Dr Andrea Fortini

Research Fellow


Krinninger P, Fischer A, Fortini A (2014) Order-disorder transition in swirled granular disks, Phys. Rev. E90
We study the order-disorder transition of horizontally swirled dry and wet granular disks by means of computer simulations. Our systematic investigation of the local order formation as a function of amplitude and period of the external driving force shows that a large cluster of hexagonally ordered particles forms for both dry and wet granular particles at intermediate driving energies. Disordered states are found at small and large driving energies. Wet granular particles reach a higher degree of local hexagonal order, with respect to the dry case. For both cases we report a qualitative phase diagram showing the amount of local order at different state points. Furthermore we find that the transition from hexagonal order to a disordered state is characterised by the appearance of particles with square local order.
Sanz E, Leunissen ME, Fortini A, van Blaaderen A, Dijkstra M (2008) Gel formation in suspensions of oppositely charged colloids: mechanism and relation to the equilibrium phase diagram., J Phys Chem B112(35)pp. 10861-10872
We study gel formation in a mixture of equally-sized oppositely charged colloids both experimentally and by means of computer simulations. Both the experiments and the simulations show that the mechanism by which a gel is formed from a dilute, homogeneous suspension is an interrupted gas-liquid phase separation. Furthermore, we use Brownian dynamics simulations to study the relation between gel formation and the equilibrium phase diagram. We find that, regardless of the interaction range, an interrupted liquid-gas phase separation is observed as the system is quenched into a state point where the gas-liquid separation is metastable. The structure of the gel formed in our experiments compares well with that of a simulated gel, indicating that gravity has only a minor influence on the local structure of this type of gel. This is supported by the experimental evidence that gels squeezed or stretched by gravity have similar structures, as well as by the fact that gels do not collapse as readily as in the case of colloid-polymer mixtures. Finally, we check whether or not crystallites are formed in the gel branches; we find crystalline domains for the longer ranged interactions and for moderate quenches to the metastable gas-liquid spinodal regime.
Hopkins P, Fortini A, Archer AJ, Schmidt M (2010) The van Hove distribution function for brownian hard spheres: dynamical test particle theory and computer simulations for bulk dynamics., J Chem Phys133(22)
We describe a test particle approach based on dynamical density functional theory (DDFT) for studying the correlated time evolution of the particles that constitute a fluid. Our theory provides a means of calculating the van Hove distribution function by treating its self and distinct parts as the two components of a binary fluid mixture, with the "self " component having only one particle, the "distinct" component consisting of all the other particles, and using DDFT to calculate the time evolution of the density profiles for the two components. We apply this approach to a bulk fluid of Brownian hard spheres and compare to results for the van Hove function and the intermediate scattering function from Brownian dynamics computer simulations. We find good agreement at low and intermediate densities using the very simple Ramakrishnan-Yussouff [Phys. Rev. B 19, 2775 (1979)] approximation for the excess free energy functional. Since the DDFT is based on the equilibrium Helmholtz free energy functional, we can probe a free energy landscape that underlies the dynamics. Within the mean-field approximation we find that as the particle density increases, this landscape develops a minimum, while an exact treatment of a model confined situation shows that for an ergodic fluid this landscape should be monotonic. We discuss possible implications for slow, glassy, and arrested dynamics at high densities.
Dijkstra M, Van Roij R, Roth R, Fortini A (2006) Effect of many-body interactions on the bulk and interfacial phase behavior of a model colloid-polymer mixture, Physical Review E - Statistical, Nonlinear, and Soft Matter Physics73(4)
We study a model suspension of sterically stabilized colloidal particles and nonadsorbing ideal polymer coils, both in bulk and adsorbed against a planar hard wall. By integrating out the degrees of freedom of the polymer coils, we derive a formal expression for the effective one-component Hamiltonian of the colloids. We employ an efficient Monte Carlo simulation scheme for this mixture based on the exact effective colloid Hamiltonian; i.e., it incorporates all many-body interactions. The many-body character of the polymer-mediated effective interactions between the colloids yields bulk phase behavior and adsorption phenomena that differ substantially from those found for pairwise simple fluids. We determine the phase behavior for size ratios q= Ãp Ãc =1, 0.6, and 0.1, where Ãc and Ãp denote the diameters of the colloids and polymer coils, respectively. For q=1 and 0.6, we find both a fluid-solid and a stable colloidal gas-liquid transition with an anomalously large bulk liquid regime caused by the many-body interactions. We compare the phase diagrams obtained from simulations with the results of the free-volume approach and with direct simulations of the true binary mixture. Although we did not simulate the polymer coils explicitly, we are able to obtain the three partial structure factors and radial distribution functions. We compare our results with those obtained from density functional theory and the Percus-Yevick approximation. We find good agreement between all results for the structure. We also study the mixture in contact with a single hard wall for q=1. Upon approach of the gas-liquid binodal, we find far from the triple point, three layering transitions in the partial wetting regime. © 2006 The American Physical Society.
Fortini A, Sanz E, Dijkstra M (2008) Crystallization and gelation in colloidal systems with short-ranged attractive interactions., Phys Rev E Stat Nonlin Soft Matter Phys78(4 Pt 1)
We systematically study the relationship between equilibrium and nonequilibrium phase diagrams of a system of short-ranged attractive colloids. Using Monte Carlo and Brownian dynamics simulations we find a window of enhanced crystallization that is limited at high interaction strength by a slowing down of the dynamics and at low interaction strength by the high nucleation barrier. We find that the crystallization is enhanced by the metastable gas-liquid binodal by means of a two-stage crystallization process. First, the formation of a dense liquid is observed and second the crystal nucleates within the dense fluid. In addition, we find at low colloid packing fractions a fluid of clusters, and at higher colloid packing fractions a percolating network due to an arrested gas-liquid phase separation that we identify with gelation. We find that this arrest is due to crystallization at low interaction energy and it is caused by a slowing down of the dynamics at high interaction strength. Likewise, we observe that the clusters which are formed at low colloid packing fractions are crystalline at low interaction energy, but glassy at high interaction energy. The clusters coalesce upon encounter.
Oliveira ABD, Fortini A, Buldyrev SV, Srolovitz D (2010) Dynamics of the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface: Molecular dynamics simulations,
We study the dynamics of the contact between a pair of surfaces (with properties designed to mimic ruthenium) via molecular dynamics simulations. In particular, we study the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface. The results of such simulations suggest that contact behavior is highly variable. The goal of this study is to investigate the source and degree of this variability. We find that during compression, the behavior of the contact force displacement curves is reproducible, while during contact separation, the behavior is highly variable. Examination of the contact surfaces suggest that two separation mechanism are in operation and give rise to this variability. One mechanism corresponds to the formation of a bridge between the two surfaces that plastically stretches as the surfaces are drawn apart and eventually separates in shear. This leads to a morphology after separation in which there are opposing asperities on the two surfaces. This plastic separation/bridge formation mechanism leads to a large work of separation. The other mechanism is a more brittle-like mode in which a crack propagates across the base of the asperity (slightly below the asperity/substrate junction) leading to most of the asperity on one surface or the other after separation and a slight depression facing this asperity on the opposing surface. This failure mode corresponds to a smaller work of separation. those in which a single mechanism operates. Furthermore, contacts made from materials that exhibit predominantly brittle-like behavior will tend to require lower work of separation than those made from ductile-like contact materials.
Fortini A, Huang K (2014) Role of defects in the onset of wall-induced granular convection,
We investigate the onset of the wall-induced convection in vertically vibrated granular matter by means of experiments and two-dimensional computer simulations. In both simulations and experiments we find that the wall-induced convection occurs inside the bouncing bed region of the parameter space in which the granular bed behaves like a bouncing ball. A good agreement between experiments and simulations is found for the peak vibration acceleration at which convection starts. By comparing the results of simulations initialised with and without defects, we find that the onset of convection occurs at lower vibration strengths in the presence of defects. Furthermore, we find that the convection of granular particles initialised in a perfect hexagonal lattice is related to the nucleation of defects and the process is described by an Arrhenius law.
Fortini A, Dijkstra M, Tuinier R (2005) Phase behaviour of charged colloidal sphere dispersions with added polymer chains,
We study the stability of mixtures of highly screened repulsive charged spheres and non-adsorbing ideal polymer chains in a common solvent using free volume theory. The effective interaction between charged colloids in an aqueous salt solution is described by a screened-Coulomb pair potential, which supplements the pure hard-sphere interaction. The ideal polymer chains are treated as spheres that are excluded from the colloids by a hard-core interaction, whereas the interaction between two ideal chains is set to zero. In addition, we investigate the phase behaviour of charged colloid-polymer mixtures in computer simulations, using the two-body (Asakura-Oosawa pair potential) approximation to the effective one-component Hamiltonian of the charged colloids. Both our results obtained from simulations and from free volume theory show similar trends. We find that the screened-Coulomb repulsion counteracts the effect of the effective polymer-mediated attraction. For mixtures of small polymers and relatively large charged colloidal spheres, the fluid-crystal transition shifts to significantly larger polymer concentrations with increasing range of the screened-Coulomb repulsion. For relatively large polymers, the effect of the screened-Coulomb repulsion is weaker. The resulting fluid-fluid binodal is only slightly shifted towards larger polymer concentrations upon increasing the range of the screened-Coulomb repulsion. In conclusion, our results show that the miscibility of dispersions containing charged colloids and neutral non-adsorbing polymers increases, upon increasing the range of the screened-Coulomb repulsion, or upon lowering the salt concentration, especially when the polymers are small compared to the colloids.
Fortini A, Hynninen AP, Dijkstra M (2006) Gas-liquid phase separation in oppositely charged colloids: stability and interfacial tension., J Chem Phys125(9)
We study the phase behavior and the interfacial tension of the screened Coulomb (Yukawa) restricted primitive model (YRPM) of oppositely charged hard spheres with diameter sigma using Monte Carlo simulations. We determine the gas-liquid and gas-solid phase transitions using free energy calculations and grand-canonical Monte Carlo simulations for varying inverse Debye screening length kappa. We find that the gas-liquid phase separation is stable for kappasigma
Fortini A, Schmidt M (2013) Effect of controlled corrugation on capillary condensation of colloid-polymer mixtures, Soft Matter8pp. 6931-6939
We investigate with Monte Carlo computer simulations the capillary phase behaviour of model colloid-polymer mixtures confined between a flat wall and a corrugated wall. The corrugation is modelled via a sine wave as a function of one of the in-plane coordinates leading to a depletion attraction between colloids and the corrugated wall that is curvature dependent. We find that for increased amplitude of corrugation the region of the phase diagram where capillary condensation occurs becomes larger. We derive a Kelvin equation for this system and compare its predictions to the simulation results. We find good agreement between theory and simulation indicating that the primary reason for the stronger capillary condensation is an increased contact area between the fluid and the corrugated substrate. On the other hand, the colloid adsorption curves at colloid gas-liquid coexistence show that the increased area is not solely responsible for the stronger capillary condensation. Additionally, we analyse the dimensional crossover from a quasi-2D to a quasi-1D system and find that the transition is characterised by the appearance of a metastable phase.
Wagner CS, Fortini A, Hofmann E, Lunkenbein T, Schmidt M, Wittemann A (2012) Particle nanosomes with tailored silhouettes, Soft Matter8(6)pp. 1928-1933
The interest in hollow structures with defined porosities has promoted the fabrication of colloidosomes, i.e. capsules from spherical colloids. The hierarchically organized architectures were built from microparticles or multiple layers of nanoparticles to make sure that the capsule walls were sufficiently robust. Herein, we present for the first time a strategy towards submicron-sized capsules with walls that consist of a single layer of nanoscopic inorganic constituents. Nanoparticles and oppositely charged polymer colloids were joined at the surface of evaporating emulsion droplets. The heteroaggregates exhibited well-defined core-shell morphologies, with clusters of the polymer colloids as the core and a dense monolayer of nanoparticles as the shell. Various complex yet well-defined global shapes can be obtained in respect to the number of polymer particles. Subsequent removal of the polymer core led to capsules, which exhibited regular compartmentalized shapes. A high density of nanopores was obtained on objects with dimensions of less than half a micron. Regardless of the fact that the capsules consisted of a single layer of nanoparticles with tiny contacts keeping them together, they did not collapse or break apart. Monte Carlo computer simulations demonstrated that the nanoscopic constituents can be trapped into structurally arrested states. © 2012 The Royal Society of Chemistry.
Fortini A, Mazzola M, Mina A, Provasi D, Coló G, Onida G, Roman HE, Broglia RA (2005) The role of quantal fluctuations in the optical response of small metal clusters, Journal of Physics B: Atomic, Molecular and Optical Physics38(11)pp. 1581-1589
We present an ab initio calculation of the line shape of the photoabsorption spectrum of Na8 and Na+9 clusters at zero temperature, including the polarization effect driven by the electron-plasmon coupling, together with the electron-phonon coupling. The electron-plasmon coupling is found to yield a significant lowering of the energy centroid of the plasmons, whereas the main effect the electron-phonon coupling has is to smooth the spectrum. © 2005 IOP Publishing Ltd.
Fortini A, Bolhuis PG, Dijkstra M (2008) Effect of excluded volume interactions on the interfacial properties of colloid-polymer mixtures., J Chem Phys128(2)
We report a numerical study of equilibrium phase diagrams and interfacial properties of bulk and confined colloid-polymer mixtures using grand canonical Monte Carlo simulations. Colloidal particles are treated as hard spheres, while the polymer chains are described as soft repulsive spheres. The polymer-polymer, colloid-polymer, and wall-polymer interactions are described by density-dependent potentials derived by Bolhuis and Louis [Macromolecules 35, 1860 (2002)]. We compared our results with those of the Asakura-Oosawa-Vrij model [J. Chem. Phys. 22, 1255 (1954); J. Polym Sci 33, 183 (1958); Pure Appl. Chem. 48, 471 (1976)] that treats the polymers as ideal particles. We find that the number of polymers needed to drive the demixing transition is larger for the interacting polymers, and that the gas-liquid interfacial tension is smaller. When the system is confined between two parallel hard plates, we find capillary condensation. Compared with the Asakura-Oosawa-Vrij model, we find that the excluded volume interactions between the polymers suppress the capillary condensation. In order to induce capillary condensation, smaller undersaturations and smaller plate separations are needed in comparison with ideal polymers.
Schweikart A, Fortini A, Wittemann A, Schmidt M, Fery A (2010) Nanoparticle assembly by confinement in wrinkles: Experiment and simulations, Soft Matter6(23)pp. 5860-5863
We created hierarchically ordered structures of nanoparticles on smooth planar hydrophilic substrates by drying colloidal dispersions in confinement under macroscopic stamps with microscopically wrinkled surfaces. Experiments were carried out with model nanoparticle suspensions that possess high colloidal stability and monodispersity. The structures ranged from single parallel lines of particles to arrays of dense prismatic ridges. The type of observed structure could be controlled by the particle concentration in the initial dispersion. Confinement between two crossed stamps led to interconnected meshes of particles. The precise morphology could be predicted in all cases by Monte Carlo computer simulations of confined hard spheres. Our findings open up possibilities for versatile nanoparticle assembly on surfaces. © 2010 The Royal Society of Chemistry.
Fortini A (2012) Clustering and gelation of hard spheres induced by the Pickering effect., Phys Rev E Stat Nonlin Soft Matter Phys85(4 Pt 1)
A mixture of hard-sphere particles and model emulsion droplets is studied with a Brownian dynamics simulation. We find that the addition of nonwetting emulsion droplets to a suspension of pure hard spheres can lead to both gas-liquid and fluid-solid phase separations. Furthermore, we find a stable fluid of hard-sphere clusters. The stability is due to the saturation of the attraction that occurs when the surface of the droplets is completely covered with colloidal particles. At larger emulsion droplet densities a percolation transition is observed. The resulting networks of colloidal particles show dynamical and mechanical properties typical of a colloidal gel. The results of the model are in good qualitative agreement with recent experimental findings [E. Koos and N. Willenbacher, Science 331, 897 (2011)] in a mixture of colloidal particles and two immiscible fluids.
Schmidt M, Fortini A, Dijkstra M (2003) Capillary condensation of colloid-polymer mixtures confined between parallel plates, Journal of Physics Condensed Matter15(48 SPEC. ISS.)
We investigate the fluid-fluid demixing phase transition of the Asakura-Oosawa model colloid-polymer mixture confined between two smooth parallel hard walls using density functional theory and computer simulations. Comparing fluid density profiles for statepoints away from colloidal gas-liquid coexistence yields good agreement of the theoretical results with simulation data. Theoretical and simulation results predict consistently a shift of the demixing binodal and the critical point towards higher polymer reservoir packing fraction and towards higher colloid fugacities upon decreasing the plate separation distance. This implies capillary condensation of the colloid liquid phase, which should be experimentally observable inside slitlike micropores in contact with a bulk colloidal gas.
Schmidt M, Fortini A, Dijkstra M (2004) Capillary evaporation in colloid-polymer mixtures selectively confined to a planar slit, Journal of Physics Condensed Matter16(38)
Using density functional theory and Monte Carlo simulations we investigate the Asakura-Oosawa-Vrij mixture of hard sphere colloids and non-adsorbing ideal polymers under selective confinement of the colloids to a planar slab geometry. This is a model for confinement of colloid-polymer mixtures by either two parallel walls with a semi-permeable polymer coating or through the use of laser tweezers. We find that such a pore favours the colloidal gas over the colloidal liquid phase and induces capillary evaporation. A treatment based on the Kelvin equation gives a good account of the location of the capillary binodal for large slit widths. The colloid density profile is found to exhibit a minimum (maximum) at contact with the wall for large (small) slit widths.
Fortini A, Mendelev MI, Buldyrev S, Srolovitz D (2008) Asperity contacts at the nanoscale: comparison of Ru and Au, J. Appl. Phys. 104 (2008) p. 074320
We develop and validate an interatomic potential for ruthenium based on the embedded atom method framework with the Finnis/Sinclair representation. We confirm that the new potential yields a stable hcp lattice with reasonable lattice and elastic constants and surface and stacking fault energies. We employ molecular dynamics simulations to bring two surfaces together; one flat and the other with a single asperity. We compare the process of asperity contact formation and breaking in Au and Ru, two materials currently in use in micro electro mechanical system switches. While Au is very ductile at 150 and 300 K, Ru shows considerably less plasticity at 300 and 600 K (approximately the same homologous temperature). In Au, the asperity necks down to a single atom thick bridge at separation. While similar necking occurs in Ru at 600 K, it is much more limited than in Au. On the other hand, at 300 K, Ru breaks by a much more brittle process of fracture/decohesion with limited plastic deformation.
Fortini A, Dijkstra M (2006) Phase behaviour of hard spheres confined between parallel hard plates: manipulation of colloidal crystal structures by confinement., J Phys Condens Matter18(28)pp. L371-L378
We study the phase behaviour of hard spheres confined between two parallel hard plates using extensive computer simulations. We determine the full equilibrium phase diagram for arbitrary densities and plate separations from one to five hard-sphere diameters using free energy calculations. We find a first-order fluid-solid transition, which corresponds to either capillary freezing or melting depending on the plate separation. The coexisting solid phase consists of crystalline layers with either triangular ([Formula: see text]) or square ([Formula: see text]) symmetry. Increasing the plate separation, we find a sequence of crystal structures from [Formula: see text], where n is the number of crystal layers, in agreement with experiments on colloids. At high densities, the transition between square to triangular phases is interrupted by intermediate structures, e.g., prism, buckled, and rhombic phases.
Fortini A, Dijkstra M, Schmidt M, Wessels PPF (2005) Wall-Fluid and Liquid-Gas Interfaces of Model Colloid-Polymer Mixtures by Simulation and Theory, Phys. Rev. E71
We perform a study of the interfacial properties of a model suspension of hard sphere colloids with diameter $\sigma_c$ and non-adsorbing ideal polymer coils with diameter $\sigma_p$. For the mixture in contact with a planar hard wall, we obtain from simulations the wall-fluid interfacial free energy, $\gamma_{wf}$, for size ratios $q=\sigma_p/\sigma_c=0.6$ and 1, using thermodynamic integration, and study the (excess) adsorption of colloids, $\Gamma_c$, and of polymers, $\Gamma_p$, at the hard wall. The interfacial tension of the free liquid-gas interface, $\gamma_{lg}$, is obtained following three different routes in simulations: i) from studying the system size dependence of the interfacial width according to the predictions of capillary wave theory, ii) from the probability distribution of the colloid density at coexistence in the grand canonical ensemble, and iii) for statepoints where the colloidal liquid wets the wall completely, from Young's equation relating $\gamma_{lg}$ to the difference of wall-liquid and wall-gas interfacial tensions, $\gamma_{wl}-\gamma_{wg}$. In addition, we calculate $\gamma_{wf}, \Gamma_c$, and $\Gamma_p$ using density functional theory and a scaled particle theory based on free volume theory. Good agreement is found between the simulation results and those from density functional theory, while the results from scaled particle theory quantitatively deviate but reproduce some essential features. Simulation results for $\gamma_{lg}$ obtained from the three different routes are all in good agreement. Density functional theory predicts $\gamma_{lg}$ with good accuracy for high polymer reservoir packing fractions, but yields deviations from the simulation results close to the critical point.
van Meel JA, Charbonneau B, Fortini A, Charbonneau P (2009) Hard-sphere crystallization gets rarer with increasing dimension., Phys Rev E Stat Nonlin Soft Matter Phys80(6 Pt 1)
We recently found that crystallization of monodisperse hard spheres from the bulk fluid faces a much higher free-energy barrier in four than in three dimensions at equivalent supersaturation, due to the increased geometrical frustration between the simplex-based fluid order and the crystal [J. A. van Meel, D. Frenkel, and P. Charbonneau, Phys. Rev. E 79, 030201(R) (2009)]. Here, we analyze the microscopic contributions to the fluid-crystal interfacial free energy to understand how the barrier to crystallization changes with dimension. We find the barrier to grow with dimension and we identify the role of polydispersity in preventing crystal formation. The increased fluid stability allows us to study the jamming behavior in four, five, and six dimensions and to compare our observations with two recent theories [C. Song, P. Wang, and H. A. Makse, Nature (London) 453, 629 (2008); G. Parisi and F. Zamponi, Rev. Mod. Phys. (to be published)].
de las Heras D, Brader JM, Fortini A, Schmidt M (2016) Particle conservation in dynamical density functional theory,JOURNAL OF PHYSICS-CONDENSED MATTER28(24)ARTN 24402 IOP PUBLISHING LTD
Fortini A, Schmidt M, Dijkstra M (2006) Phase behavior and structure of model colloid-polymer mixtures confined between two parallel planar walls., Phys Rev E Stat Nonlin Soft Matter Phys73(5 Pt 1)
Using Gibbs ensemble Monte Carlo simulations and density functional theory we investigate the fluid-fluid demixing transition in inhomogeneous colloid-polymer mixtures confined between two parallel plates with separation distances between one and ten colloid diameters covering the complete range from quasi-two-dimensional to bulklike behavior. We use the Asakura-Oosawa-Vrij model in which colloid-colloid and colloid-polymer interactions are hard-sphere like, while the pair potential between polymers vanishes. Two different types of confinement induced by a pair of parallel walls are considered--namely, either through two hard walls or through two semipermeable walls that repel colloids but allow polymers to freely penetrate. For hard (semipermeable) walls we find that the capillary binodal is shifted towards higher (lower) polymer fugacities and lower (higher) colloid fugacities as compared to the bulk binodal; this implies capillary condensation (evaporation) of the colloidal liquid phase in the slit. A macroscopic treatment is provided by a symmetric Kelvin equation for general binary mixtures based on the proximity in chemical potentials of statepoints at capillary coexistence and the reference bulk coexistence. Results for capillary binodals compare well with those obtained from the classic version of the Kelvin equation due to [Evans and Marini Bettolo Marconi, J. Chem. Phys. 86, 7138 (1987)] and are quantitatively accurate away from the fluid-fluid critical point, even at small wall separations. However, the significant shift of the critical polymer fugacity towards higher values upon increasing confinement, as found in simulations, is not reproduced. For hard walls the density profiles of polymers and colloids inside the slit display oscillations due to packing effects for all statepoints. For semipermeable walls either similar structuring or flat profiles are found, depending on the statepoint considered.
Sanz E, Valeriani C, Vissers T, Fortini A, Leunissen ME, Blaaderen AV, Frenkel D, Dijkstra M (2009) Out-of-equilibrium processes in suspensions of oppositely charged colloids: liquid-to-crystal nucleation and gel formation, J. Phys.: Condens. Matter20
We study the kinetics of the liquid-to-crystal transformation and of gel formation in colloidal suspensions of oppositely charged particles. We analyse, by means of both computer simulations and experiments, the evolution of a fluid quenched to a state point of the phase diagram where the most stable state is either a homogeneous crystalline solid or a solid phase in contact with a dilute gas. On the one hand, at high temperatures and high packing fractions, close to an ordered-solid/disordered-solid coexistence line, we find that the fluid-to-crystal pathway does not follow the minimum free energy route. On the other hand, a quench to a state point far from the ordered-crystal/disordered-crystal coexistence border is followed by a fluid-to-solid transition through the minimum free energy pathway. At low temperatures and packing fractions we observe that the system undergoes a gas-liquid spinodal decomposition that, at some point, arrests giving rise to a gel-like structure. Both our simulations and experiments suggest that increasing the interaction range favors crystallization over vitrification in gel-like structures.
Fortini A, Schmidt M (2011) Computer simulations of colloidal transport on a patterned magnetic substrate., Phys Rev E Stat Nonlin Soft Matter Phys83(4 Pt 1)
We study the transport of paramagnetic colloidal particles on a patterned magnetic substrate with kinetic Monte Carlo and Brownian dynamics computer simulations. The planar substrate is decorated with point dipoles in either parallel or zigzag stripe arrangements and exposed to an additional external magnetic field that oscillates in time. For the case of parallel stripes we find that the magnitude and direction of the particle current is controlled by the tilt angle of the external magnetic field. The effect is reliably obtained in a wide range of ratios between temperature and magnetic permeability. Particle transport is achieved only when the period of oscillation of the external field is greater than a critical value. For the case of zigzag stripes a current is obtained using an oscillating external field normal to the substrate. In this case, transport is possible only in the vertex of the zigzag, giving rise to a narrow stream of particles. The magnitude and direction of the particle current are found to be controlled by a combination of the zigzag angle and the distance of the colloids from the substrate. Metropolis Monte Carlo and Brownian dynamics simulations predict results that are in good agreement with each other. Using kinetic Monte Carlo we find that at high density the particle transport is hindered by jamming.
Schwarz I, Fortini A, Wagner CS, Wittemann A, Schmidt M (2011) Monte Carlo computer simulations and electron microscopy of colloidal cluster formation via emulsion droplet evaporation., J Chem Phys135(24)
We consider a theoretical model for a binary mixture of colloidal particles and spherical emulsion droplets. The hard sphere colloids interact via additional short-ranged attraction and long-ranged repulsion. The droplet-colloid interaction is an attractive well at the droplet surface, which induces the Pickering effect. The droplet-droplet interaction is a hard-core interaction. The droplets shrink in time, which models the evaporation of the dispersed (oil) phase, and we use Monte Carlo simulations for the dynamics. In the experiments, polystyrene particles were assembled using toluene droplets as templates. The arrangement of the particles on the surface of the droplets was analyzed with cryogenic field emission scanning electron microscopy. Before evaporation of the oil, the particle distribution on the droplet surface was found to be disordered in experiments, and the simulations reproduce this effect. After complete evaporation, ordered colloidal clusters are formed that are stable against thermal fluctuations. Both in the simulations and with field emission scanning electron microscopy, we find stable packings that range from doublets, triplets, and tetrahedra to complex polyhedra of colloids. The simulated cluster structures and size distribution agree well with the experimental results. We also simulate hierarchical assembly in a mixture of tetrahedral clusters and droplets, and find supercluster structures with morphologies that are more complex than those of clusters of single particles.
Müller M, Karg M, Fortini A, Hellweg T, Fery A (2012) Wrinkle-assisted linear assembly of hard-core/soft-shell particles: impact of the soft shell on the local structure., Nanoscale4(7)pp. 2491-2499
This article addresses wrinkle assisted assembly of core-shell particles with hard cores and soft poly-(N-isopropylacrylamide) shells. As core materials we chose silica as well as silver nanoparticles. The assembled structures show that the soft shells act as a separator between the inorganic cores. Anisotropic alignment is found on two length scales, macroscopically guided through the wrinkle structure and locally due to deformation of the polymer shell leading to smaller inter-core separations as compared to assembly on flat substrates without confinement. The structures were analysed by means of scanning electron microscopy. Radial distribution functions are shown, clearly highlighting the impact of confinement on nearest neighbour distances and symmetry. The observed ordering is directly compared to Monte-Carlo simulations for hard-core/soft-shell particles, showing that the observed symmetries are a consequence of the soft interaction potential and differ qualitatively from a hard-sphere situation. For the silver-poly-(N-isopropylacrylamide) particles, we show UV-vis absorbance measurements revealing optical anisotropy of the generated structures due to plasmon coupling. Furthermore, the high degree of order of the assembled structures on macroscopic areas is demonstrated by laser diffraction effects.
Fortini A, Heras DDL, Brader JM, Schmidt M (2014) Superadiabatic forces in Brownian many-body dynamics, Phys. Rev. Lett.113
Theoretical approaches to nonequilibrium many-body dynamics generally rest upon an adiabatic assumption, whereby the true dynamics is represented as a sequence of equilibrium states. Going beyond this simple approximation is a notoriously difficult problem. For the case of classical Brownian many-body dynamics we present a simulation method that allows to isolate and precisely evaluate superadiabatic correlations and the resulting forces. Application of the method to a system of one-dimensional hard particles reveals the importance for the dynamics, as well as the complexity, of these nontrivial out-of-equilibrium contributions. Our findings help clarify the status of dynamical density functional theory and provide a rational basis for the development of improved theories.
Utgenannt A, Maspero Ross, Fortini Andrea, Turner R, Florescu Marian, Jeynes Christopher, Kanaras AG, Muskens OL, Sear Richard, Keddie Joseph (2016) Fast Assembly of Gold Nanoparticles in Large-Area 2-D Nanogrids Using a One-Step, Near-Infrared Radiation-Assisted Evaporation Process,ACS Nano10(2)pp. 2232-2242 American Chemical Society
When fabricating photonic crystals from suspensions in volatile liquids using the horizontal deposition method, the conventional approach is to evaporate slowly to increase the time for particles to settle in an ordered, periodic close-packed structure. Here, we show that the greatest ordering of 10 nm aqueous gold nanoparticles (AuNPs) in a template of larger spherical polymer particles (mean diameter of 338 nm) is achieved with very fast water evaporation rates obtained with near-infrared radiative heating. Fabrication of arrays over areas of a few cm2 takes only seven minutes. The assembly process requires that the evaporation rate is fast relative to the particles? Brownian diffusion. Then a two-dimensional colloidal crystal forms at the falling surface, which acts as a sieve through which the AuNPs pass, according to our Langevin dynamics computer simulations. With sufficiently fast evaporation rates, we create a hybrid structure consisting of a two-dimensional AuNP nanoarray (or ?nanogrid?) on top of a three-dimensional polymer opal. The process is simple, fast and one-step. The interplay between the optical response of the plasmonic Au nanoarray and the microstructuring of the photonic opal results in unusual optical spectra with two extinction peaks, which are analyzed via finite-difference time-domain method simulations. Comparison between experimental and modelling results reveals a strong interplay of plasmonic modes and collective photonic effects, including the formation of a high-order stop band and slow-light enhanced plasmonic absorption. The structures, and hence their optical signatures, are tuned by adjusting the evaporation rate via the infrared power density.
Fortini Andrea, Martin-Fabiani Ignacio, De La Haye Jennifer Lesage, Dugas Pierre-Yves, Lansalot Muriel, D'Agosto Franck, Bourgeat-Lami Elodie, Keddie Joseph, Sear Richard (2016) Dynamic stratification in drying films of colloidal mixtures,Physical Review Letters116(11) American Physical Society
In simulations and experiments, we study the drying of films containing mixtures of large and small colloidal particles in water. During drying, the mixture stratifies into a layer of the larger particles at the bottom with a layer of the smaller particles on top. We developed a model to show that a gradient in osmotic pressure, which develops dynamically during drying, is responsible for the segregation mechanism behind stratification.
Makepeace D, Fortini A, Markov A, Locatelli P, Lindsay C, Moorhouse S, Lind R, Sear R, Keddie J (2017) Stratification in Binary Colloidal Polymer Films: Experiment and Simulations,Soft Matter13pp. 6969-6980 Royal Society of Chemistry
When films are deposited from mixtures of colloidal particles of two different sizes, a diverse range of functional structures can result. One structure of particular interest is a stratified film in which the top surface layer has a composition different than in the interior. Here, we explore the conditions under which a stratified layer of small particles develops spontaneously in a colloidal film that is cast from a binary mixture of small and large polymer particles that are suspended in water. A recent model, which considers the cross-interaction between the large and small particles (Zhou et al., Phys. Rev. Lett. (2017) 118, 108002), predicts that stratification will develop from dilute binary mixtures when the particle size ratio (a), initial volume fraction of small particles (f s), and Péclet number are high. In experiments and Langevin dynamics simulations, we systematically vary a and fs in both dilute and concentrated suspensions. We find that stratified films develop when f s is increased, which is in agreement with the model. In dilute suspensions, there is reasonable agreement between the experiments and the Zhou et al. model. In concentrated suspensions, stratification occurs in experiments only for the higher size ratio a = 7. Simulations using a high Péclet number, additionally find stratification with a = 2, when f s is high enough. Our results provide a quantitative understanding of the conditions under which stratified colloidal films assemble. Our research has relevance for the design of coatings with targeted optical and mechanical properties at their surface.
Martin-Fabiani I, Fortini Andrea, Lesage de la Haye J, Koh ML, Taylor Spencer, Bourgeat-Lami E, Lansalot M, D?Agosto F, Sear Richard, Keddie Joseph (2016) pH-Switchable Stratification of Colloidal Coatings: Surfaces ?On Demand?,ACS Applied Materials and Interfaces8(50)pp. 34755-34761 American Chemical Society
Stratified coatings are used to provide properties at a surface, such as hardness or refractive index, which are different from underlying layers. Although time-savings are offered by self-assembly approaches, there have been no methods yet reported to offer stratification on demand. Here, we demonstrate a strategy to create self-assembled stratified coatings, which can be switched to homogenous structures when required. We use blends of large and small colloidal polymer particle dispersions in water that self-assemble during drying because of an osmotic pressure gradient that leads to a downward velocity of larger particles. Our confocal fluorescent microscopy images reveal a distinct surface layer created by the small particles. When the pH of the initial dispersion is raised, the hydrophilic shells of the small particles swell substantially, and the stratification is switched off. Brownian dynamics simulations explain the suppression of stratifi-cation when the small particles are swollen as a result of reduced particle mobility, a drop in the pressure gradient, and less time available before particle jamming. Our strategy paves the way for applications in antireflection films and pro-tective coatings in which the required surface composition can be achieved on demand, simply by adjusting the pH prior to deposition.
Dehan Véronique, Bourgeat-Lami Elodie, D'Agosto Franck, Duffy Brendan, Fortini Andrea, Hilton Sharon, Krassa Kalliopi, Keddie Joseph, Koh Ming L., Lansalot Muriel, Lee Michelle, Lesage de la Haye Jennifer, Martin-Fabiani Ignacio, Mantzaridis Christos, Mazeffa Douglas P., Sear Richard, Schulz Malin, Sibbald Morgan, Skerry Brian, Thomas Brett (2017) High-performance water-based barrier coatings for the corrosion protection of structural steel,Steel Construction10(3)pp. 254-259 Ernst und Sohn
This article provides an overview of the outcomes of a European-funded project called BarrierPlus. A new type of water-based barrier coating was developed for structural steel applications. The advantages of this coating include enhanced moisture resistance, low volatile organic compounds (VOCs) and one-component self-crosslinking free of isocyanates. To enable this performance, a latex polymer binder was uniquely designed without using soap-like molecules, known as surfactants, to form the dispersion. By minimizing surfactants in the coating, the barrier properties were significantly enhanced. The latex was successfully scaled up to 15 kg quantities by an SME, coating formulations were scaled to pilot quantities and a variety of characterization and coating performance tests were completed. A life cycle assessment found that the BarrierPlus coating has a better environmental profile than an industry benchmark solvent-borne coating and showed promising results relative to commercial waterborne benchmarks.