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Paul Bartlett

Publications and source records attributed to Paul Bartlett.

At least 19 recordsLinked to original sources
arXiv2020

Interaction between Nearly Hard Colloidal Spheres at an Oil-Water Interface

We show that the interaction potential between sterically stabilized, nearly hard-sphere [poly(methylmethacrylate)-poly(lauryl methacrylate) (PMMA-PLMA)] colloids at a water-oil interface has a negligible unscreened-dipole contribution, suggesting that models previously developed for charged particles at liquid interfaces are not necessarily applicable to sterically stabilized particles. Interparticle potentials, $U(r)$, are extracted from radial distribution functions [$g(r)$, measured by fluorescence microscopy] via Ornstein-Zernike inversion and via a reverse Monte Carlo scheme. The results are then validated by particle tracking in a blinking optical trap. Using a Bayesian model comparison, we find that our PMMA-PLMA data is better described by a screened monopole only rather than a functional form having a screened monopole plus an unscreened dipole term. We postulate that the long range repulsion we observe arises mainly through interactions between neutral holes on a charged interface, i.e., the charge of the liquid interface cannot, in general, be ignored. In agreement with this interpretation, we find that the interaction can be tuned by varying salt concentration in the aqueous phase. Inspired by recent theoretical work on point charges at dielectric interfaces, which we explain is relevant here, we show that a screened $\frac{1}{r^2}$ term can also be used to fit our data. Finally, we present measurements for poly(methyl methacrylate)-poly(12-hydroxystearic acid) (PMMA-PHSA) particles at a water-oil interface. These suggest that, for PMMA-PHSA particles, there is an additional contribution to the interaction potential. This is in line with our optical-tweezer measurements for PMMA-PHSA colloids in bulk oil, which indicate that they are slightly charged.

cond-mat.soft↗
arXiv2018

Transmission of torque at the nanoscale

In macroscopic mechanical devices torque is transmitted through gearwheels and clutches. In the construction of devices at the nanoscale, torque and its transmission through soft materials will be a key component. However, this regime is dominated by thermal fluctuations leading to dissipation. Here we demonstrate the principle of torque transmission for a disc-like colloidal assembly exhibiting clutch-like behaviour, driven by $27$ particles in optical traps. These are translated on a circular path to form a rotating boundary that transmits torque to additional particles confined to the interior. We investigate this transmission and find that it is determined by solid-like or fluid-like behaviour of the device and a stick-slip mechanism reminiscent of macroscopic gearwheels slipping. The transmission behaviour is predominantly governed by the rotation rate of the boundary and the density of the confined system. We determine the efficiency of our device and thus optimise conditions to maximise power output.

cond-mat.soft↗
arXiv2018

Composition inversion in mixtures of binary colloids and polymer

Understanding the phase behaviour of mixtures continues to pose challenges, even for systems that might be considered "simple". Here we consider a very simple mixture of two colloidal and one non-adsorbing polymer species which can be simplified even further to a size-asymmetrical binary mixture, in which the effective colloid-colloid interactions depend on the polymer concentration. We show that this basic system exhibits surprisingly rich phase behaviour. In particular, we enquire whether such a system features only a liquid-vapor phase separation (as in one-component colloid-polymer mixtures) or whether, additionally, liquid-liquid demixing of two colloidal phases can occur. Particle-resolved experiments show demixing-like behaviour, but when combined with bespoke Monte Carlo simulations, this proves illusory, and we reveal that only a single liquid-vapor transition occurs. Progressive migration of the small particles to the liquid phase as the polymer concentration increases gives rise to composition inversion - a maximum in the large particle concentration in the liquid phase. Near criticality the density fluctuations are found to be dominated by the larger colloids.

cond-mat.soft↗
arXiv2017

Charge regulation of nonpolar colloids

Individual colloids often carry a charge as a result of the dissociation (or adsorption) of weakly-ionized surface groups. The magnitude depends on the precise chemical environment surrounding a particle, which in a concentrated dispersion is a function of the colloid packing fraction $η$. Theoretical studies have suggested that the effective charge $Z_{\rm{eff}}$ in regulated systems could, in general, decrease with increasing $η$. We test this hypothesis for nonpolar dispersions by determining $Z_{\rm{eff}}(η)$ over a wide range of packing fractions ($10^{-5} \le η\le 0.3$) using a combination of small-angle X-ray scattering and electrophoretic mobility measurements. We find a complex dependence of the particle charge as a function of the packing fraction, with $Z_{\rm{eff}}$ initially decreasing at low concentrations before finally increasing at high $η$. We attribute the non-monotonic density dependence to a crossover from concentration-independent screening at low $η$, to a high packing fraction regime in which counterions outnumber salt ions and electrostatic screening becomes $η$-dependent. The efficiency of charge stabilization at high concentrations may explain the unusually high stability of concentrated nanoparticle dispersions which has been reported.

cond-mat.soft↗
arXiv2016

Non-additivity of pair interactions in charged colloids

It is general wisdom that the pair potential of charged colloids in a liquid may be closely approximated by a Yukawa interaction, as predicted by the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. We experimentally determine the effective forces in a binary mixture of like-charged particles, of species 1 and 2, with blinking optical tweezers. The measured forces are consistent with a Yukawa pair potential but the (12) cross-interaction is not equal to the geometric mean of the (11) and (22) like-interactions, as expected from DLVO. The deviation is a function of the electrostatic screening length and the size ratio, with the cross-interaction measured being consistently weaker than DLVO predictions. The corresponding non-additivity parameter is negative and grows in magnitude with increased size asymmetry.

cond-mat.soft↗
arXiv2014

Gels under stress: the origins of delayed collapse

Attractive colloidal particles can form a disordered elastic solid or gel when quenched into a two-phase region, if the volume fraction is sufficiently large. When the interactions are comparable to thermal energies the stress-bearing network within the gel restructures over time as individual particle bonds break and reform. Typically, under gravity such weak gels show a prolonged period of either no or very slow settling, followed by a sudden and rapid collapse - a phenomenon known as delayed collapse. The link between local bond breaking events and the macroscopic process of delayed collapse is not well understood. Here we summarize the main features of delayed collapse and discuss the microscopic processes which cause it. We present a plausible model which connects the kinetics of bond breaking to gel collapse and test the model by exploring the effect of an applied external force on the stability of a gel.

cond-mat.soft↗
arXiv2013

The effect of boundary adaptivity on hexagonal ordering and bistability in circularly confined quasi hard discs

The behaviour of materials under spatial confinement is sensitively dependent on the nature of the confining boundaries. In two dimensions, confinement within a hard circular boundary inhibits the hexagonal ordering observed in bulk systems at high density. Using colloidal experiments and Monte Carlo simulations, we investigate two model systems of quasi hard discs under circularly symmetric confinement. The first system employs an adaptive circular boundary, defined experimentally using holographic optical tweezers. We show that deformation of this boundary allows, and indeed is required for, hexagonal ordering in the confined system. The second system employs a circularly symmetric optical potential to confine particles without a physical boundary. We show that, in the absence of a curved wall, near perfect hexagonal ordering is possible. We propose that the degree to which hexagonal ordering is suppressed by a curved boundary is determined by the `strictness' of that wall.

cond-mat.soft↗
arXiv2013

Counterion Condensation on Spheres in the Salt-free Limit

A highly-charged spherical colloid in a salt-free environment exerts such a powerful attraction on its counterions that a certain fraction condenses onto the surface of a particle. The degree of condensation depends on the curvature of the surface. So, for instance, condensation is triggered on a highly-charged sphere only if the radius exceeds a certain critical radius $\collrad^{*}$. $\collrad^{*}$ is expected to be a simple function of the volume fraction of particles. To test these predictions, we prepare spherical particles which contain a covalently-bound ionic liquid, which is engineered to dissociate efficiently in a low-dielectric medium. By varying the proportion of ionic liquid to monomer we synthesise nonpolar dispersions of highly-charged spheres which contain essentially no free co-ions. The only ions in the system are counterions generated by the dissociation of surface-bound groups. We study the electrophoretic mobility of this salt-free system as a function of the colloid volume fraction, the particle radius, and the bare charge density and find evidence for extensive counterion condensation. At low electric fields, we observe excellent agreement with Poisson-Boltzmann predictions for counterion condensation on spheres. At high electric fields however, where ion advection is dominant, the electrophoretic mobility is enhanced significantly which we attribute to hydrodynamic stripping of the condensed layer of counterions from the surface of the particle.

cond-mat.soft↗
arXiv2012

Phase separation dynamics in colloid-polymer mixtures: the effect of interaction range

Colloid-polymer mixtures may undergo either fluid-fluid phase separation or gelation. This depends on the depth of the quench (polymer concentration) and polymer-colloid size ratio. We present a real-space study of dynamics in phase separating colloid-polymer mixtures with medium- to long-range attractions (polymer-colloid size ratio q_R=0.45-0.89, with the aim of understanding the mechanism of gelation as the range of the attraction is changed. In contrast to previous studies of short-range attractive systems, where gelation occurs shortly after crossing the equilibrium phase boundary, we find a substantial region of fluid-fluid phase separation. On deeper quenches the system undergoes a continuous crossover to gel formation. We identify two regimes, `classical' phase separation, where single particle relaxation is faster than the dynamics of phase separation, and `viscoelastic' phase separation, where demixing is slowed down appreciably due to slow dynamics in the colloid-rich phase. Particles at the surface of the strands of the network exhibit significantly greater mobility than those buried inside the gel strand which presents a method for coarsening.

cond-mat.soft↗
arXiv2012

Sudden collapse of a colloidal gel

Metastable gels formed by weakly attractive colloidal particles display a distinctive two-stage time-dependent settling behavior under their own weight. Initially a space-spanning network is formed that for a characteristic time, which we define as the lag time $\taud$, resists compaction. This solid-like behavior persists only for a limited time. Gels whose age $\tw$ is greater than $\taud$ yield and suddenly collapse. We use a combination of confocal microscopy, rheology and time-lapse video imaging to investigate both the process of sudden collapse and its microscopic origin in an refractive-index matched emulsion-polymer system. We show that the height $h$ of the gel in the early stages of collapse is well described by the surprisingly simple expression, $h(\ts) = \h0 - A \ts^{3/2}$, with $\h0$ the initial height and $\ts = \tw-\taud$ the time counted from the instant where the gel first yields. We propose that this unexpected result arises because the colloidal network progressively builds up internal stress as a consequence of localized rearrangement events which leads ultimately to collapse as thermal equilibrium is re-established.

cond-mat.soft↗
arXiv2007

Electrostatic charging of non-polar colloids by reverse micelles

Colloids dispersed in a non-polar solvent become charged when reverse micelles are added. We study the charge of individual sterically-stabilized poly(methyl methacrylate) spheres dispersed in micellar solutions of the surfactants sodium bis(2-ethyl 1-hexyl) sulfosuccinate [AOT], zirconyl 2-ethyl hexanoate [Zr(Oct)$_{2}$], and a copolymer of poly(12-hydroxystearic acid)--poly(methyl methacrylate) [PHSA-PMMA]. Although the sign of the particle charge is positive for Zr(Oct)$_{2}$, negative for AOT, and essentially neutral for PHSA-PMMA the different micellar systems display a number of common features. In particular, we demonstrate that, over a wide range of concentrations, the colloid charge is independent of the number of micelles added and scales linearly with the colloid size. A simple thermodynamic model, in which the particle charge is generated by the competitive adsorption of both positive and negative micelles, is in good agreement with the experimental data.

cond-mat.soft↗
arXiv2007

Direct measurement of the effective charge in nonpolar suspensions by optical tracking of single particles

We demonstrate a novel technique for the measurement of the charge carried by a colloidal particle. The technique uses the phenomenon of the resonance of a particle held in an optical tweezers trap and driven by a sinusoidal electric field. The trapped particle forms a strongly damped harmonic oscillator whose fluctuations are a function of $γ$, the ratio of the root-mean square average of the electric and thermal forces on the particle. At low applied fields, where $γ\ll 1$, the particle is confined to the optical axis while at high fields ($γ\gg 1$) the probability distribution of the particle is double-peaked. The periodically-modulated thermal fluctuations are measured with nanometer sensitivity using an interferometric position detector. Charges, as low as a few elementary charges, can be measured with an uncertainty of about 0.25 $e$. This is significantly better than previous techniques and opens up new possibilities for the study of nonpolar suspensions.

cond-mat.soft↗
arXiv2006

Measurement of Effective Temperatures in an Aging Colloidal Glass

We study the thermal fluctuations of an optically confined probe particle, suspended in an aging colloidal suspension, as the suspension transforms from a viscous liquid into an elastic glass. The micron-sized bead forms a harmonic oscillator. By monitoring the equal-time fluctuations of the tracer, at two different laser powers, we determine the temperature of the oscillator, $T_{\text{o}}$. In the ergodic liquid the temperatures of the oscillator and its environment are equal while, in contrast, in a nonequilibrium glassy phase we find that $T_{\text{o}}$ substantially exceeds the bath temperature.

cond-mat.soft↗
arXiv2005

Equilibrium cluster formation and gelation

We study the formation and growth of equilibrium clusters in a suspension of weakly-charged colloidal particles and small non-adsorbing polymers. The effective potential is characterised by a short-range attraction and a long-range repulsion. The size, shape and local structure of the clusters are studied using three-dimensional particle microscopy. We observe a rapid growth in the mean cluster size and the average number of nearest neighbours approaching the gel boundary.

cond-mat.soft↗
arXiv2005

Dynamical Arrest in Attractive Colloids: The Effect of Long-Range Repulsion

We study gelation in suspensions of model colloidal particles with short-ranged attractive and long-ranged repulsive interactions by means of three-dimensional fluorescence confocal microscopy. At low packing fractions, particles form stable equilibrium clusters. Upon increasing the packing fraction the clusters grow in size and become increasingly anisotropic until finally associating into a fully connected network at gelation. We find a surprising order in the gel structure. Analysis of spatial and orientational correlations reveals that the gel is composed of dense chains of particles constructed from face-sharing tetrahedral clusters. Our findings imply that dynamical arrest occurs via cluster growth and association.

cond-mat.soft↗
arXiv2005

Three-dimensional Binary Superlattices of Oppositely-charged Colloids

We report the equilibrium self-assembly of binary crystals of oppositely-charged colloidal microspheres at high density. By varying the magnitude of the charge on near equal-sized spheres we show that the structure of the binary crystal may be switched between face-centered cubic, cesium chloride and sodium chloride. We interpret these transformations in terms of a competition between entropic and Coulombic forces.

cond-mat.soft↗
arXiv2002

Colloidal dynamics in polymer solutions: Optical two-point microrheology measurements

We present an extension of the two-point optical microrheology technique introduced by Crocker \textit{et al.} [Phys. Rev. Lett. \textbf{85}, 888 (2000)] to high frequencies. The correlated fluctuations of two probe spheres held by a pair of optical tweezers within a viscoelastic medium are determined using optical interferometry. A theoretical model is developed to yield the frequency-dependent one- and two-particle response functions from the correlated motion. We demonstrate the validity of this method by determining the one- and two-particle correlations in a semi-dilute solution of polystyrene in decalin. We find that the ratio of the one- and two-particle response functions is anomalous which we interpret as evidence for a slip boundary condition caused by depletion of polymer from the surface of the particle.

cond-mat.soft↗