localized rotational modes and extended translational modes. Low-frequency quasilocalized soft modes commonly found in sphere glasses are absent in the translational phonon modes of kite glasses. Soft modes are observed predominantly in the rotational vibrations and correlate well with the spatial distribution of Debye-Waller factors. The local structural entropy field shows a strong correlation with the observed dynamic heterogeneity.

Crossover between Athermal Jamming and the Thermal Glass Transition of Suspensions.

The non-Newtonian flow behavior of thermal and athermal disordered systems of dispersed uniform particles at high densities have strikingly similar features. By investigating the flow curves of yield-stress fluids and colloidal glasses having different volume fractions, particle sizes, and interactions, we show that both thermal and athermal systems exhibit power-law scaling with respect to the glass and jamming point, respectively, with the same exponents. All yield-stress flow curves can be scaled onto a single universal curve using the Laplace pressure as the stress scale for athermal systems and the osmotic pressure for the thermal systems. Strikingly, the details of interparticle interactions do not matter for the rescaling, showing that they are akin to usual phase transitions of the same universality class. The rescaling allows us to predict the flow properties of these systems from the volume fraction and known material properties.

Apparent strength versus universality in glasses of soft compressible colloids

Microgel colloids, solvent swollen hydrogel particles of microscopic size, are in osmotic equilibrium with their surroundings. This has a profound effect on the behaviour of dense solutions of these polymeric colloids, most notably their ability to swell and deswell depending on the osmotic pressure of the system as a whole. Here we develop a minimal simulation model to treat this intrinsic volume regulation in order to explore the effects this has on the properties of dense solutions close to a liquid-solid transition. We demonstrate how the softness dependent volume regulation of particles gives rise to an apparent change in the fragility of the colloidal glass transition, which can be scaled out through the use of an adjusted volume fraction that accounts for changes in particle size. Moreover, we show how the same model can be used to explain the selective deswelling of soft microgels in a crystalline matrix of harder particles leading to robust crystals free of defects. Our results not only highlight the non-trivial effects of osmotic regulation in governing the apparent physics of microgel suspensions, but also provides a platform to efficiently account for particle deswelling in simulations.

Enhanced light absorption in simulations of ultra-thin ZnO layers structured by a SiO2 photonic glass

Hierarchically organized nanostructures are often employed to improve the energy conversion efficiency of photovoltaic and photoelectrochemical cells. Ultra-thin semiconductors can improve the internal carrier collection yield in materials with poor carrier lifetimes by reducing the characteristic length scales of collection. However, reducing the dimension of the light absorber requires strategies to increase absorption and the overall photogeneration when the material is to be used in broadband solar energy conversion applications. Here, we explore a strategy for improving light absorption in nanometer-scale, ultra-thin film ZnO layers by integrating them into a SiO2 colloidal crystal-based photonic glass. We use three-dimensional finite-difference electromagnetic simulations to study the local and total absorption improvements on composite films of close-packed, randomized colloidal structures coated with a thin layer of ZnO. These simulations show that the near band-gap absorption in the ZnO coating is dependent on the degree of vacancies in the colloidal crystal that templates the photonic glass. With these results, we show that disordered, defective colloidal composites can potentially be used to fabricate nanostructured photoelectrodes based on ultra-thin semiconductor layers with improved light absorption characteristics.

Microstructure and Soft Glassy Dynamics of an Aqueous Laponite Dispersion.

Synthetic hectorite clay Laponite RD/XLG is composed of disk-shaped nanoparticles that acquire dissimilar charges when suspended in an aqueous medium. Owing to their property to spontaneously self-assemble, Laponite is used as a rheology modifier in a variety of commercial water-based products. In particular, an aqueous dispersion of Laponite undergoes a liquid-to-solid transition at about 1 vol % concentration. The evolution of the physical properties as the dispersion transforms to the solid state is reminiscent of physical aging in molecular as well as colloidal glasses. The corresponding soft glassy dynamics of an aqueous Laponite dispersion, including the rheological behavior, has been extensively studied in the literature. In this feature article, we take an overview of recent advances in understanding soft glassy dynamics and various efforts taken to understand the peculiar rheological behavior. Furthermore, the continuously developing microstructure that is responsible for the eventual formation of a soft solid state that supports its own weight against gravity has also been a topic of intense debate and discussion. In particularly, extensive experimental and theoretical studies lead to two types of microstructures for this system: an attractive gel-like or a repulsive glass-like structure. We carefully examine and critically analyze the literature and propose a state (phase) diagram that suggests an aqueous Laponite dispersion to be present in an attractive gel state.

A crucial role of long-range hydrodynamic interactions near the colloidal glass transition based on time-convolutionless mode-coupling theory

The time-convolutionless mode-coupling theory (TMCT) recently proposed for molecular systems is employed to derive a TMCT equation for the collective-intermediate scattering function in suspensions of hard-sphere colloids from the nonlinear Langevin equations with the hydrodynamic interactions between colloids. The nonlinear memory function contained in the TMCT equation consists of two types of interactions between colloids; a mechanical interaction and a hydrodynamic interaction. It is predicted from the TMCT equation how the hydrodynamic interactions can affect the ergodic to non-ergodic transition at a critical point. Then, such a hydrodynamic effect is tested by the experimental data for suspensions of hard-sphere colloids with size polydispersities. Thus, it is emphasized that the long-range hydrodynamic interactions are indispensable to explain the polydispersity dependence of the experimental critical points which is quite different from that of simulations where only the mechanical interactions are taken into.

Soft Colloidal Glasses as Solid-State Electrolytes

Solid-state electrolytes are an attractive alternative to conventional liquid electrolytes in lithium batteries because of their intrinsic safety features and superior mechanical properties. Maintaining high bulk and interfacial ion fluxes in batteries that utilize solid-state electrolytes remains a significant challenge. We report on synthesis and electrochemical properties of a class of solid-state polymer electrolytes composed of silica nanoparticles covalently grafted with poly(ethylene oxide) chains. By regulating the salt content in the materials, we find that it is possible to drive microstructural changes, including nanoparticle arrangements, to achieve appreciable levels of bulk and interfacial ionic conductivity at room temperature. Additionally, we show that electrolyte salt additives can be used to create cathode-electrolyte interphases (CEI) that increase the oxidative stability of all PEO-based electrolytes. Finally, we report that solid-state lithium batteries comprised of a high-voltage ni...

Nonequilibrium free energy of colloidal glasses under shear

The free energy of hard-sphere systems provides a direct link between the particle-scale structure and macroscopic thermodynamic properties. Here, we employ this framework to investigate the shear-induced structure of a colloidal glass, and link it to its macroscopic mechanical and thermodynamic state. We measure the nonequilibrium free energy under shear from the free volumes of the particles, and monitor its evolution with the applied strain. Unlike crystals, for which the elastic energy increases quadratically with strain due to affine particle displacements, for glasses the free energy decreases due to non-affine displacements and dissipation, reflecting the ability of the glass to reach deeper free-energy minima. We model this decrease using the nonaffine shear modulus and a standard viscous dissipative term. Our model and measurements allow us to disentangle the complex contributions of affine and nonaffine particle displacements in the transient shear deformation of glasses.