Confinement effects on the random sequential adsorption packings of elongated particles in a slit.

The behavior of a system of two-dimensional elongated particles (discorectangles) packed in a slit between the two parallel walls was analyzed using a simulation approach. The packings were produced using the random sequential adsorption model with continuous positional and orientational degrees of freedom. The aspect ratio (length-to-width ratio, ɛ=l/d) of the particles was varied within the range ɛ∈[1;32] while the distance between the walls was varied within the range h/d∈[1;80]. The properties of deposits in jammed state [the coverage, the order parameter, and the long-range (percolation) connectivity between particles] were studied numerically. The values of ɛ and h significantly affected the structure of the packings and the percolation connectivity. Particularly, the observed nontrivial dependencies of the jamming coverage φ(ɛ) or φ(h) were explained by the interplay of the different geometrical factors related to confinement, particle orientation degrees of freedom and excluded volume effects.

Connectedness percolation in the random sequential adsorption packings of elongated particles.

Connectedness percolation phenomena in the two-dimensional packing of elongated particles (discorectangles) were studied numerically. The packings were produced using random sequential adsorption off-lattice models with preferential orientations of the particles along a given direction. The partial ordering was characterized by the order parameter S, with S=0 for completely disordered films (random orientation of particles) and S=1 for completely aligned particles along the horizontal direction x. The aspect ratio (length-to-width ratio) of the particles was varied within the range ɛ∈[1;100]. Analysis of connectivity was performed assuming a core-shell structure of the particles. The value of S affected the structure of the packings, the formation of long-range connectivity, and the behavior of the electrical conductivity. The effects can be explained by taking accounting of the competition between the particles' orientational degrees of freedom and excluded volume effects. For aligned deposition, anisotropy in the electrical conductivity was observed with the values along the alignment direction σ_{x} being larger than the values in the perpendicular direction σ_{y}. Anisotropy in the localization of the percolation threshold was also observed in finite-sized packings, but it disappeared in the limit of infinitely large systems.

Relaxation of saturated random sequential adsorption packings of discorectangles aligned on a line.

Relaxation of the packing of elongated particles (discorectangles) aligned on a line was studied numerically. The aspect ratio (length-to-width ratio) for the discorectangles was varied within the range ɛ∈[1;50]. The initial jamming (saturated) state was produced using the basic variant of the random sequential adsorption model with random positions and orientations of particles. The relaxation was performed by allowing rotational and translational diffusion motions of the particles while their centers remained located on the line. The effects of the aspect ratio ɛ on the kinetics of relaxation, the orientation order parameter, and the distribution function of the distances between nearest-neighbor discorectangles were analyzed. The transport properties of the resulting one-dimensional systems were also analyzed by using the diffusion of a tracer particle (random walker) between the nearest-neighbor discorectangles. In the relaxed states the anomalous diffusion was observed having a hopping exponent d_{w}>2 dependent upon ɛ.

Random sequential adsorption of partially ordered discorectangles onto a continuous plane.

A computer simulation was used to study the random sequential adsorption of identical discorectangles onto a continuous plane. The problem was analyzed for a wide range of discorectangle aspect ratios (ɛ∈[1;100]). We studied the anisotropic deposition, i.e., the orientations of the deposited particles were uniformly distributed within some interval such that the particles were preferentially aligned along a given direction. The kinetics of the changes in the packing fraction found at different values of such the alignment are discussed. Partial ordering of the discorectangles significantly affected the packing fraction at the jamming state, φ_{j}, and shifted the cusps in the φ_{j}(ɛ) dependencies. The structure of the jammed state was analyzed using the adsorption of disks of different diameters into the porous space between the deposited discorectangles. The analysis of the connectivity between the discorectangles was performed assuming a core-shell structure of particles.

Paris car parking problem for partially oriented discorectangles on a line.

The random sequential adsorption (RSA) of identical elongated particles (discorectangles) on a line ("Paris car parking problem") was studied numerically. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The possible orientations of the discorectanles were restricted between θ∈[-θ_{m};θ_{m}] while the aspect ratio (length-to-width ratio) for the discorectangles was varied within the range ɛ∈[1;100]. Additionally, the limiting case ɛ=∞ (i.e., widthless sticks) was considered. We observed that the RSA deposition for the problem under consideration was governed by the formation of rarefied holes (containing particles oriented along a line) surrounded by comparatively dense stacks (filled with almost parallel particles oriented in the vertical direction). The kinetics of the changes of the order parameter and the packing density are discussed. Partial ordering of the discorectangles significantly affected the packing density at the jamming state, φ_{j}, and shifted the cusps in the φ_{j}(ɛ) dependencies. This can be explained by the effects on the competition between the particles' orientational degrees of freedom and the excluded volume effects.

Electrokinetic Behavior of Laponite RD in Aqueous Suspensions Containing Poly(ethylene oxide) and Cetyltrimethylammonium Bromide.

The aqueous suspensions of Laponite RD (Lap) platelets demonstrate rich phase diagrams. Both poly(ethylene oxide) (PEO) and cetyltrimethylammonium bromide (CTAB) molecules competitively adsorb on the surface of Lap, and strong interactions between PEO and CTAB exist. The stability of ternary systems Lap + PEO + CTAB can be finely regulated by changing the balance of these interactions. The electrokinetic technique was used to study 0.065 and 2% wt Lap suspensions in the presence of different amounts of PEO of various molecular masses Mw (400-20,000 g/mol) and CTAB (0-1 mM). For 0.065% wt Lap suspension, the additives of PEO did not affect the position of the isoelectric point (IEP), but the impact of PEO in the regions below or above the IEP was significant, especially for a large Mw. The observed effects were explained, accounting the model for the adsorption of PEO in the form of loops and tails as well as for the changes in the packing balance of CTAB and PEO on the surface of Lap. For 2% wt suspension, the strong effects of Mw on the ζ-potential and aggregation of particles were explained by screening the repulsive double layers by PEO chains, by bridging the Lap particles via PEO molecules, and by the impact of CTAB molecules on the bridging between Lap aggregates.

Relaxation in two-dimensional suspensions of rods as driven by Brownian diffusion.

Relaxation in a two-dimensional suspensions containing rods was studied by using dynamic Monte Carlo simulations. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The initial state was produced by using a random sequential adsorption model. During the relaxation, the rods underwent translational and rotational Brownian motions. The simulations were run at different values of number density ρ (the number of rods per unit area) and of the initial orientation order parameter S_{i}. The rods were assumed to have core-shell structures. The evolutions of both the connectivity and the order parameter have revealed different relaxation behavior.

Sedimentation of a suspension of rods: Monte Carlo simulation of a continuous two-dimensional problem.

The sedimentation of a two-dimensional suspension containing rods was studied by means of Monte Carlo (MC) simulations. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The initial state before sedimentation was produced using a model of random sequential adsorption. During such sedimentation, the rods undergo translational and rotational Brownian motions. The MC simulations were run at different initial number densities (the numbers of rods per unit area), ρ_{i}, and sedimentation rates, u. For sediment films, the spatial distributions of the rods, the order parameters, and the electrical conductivities were examined. Different types of sedimentation-driven self-assembly and anisotropy of the electrical conductivity were revealed inside the sediment films. This anisotropy can be finely regulated by changes in the values of ρ_{i} and u.

Anisotropy in electrical conductivity of films of aligned intersecting conducting rods.

Numerical simulations by means of the Monte Carlo method have been performed to study the electrical properties of a two-dimensional composite filled with rodlike particles. The main goal was to study the effect of the alignment of such rods on the anisotropy of its electrical conductivity. A continuous model was used. In this model, the rods have zero-width (i.e., infinite aspect ratio) and they may intersect each other. To involve both the low conductive host matrix and highly conductive fillers (rods) in the consideration, a discretization algorithm based on the use of a supporting mesh was applied. The discretization is equivalent to the substitution of rods with the polyominoes. Once discretized, the Frank-Lobb algorithm was applied to evaluate the electrical conductivity. Our main findings are (i) the alignment of the rods essentially affects the electrical conductivity and its anisotropy, (ii) the discrete nature of computer simulations is crucial. For slightly disordered system, high electrical anisotropy was observed at small filler content, suggesting a method to enable the production of optically transparent and highly anisotropic conducting films.

Anisotropy in electrical conductivity of two-dimensional films containing aligned nonintersecting rodlike particles: Continuous and lattice models.

The electrical conductivity of two-dimensional films filled with rodlike particles (rods) was simulated by the Monte Carlo method. The main attention has been paid to the investigation of the effect of the rod alignment on the electrical properties of the films. Both continuous and lattice approaches were used. Intersections of particles were forbidden. Our main findings are (i) both models demonstrate similar behaviors, (ii) at low concentration of rods, both approaches lead to the same dependencies of the electrical conductivity on the concentration of the rods, (iii) the alignment of the rods essentially affects the electrical conductivity, (iv) at some concentrations of partially aligned rods, the films may be conducting only in one direction, and (v) the films may simultaneously be both highly transparent and electrically anisotropic.

Vertical drying of a suspension of sticks: Monte Carlo simulation for continuous two-dimensional problem.

The vertical drying of a two-dimensional colloidal film containing zero-thickness sticks (lines) was studied by means of kinetic Monte Carlo (MC) simulations. The continuous two-dimensional problem for both the positions and orientations was considered. The initial state before drying was produced using a model of random sequential adsorption with isotropic orientations of the sticks. During the evaporation, an upper interface falls with a linear velocity in the vertical direction, and the sticks undergo translational and rotational Brownian motions. The MC simulations were run at different initial number concentrations (the numbers of sticks per unit area), p_{i}, and solvent evaporation rates, u. For completely dried films, the spatial distributions of the sticks, the order parameters, and the electrical conductivities of the films in both the horizontal, x, and vertical, y, directions were examined. Significant evaporation-driven self-assembly and stratification of the sticks in the vertical direction was observed. The extent of stratification increased with increasing values of u. The anisotropy of the electrical conductivity of the film can be finely regulated by changes in the values of p_{i} and u.

Diffusion-driven self-assembly of rodlike particles: Monte Carlo simulation on a square lattice.

The diffusion-driven self-assembly of rodlike particles was studied by means of Monte Carlo simulation. The rods were represented as linear k-mers (i.e., particles occupying k adjacent sites). In the initial state, they were deposited onto a two-dimensional square lattice of size L×L up to the jamming concentration using a random sequential adsorption algorithm. The size of the lattice, L, was varied from 128 to 2048, and periodic boundary conditions were applied along both x and y axes, while the length of the k-mers (determining the aspect ratio) was varied from 2 to 12. The k-mers oriented along the x and y directions (k_{x}-mers and k_{y}-mers, respectively) were deposited equiprobably. In the course of the simulation, the numbers of intraspecific and interspecific contacts between the same sort and between different sorts of k-mers, respectively, were calculated. Both the shift ratio of the actual number of shifts along the longitudinal or transverse axes of the k-mers and the electrical conductivity of the system were also examined. For the initial random configuration, quite different self-organization behavior was observed for short and long k-mers. For long k-mers (k≥6), three main stages of diffusion-driven spatial segregation (self-assembly) were identified: the initial stage, reflecting destruction of the jamming state; the intermediate stage, reflecting continuous cluster coarsening and labyrinth pattern formation; and the final stage, reflecting the formation of diagonal stripe domains. Additional examination of two artificially constructed initial configurations showed that this pattern of diagonal stripe domains is an attractor, i.e., any spatial distribution of k-mers tends to transform into diagonal stripes. Nevertheless, the time for relaxation to the steady state essentially increases as the lattice size growth.

Electrical conductivity of a monolayer produced by random sequential adsorption of linear k-mers onto a square lattice.

The electrical conductivity of a monolayer produced by the random sequential adsorption (RSA) of linear k-mers (particles occupying k adjacent adsorption sites) onto a square lattice was studied by means of computer simulation. Overlapping with predeposited k-mers and detachment from the surface were forbidden. The RSA process continued until the saturation jamming limit, p_{j}. The isotropic (equiprobable orientations of k-mers along x and y axes) and anisotropic (all k-mers aligned along the y axis) depositions for two different models-of an insulating substrate and conducting k-mers (C model) and of a conducting substrate and insulating k-mers (I model)-were examined. The Frank-Lobb algorithm was applied to calculate the electrical conductivity in both the x and y directions for different lengths (k=1 - 128) and concentrations (p=0 - p_{j}) of the k-mers. The "intrinsic electrical conductivity" and concentration dependence of the relative electrical conductivity Σ(p) (Σ=σ/σ_{m} for the C model and Σ=σ_{m}/σ for the I model, where σ_{m} is the electrical conductivity of substrate) in different directions were analyzed. At large values of k the Σ(p) curves became very similar and they almost coincided at k=128. Moreover, for both models the greater the length of the k-mers the smoother the functions Σ_{xy}(p),Σ_{x}(p) and Σ_{y}(p). For the more practically important C model, the other interesting findings are (i) for large values of k (k=64,128), the values of Σ_{xy} and Σ_{y} increase rapidly with the initial increase of p from 0 to 0.1; (ii) for k≥16, all the Σ_{xy}(p) and Σ_{x}(p) curves intersect with each other at the same isoconductivity points; (iii) for anisotropic deposition, the percolation concentrations are the same in the x and y directions, whereas, at the percolation point the greater the length of the k-mers the larger the anisotropy of the electrical conductivity, i.e., the ratio σ_{y}/σ_{x} (>1).

Monte Carlo simulation of evaporation-driven self-assembly in suspensions of colloidal rods.

The vertical drying of a colloidal film containing rodlike particles was studied by means of kinetic Monte Carlo (MC) simulation. The problem was approached using a two-dimensional square lattice, and the rods were represented as linear k-mers (i.e., particles occupying k adjacent sites). The initial state before drying was produced using a model of random sequential adsorption (RSA) with isotropic orientations of the k-mers (orientation of the k-mers along horizontal x and vertical y directions are equiprobable). In the RSA model, overlapping of the k-mers is forbidden. During the evaporation, an upper interface falls with a linear velocity of u in the vertical direction and the k-mers undergo translation Brownian motion. The MC simulations were run at different initial concentrations, p_{i}, (p_{i}∈[0,p_{j}], where p_{j} is the jamming concentration), lengths of k-mers (k∈[1,12]), and solvent evaporation rates, u. For completely dried films, the spatial distributions of k-mers and their electrical conductivities in both x and y directions were examined. Significant evaporation-driven self-assembly and orientation stratification of the k-mers oriented along the x and y directions were observed. The extent of stratification increased with increasing value of k. The anisotropy of the electrical conductivity of the film can be finely regulated by changes in the values of p_{i}, k, and u.

Impact of defects on percolation in random sequential adsorption of linear k-mers on square lattices.

The effect of defects on the percolation of linear k-mers (particles occupying k adjacent sites) on a square lattice is studied by means of Monte Carlo simulation. The k-mers are deposited using a random sequential adsorption mechanism. Two models L(d) and K(d) are analyzed. In the L(d) model it is assumed that the initial square lattice is nonideal and some fraction of sites d is occupied by nonconducting point defects (impurities). In the K(d) model the initial square lattice is perfect. However, it is assumed that some fraction of the sites in the k-mers d consists of defects, i.e., is nonconducting. The length of the k-mers k varies from 2 to 256. Periodic boundary conditions are applied to the square lattice. The dependences of the percolation threshold concentration of the conducting sites p(c) vs the concentration of defects d are analyzed for different values of k. Above some critical concentration of defects d(m), percolation is blocked in both models, even at the jamming concentration of k-mers. For long k-mers, the values of d(m) are well fitted by the functions d(m)∝k(m)(-α)-k(-α) (α=1.28±0.01 and k(m)=5900±500) and d(m)∝log(10)(k(m)/k) (k(m)=4700±1000) for the L(d) and K(d) models, respectively. Thus, our estimation indicates that the percolation of k-mers on a square lattice is impossible even for a lattice without any defects if k⪆6×10(3).

S. cerevisiae fermentation activity after moderate pulsed electric field pre-treatments.

The batch fermentation process, inoculated by Pulsed Electric Field (PEF) treated wine yeasts (Saccharomyces cerevisiae Actiflore F33), was studied. PEF treatment was applied to the aqueous yeast suspensions ([Y] = 0.012 g/L) at the electric field strengths of E = 100 and 6000 V/cm using the same treatment protocol (number of pulses n = 1000, pulse duration ti = 100 µs, and pulse repetition time Δt = 100 ms). Electrical conductivity was increasing during and after the PEF treatment, which reflected cell electroporation. Then, fermentation was run for 150 h in an incubator (30 °C) with synchronic agitation. Electro-stimulation was revealing itself by the improvement of fermentation characteristics, and thus increased yeast metabolism. At the end of the lag phase (t = 40 h), fructose consumption in samples with electrically activated inoculum exceeded that of the control samples by ≈ 2.33 times for E = 100 V/cm and by ≈ 3.98 for E = 6000 V/cm. At the end of the log phase (120 h of fermentation), ≈ 30% mass reduction was reached in samples with PEF-treated inocula (E = 6000 V/cm), whereas the same mass reduction of the control sample required approximately 20 extra hours of fermentation.

Jamming and percolation in generalized models of random sequential adsorption of linear k-mers on a square lattice.

The jamming and percolation for two generalized models of random sequential adsorption (RSA) of linear k-mers (particles occupying k adjacent sites) on a square lattice are studied by means of Monte Carlo simulation. The classical RSA model assumes the absence of overlapping of the new incoming particle with the previously deposited ones. The first model is a generalized variant of the RSA model for both k-mers and a lattice with defects. Some of the occupying k adjacent sites are considered as insulating and some of the lattice sites are occupied by defects (impurities). For this model even a small concentration of defects can inhibit percolation for relatively long k-mers. The second model is the cooperative sequential adsorption one where, for each new k-mer, only a restricted number of lateral contacts z with previously deposited k-mers is allowed. Deposition occurs in the case when z≤(1-d)z(m) where z(m)=2(k+1) is the maximum numbers of the contacts of k-mer, and d is the fraction of forbidden contacts. Percolation is observed only at some interval k(min)≤k≤k(max) where the values k(min) and k(max) depend upon the fraction of forbidden contacts d. The value k(max) decreases as d increases. A logarithmic dependence of the type log(10)(k(max))=a+bd, where a=4.04±0.22,b=-4.93±0.57, is obtained.

Percolation and jamming of linear k-mers on a square lattice with defects: Effect of anisotropy.

Using the Monte Carlo simulation, we study the percolation and jamming of oriented linear k-mers on a square lattice that contains defects. The point defects with a concentration d are placed randomly and uniformly on the substrate before deposition of the k-mers. The general case of unequal probabilities for orientation of depositing of k-mers along different directions of the lattice is analyzed. Two different relaxation models of deposition that preserve the predetermined order parameter s are used. In the relaxation random sequential adsorption (RRSA) model, the deposition of k-mers is distributed over different sites on the substrate. In the single-cluster relaxation (RSC) model, the single cluster grows by the random accumulation of k-mers on the boundary of the cluster (Eden-like model). For both models, a suppression of growth of the infinite (percolation) cluster at some critical concentration of defects d(c) is observed. In the zero-defect lattices, the jamming concentration p(j) (RRSA model) and the density of single clusters p(s) (RSC model) decrease with increasing length k-mers and with a decrease in the order parameter. For the RRSA model, the value of d(c) decreases for short k-mers (k<16) as the value of s increases. For k=16 and 32, the value of d(c) is almost independent of s. Moreover, for short k-mers, the percolation threshold is almost insensitive to the defect concentration for all values of s. For the RSC model, the growth of clusters with ellipselike shapes is observed for nonzero values of s. The density of the clusters p(s) at the critical concentration of defects d(c) depends in a complex manner on the values of s and k. An interesting finding for disordered systems (s=0) is that the value of p(s) tends towards zero in the limits of the very long k-mers, k→∞, and very small critical concentrations d(c)→0. In this case, the introduction of defects results in a suppression of k-mer stacking and in the formation of empty or loose clusters with very low density. On the other hand, denser clusters are formed for ordered systems with p(s)≈0.065 at s=0.5 and p(s)≈0.38 at s=1.0.

Percolation of linear k-mers on a square lattice: from isotropic through partially ordered to completely aligned states.

Numerical simulations by means of Monte Carlo method and finite-size scaling analysis have been performed to study the percolation behavior of linear k-mers (also denoted in publications as rigid rods, needles, sticks) on two-dimensional square lattices L × L with periodic boundary conditions. Percolation phenomena are investigated for anisotropic relaxation random sequential adsorption of linear k-mers. Especially, effect of anisotropic placement of the objects on the percolation threshold has been investigated. A detailed study of the behavior of percolation probability R(L)(p) that a lattice of size L percolates at concentration p in dependence on k, anisotropy, and lattice size L has been performed. A nonmonotonic size dependence for the percolation threshold has been confirmed in the isotropic case. We propose a fitting formula for percolation threshold, p(c) = a/k(α)+blog(10)k+c, where a, b, c, and α are the fitting parameters depending on anisotropy. We predict that for large k-mers (k >/≈ 1.2 × 10(4)) isotropically placed at the lattice, percolation cannot occur, even at jamming concentration.

Random sequential adsorption of partially oriented linear k-mers on a square lattice.

Jamming phenomena on a square lattice are investigated for two different models of anisotropic random sequential adsorption (RSA) of linear k-mers (particles occupying k adjacent adsorption sites along a line). The length of a k-mer varies from 2 to 256. The effect of k-mer alignment on the jamming threshold is examined. For completely ordered systems where all the k-mers are aligned along one direction (e.g., vertical), the obtained simulation data are very close to the known analytical results for one-dimensional systems. In particular, the jamming threshold tends to the Rényi's parking constant for large k. In the other extreme case, when k-mers are fully disordered, our results correspond to the published results for short k-mers. It was observed that for partially oriented systems the jamming configurations consist of the blocks of vertically and horizontally oriented k-mers (v and h blocks, respectively) and large voids between them. The relative areas of different blocks and voids depend on the order parameter s, k-mer length, and type of the model. For small k-mers (k⩽4), denser configurations are observed in disordered systems as compared to those of completely ordered systems. However, longer k-mers exhibit the opposite behavior.