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Register a new userShort and soft: multi-domain organization, tunable dynamics and jamming in suspensions of grafted colloidal cylinders with small aspect ratio
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Added by
Dimitris Vlassopoulos
Publication date
2020
fields
Physics
and research's language is
English
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The yet virtually unexplored class of soft colloidal rods with small aspect ratio is investigated and shown to exhibit a very rich phase and dynamic behavior, spanning from liquid to nearly melt state. Instead of nematic order, these short and soft nanocylinders alter their organization with increasing concentration from isotropic liquid with random orientation to one with preferred local orientation and eventually a multi-domain arrangement with local orientational order. The latter gives rise to a kinetically suppressed state akin to structural glass with detectable terminal relaxation, which, on increasing concentration reveals features of hexagonally packed order as in ordered block copolymers. The respective dynamic response comprises four regimes, all above the overlapping concentration of 0.02 g/ml: I) from 0.03 to 0.1 g/mol the system undergoes a liquid-to-solid like transition with a structural relaxation time that grows by four orders of magnitude. II) from 0.1 to 0.2 g/ml a dramatic slowing-down is observed and is accompanied by an evolution from isotropic to multi-domain structure. III) between 0.2 and 0.6 g/mol the suspensions exhibit signatures of shell interpenetration and jamming, with the colloidal plateau modulus depending linearly on concentration. IV) at 0.74 g/ml in the densely jammed state, the viscoelastic signature of hexagonally packed cylinders from microphase-separated block copolymers is detected. These properties set short and soft nanocylinders apart from long colloidal rods (with large aspect ratio) and provide insights for fundamentally understanding the physics in this intermediate soft colloidal regime, as well as and for tailoring the flow properties of non-spherical soft colloids.
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We report on a comprehensive theory-simulation-experimental study of collective and self-diffusion in suspensions of charge-stabilized colloidal spheres. In simulation and theory, the spheres interact by a hard-core plus screened Coulomb pair potential. Intermediate and self-intermediate scattering functions are calculated by accelerated Stokesian Dynamics simulations where hydrodynamic interactions (HIs) are fully accounted for. The study spans the range from the short-time to the colloidal long-time regime. Additionally, Brownian Dynamics simulation and mode-coupling theory (MCT) results are generated where HIs are neglected. It is shown that HIs enhance collective and self-diffusion at intermediate and long times, whereas at short times self-diffusion, and for certain wavenumbers also collective diffusion, are slowed down. MCT significantly overestimate the slowing influence of dynamic particle caging. The simulated scattering functions are in decent agreement with our dynamic light scattering (DLS) results for suspensions of charged silica spheres. Simulation and theoretical results are indicative of a long-time exponential decay of the intermediate scattering function. The approximate validity of a far-reaching time-wavenumber factorization of the scattering function is shown to be a consequence of HIs. Our study of collective diffusion is amended by simulation and theoretical results for the self-intermediate scattering function and the particle mean squared displacement (MSD). Since self-diffusion is not assessed in DLS measurements, a method to deduce the MSD approximately in DLS is theoretically validated.
A universal secondary relaxation process, known as the Johari-Goldstein (JG) $beta$-relaxation process, appears in glass formers. It involves all parts of the molecule and is particularly important in glassy systems because of its very close relationship with the $alpha$-relaxation process. However, the absence of a J-G $beta$-relaxation mode in colloidal glasses raises questions regarding its universality. In the present work, we study the microscopic relaxation processes in Laponite suspensions, a model soft glassy material, by dynamic light scattering (DLS) experiments. $alpha$ and $beta$-relaxation timescales are estimated from the autocorrelation functions obtained by DLS measurements for Laponite suspensions with different concentrations, salt concentrations and temperatures. Our experimental results suggest that the $beta$-relaxation process in Laponite suspensions involves all parts of the constituent Laponite particle. The ergodicity breaking time is also seen to be correlated with the characteristic time of the $beta$-relaxation process for all Laponite concentrations, salt concentrations and temperatures. The width of the primary relaxation process is observed to be correlated with the secondary relaxation time. The secondary relaxation time is also very sensitive to the concentration of Laponite. We measure primitive relaxation timescales from the $alpha$-relaxation time and the stretching exponent ($beta$) by applying the coupling model for highly correlated systems. The order of magnitude of the primitive relaxation time is very close to the secondary relaxation time. These observations indicate the presence of a J-G $beta$-relaxation mode for soft colloidal suspensions of Laponite.
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Microscopic relaxation timescales are estimated from the autocorrelation functions obtained by dynamic light scattering experiments for Laponite suspensions with different concentrations ($C_{L}$), added salt concentrations ($C_{S}$) and temperatures ($T$). It has been shown in an earlier work [Soft Matter, 10, 3292-3300 (2014)] that the evolutions of relaxation timescales of colloidal glasses can be compared with molecular glass formers by mapping the waiting time ($t_{w}$) of the former with the inverse of thermodynamic temperature ($1/T$) of the latter. In this work, the fragility parameter $D$, which signifies the deviation from Arrhenius behavior, is obtained from fits to the time evolutions of the structural relaxation timescales. For the Laponite suspensions studied in this work, $D$ is seen to be independent of $C_{L}$ and $C_{S}$, but is weakly dependent on $T$. Interestingly, the behavior of $D$ corroborates the behavior of fragility in molecular glass formers with respect to equivalent variables. Furthermore, the stretching exponent $beta$, which quantifies the width $w$ of the spectrum of structural relaxation timescales is seen to depend on $t_{w}$. A hypothetical Kauzmann time $t_{k}$, analogous to the Kauzmann temperature for molecular glasses, is defined as the timescale at which $w$ diverges. Corresponding to the Vogel temperature defined for molecular glasses, a hypothetical Vogel time $t^{infty}_{alpha}$ is also defined as the time at which the structural relaxation time diverges. Interestingly, a correlation is observed between $t_{k}$ and $t^{infty}_{alpha}$, which is remarkably similar to that known for fragile molecular glass formers. A coupling model that accounts for the $t_{w}$-dependence of the stretching exponent is used to analyse and explain the observed correlation between $t_{k}$ and $t^{infty}_{alpha}$.
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