Molecular dynamics study of nanoparticle stability at liquid interfaces: effect of nanoparticle-solvent interaction and capillary waves

While the interaction of colloidal particles (sizes in excess of 100 nm) with liquid interfaces may be understood in terms of continuum models, which are grounded in macroscopic properties such as surface and line tensions, the behaviour of nanoparticles at liquid interfaces may be more complex. Recent simulations [D. L. Cheung and S. A. F. Bon, Phys. Rev. Lett. 102, 066103 (2009)] of nanoparticles at an idealised liquid-liquid interface showed that the nanoparticle-interface interaction range was larger than expected due, in part, to the action of thermal capillary waves. In this paper, molecular dynamics simulations of a Lennard-Jones nanoparticle in a binary Lennard-Jones mixture are used to confirm that these previous results hold for more realistic models. Furthermore by including attractive interactions between the nanoparticle and the solvent, it is found that the detachment energy decreases as the nanoparticle-solvent attraction increases. Comparison between the simulation results and recent theoretical predictions [H. Lehle and M. Oettel, J. Phys. Condens. Matter 20, 404224 (2008)] shows that for small particles the incorporation of capillary waves into the predicted effective nanoparticle-interface interaction improves agreement between simulation and theory.     

Structure and diffusion of nanoparticle monolayers floating at liquid/vapor interfaces: a molecular dynamics study

Large-scale molecular dynamics simulations are used to simulate a layer of nanoparticles floating on the surface of a liquid. Both a low viscosity liquid, represented by Lennard-Jones monomers, and a high viscosity liquid, represented by linear homopolymers, are studied. The organization and diffusion of the nanoparticles are analyzed as the nanoparticle density and the contact angle between the nanoparticles and liquid are varied. When the interaction between the nanoparticles and liquid is reduced the contact angle increases and the nanoparticles ride higher on the liquid surface, which enables them to diffuse faster. In this case the short-range order is also reduced as seen in the pair correlation function. For the polymeric liquids, the out-of-layer fluctuation is suppressed and the short-range order is slightly enhanced. However, the diffusion becomes much slower and the mean square displacement even shows sub-linear time dependence at large times. The relation between diffusion coefficient and viscosity is found to deviate from that in bulk diffusion. Results are compared to simulations of the identical nanoparticles in 2-dimensions.     

Interactions between nanocolloidal particles in polymer solutions: effect of attractive interactions

We present a density-functional theory study of nanoparticle interactions in a concentrated polymer solution. The polymers are modeled as freely jointed tangent chains; all nonbonded interactions between polymer segments and nanoparticles are described by Lennard-Jones potentials. We test several recently proposed methods of treating attractive interactions within the density-functional theory framework by comparing theoretical results with recent simulation data. We find that the simple van der Waals approach provides the most accurate results for the polymer-mediated potential of mean force between two dilute nanoparticles. We employ this approach to study nanoparticle interactions as a function of nanoparticle-segment interaction strength and polymer solution density and temperature.     

Simulation of interaction forces between nanoparticles in the presence of Lennard-Jones polymers: freely adsorbing homopolymer modifiers

The force between two nanoscale colloidal particles dispersed in a solution of freely adsorbing Lennard-Jones homopolymer modifiers is calculated using the expanded grand canonical Monte Carlo simulation method. We investigate the effect of polymer chain length (N), nanoparticle diameter (sigma(c)), and colloid-polymer interaction energy (epsilon(cp)) on polymer adsorption (Gamma) and polymer-induced forces (F(P)(r)) between nanoparticles in the full thermodynamic equilibrium condition. There is a strong correlation between polymer adsorption and the polymer-mediated nanoparticle forces. When the polymer adsorption is weak, as in the case of smaller diameters and short polymer chain lengths (sigma(c) = 5, N = 10), the polymers do not have any significant effect on the bare nanoparticle interactions. The adsorbed amount increases with increasing particle diameter, polymer chain length, and colloid-polymer interaction energy. In general, for strong polymer-particle adsorption the polymer-governed force profiles between nanoparticles show short-range repulsion and long-ranged attraction, suggesting that homopolymers would not be ideal for achieving stabilization in nanoparticle dispersions. The attraction is likely due to bridging, as well as polymer segment-segment interactions. The location and magnitude of attractive minimum in the force profile can be controlled by varying N and epsilon(cp). The results show partial agreement and some marked differences with previous theoretical and experimental studies of forces in the limit of flat walls in an adsorbing polymer solution. The difference could be attributed to incorporation of long-ranged colloid-polymer potential in our simulations and the influence of the curvature of the nanoparticles.     

Thermodiffusion in model nanofluids by molecular dynamics simulations

In this work, a new algorithm is proposed to compute single particle (infinite dilution) thermodiffusion using nonequilibrium molecular dynamics simulations through the estimation of the thermophoretic force that applies on a solute particle. This scheme is shown to provide consistent results for model nanofluids in the liquid state (spherical nonmetallic nanoparticles+Lennard-Jones fluid) where it appears that thermodiffusion amplitude, as well as thermal conductivity, decreases with nanoparticle concentration. Then, by changing the nature of the nanoparticle (size, mass, and internal stiffness) and that of the solvent (quality and viscosity), various trends are exhibited. In all cases, the single particle thermodiffusion is positive, i.e., the nanoparticle tends to migrate toward the cold area. The single particle thermal diffusion coefficient is shown to be independent of the size of the nanoparticle (diameter of 0.8-4 nm), whereas it increases with the quality of the solvent and is inversely proportional to the viscosity of the fluid. In addition, this coefficient is shown to be independent of the mass of the nanoparticle and to increase with the stiffness of the nanoparticle internal bonds. Besides, for these configurations, the mass diffusion coefficient behavior appears to be consistent with a Stokes-Einstein-like law.     

A novel algorithm for creating coarse-grained, density dependent implicit solvent models

Implicit solvent simulations are those in which solvent molecules are not explicitly simulated, and the solute-solute interaction potential is modified to compensate for the implicit solvent effect. Implicit solvation is well known in Brownian dynamics of dilute solutions but offers promise to speed up many other types of molecular simulations as well, including studies of proteins and colloids where the local density can vary considerably. This work examines implicit solvent potentials within a more general coarse-graining framework. While a pairwise potential between solute sites is relatively simple and ubiquitous, an additional parametrization based on the local solute concentration has the possibility to increase the accuracy of the simulations with only a marginal increase in computational cost. We describe here a method in which the radial distribution function and excess chemical potential of solute insertion for a system of Lennard-Jones particles are first measured in a fully explicit, all-particle simulation, and then reproduced across a range of solute particle densities in an implicit solvent simulation.     

Atomistic simulations of calcite nanoparticles and their interaction with water

Molecular dynamics (MD) simulations have been used to study the stability of calcite nanoparticles ranging in size from 18 to 324 f.u., both in vacuo and in the presence of explicit water molecules. In vacuo, the smallest particles become highly disordered during the MD simulation due to rotation and translation of the undercoordinated CO(3) (2-) anions at the edges of the particles. As the nanoparticle size increases, the influence of the fully coordinated bulk ions begins to dominate and long-range order is seen both in the Ca-C pair distribution functions and in the degree of rotational order of the CO(3) (2-) anions. However, when explicit water is added to the system, the molecules in the first hydration layer complete the coordination shell of the surface ions, preserving structural order even in the smallest of the nanoparticles. Close to particle surface, the structure of the water itself shows features similar to those seen close to planar periodic (1014) surfaces, although the molecules are far less tightly bound.     

Tunable solvation effects on the size-selective fractionation of metal nanoparticles in CO2 gas-expanded solvents

This paper presents an environmentally friendly, inexpensive, rapid, and efficient process for size-selective fractionation of polydisperse metal nanoparticle dispersions into multiple narrow size populations. The dispersibility of ligand-stabilized silver and gold nanoparticles is controlled by altering the ligand tails-solvent interaction (solvation) by the addition of carbon dioxide (CO2) gas as an antisolvent, thereby tailoring the bulk solvent strength. This is accomplished by adjusting the CO2 pressure over the liquid, resulting in a simple means to tune the nanoparticle precipitation by size. This study also details the influence of various factors on the size-separation process, such as the types of metal, ligand, and solvent, as well as the use of recursive fractionation and the time allowed for settling during each fractionation step. The pressure range required for the precipitation process is the same for both the silver and gold particles capped with dodecanethiol ligands. A change in ligand or solvent length has an effect on the interaction between the solvent and the ligand tails and therefore the pressure range required for precipitation. Stronger interactions between solvent and ligand tails require greater CO2 pressure to precipitate the particles. Temperature is another variable that impacts the dispersibility of the nanoparticles through changes in the density and the mole fraction of CO2 in the gas-expanded liquids. Recursive fractionation for a given system within a particular pressure range (solvent strength) further reduces the polydispersity of the fraction obtained within that pressure range. Specifically, this work utilizes the highly tunable solvent properties of organic/CO2 solvent mixtures to selectively size-separate dispersions of polydisperse nanoparticles (2 to 12 nm) into more monodisperse fractions (+/-2 nm). In addition to providing efficient separation of the particles, this process also allows all of the solvent and antisolvent to be recovered, thereby rendering it a green solvent process.     

Two-particle friction in a mesoscopic solvent

The effects of hydrodynamic interactions on the friction tensors for two particles in solution are studied. The particles have linear dimensions on nanometer scales and are either simple spherical particles interacting with the solvent through repulsive Lennard-Jones forces or are composite cluster particles whose atomic components interact with the solvent through repulsive Lennard-Jones forces. The solvent dynamics is modeled at a mesoscopic level through multiparticle collisions that conserve mass, momentum, and energy. The dependence of the two-particle relative friction tensors on the interparticle separation indicates the importance of hydrodynamic interactions for these nanoparticles.     

Molecular dynamics simulation of the forces between colloidal nanoparticles in n-decane solvent

Molecular dynamics is utilized to simulate solvation forces between two nanoparticles immersed in liquid n-decane. Three types of solvophilic nanoparticles are investigated with sizes in the 1-6 nm range: small and large amorphous spheres and crystalline cubes. We find that the solvation forces are negligible for the small spheres, which have diameters comparable to the end-to-end distance of all-trans decane, and we attribute this to the inability of the small spheres to induce decane ordering in the interparticle gap. The cubic nanoparticles (and to a lesser extent, the large spheres) are able to induce the formation of solidlike, n-decane layers in their gap for certain nanoparticle separations, and the transition between layered and disordered structures leads to solvation forces that oscillate between repulsion and attraction as the nanoparticle separation is varied. We find that the Derjaguin approximation [B. V. Derjaguin, Kolloid-Z. 69, 155 (1934)] is not effective at describing the dependence of the solvation forces on nanoparticle size and shape-contrasting results from a previous study involving these nanoparticles in Lennard-Jones solvent [Y. Qin and K. A. Fichthorn, J. Chem. Phys. 119, 9745 (2003)]. In particular, we find that for decane, the magnitude of the repulsive solvation forces is sensitive to nanoparticle size and shape, a phenomenon we attribute to the size and rigid-rod structure of n-decane, which makes its ordering in the interparticle gap sensitive to the size and the surface roughness of the nanoparticles.     

Effective interaction between charged nanoparticles and DNA

We investigate the effective interaction mediated by salt ions between charged nanoparticles (NPs) and DNA. DNA is modeled as an infinite cylinder with a constant surface charge in an implicit solvent. Monte Carlo simulations are used to compute the free energy of the system described in the framework of the primitive model of electrolytes, which accounts for excluded volumes of salt ions. A mean-field Poisson-Boltzmann theory also allows us to compute the free energy and provides us with explicit formulae for its main characteristics (position and depth of the minimum). We intend here to identify the physical parameters that have a major impact on the NP-DNA interaction, in an attempt to evaluate physico-chemical properties which could play a role in genotoxicity or, which could be exploited for therapeutic use. Thus, we investigate the influence on the effective interaction of: the shape of the nanoparticle, the magnitude of the nanoparticle charge and its distribution, the value of the pH of the solution, the magnitude of Van der Waals interactions depending on the nature of the constitutive material of the NP (metal vs. dielectric). We show that for positively charged concave NPs the effective interaction is repulsive at short distance, so that it presents a minimum at distance from the DNA. This short-range repulsion is specific to indented particles and is a robust property that holds for a large range of materials and charge densities.     

Ion-mediated interactions between charged and neutral nanoparticles

Monte-Carlo simulations are used to study the ion-mediated effective interaction between weakly charged and highly charged nanoparticles in an implicit solvent. Three models of nanoparticles are successively studied, from crude charged hard spheres to dipolar and non-spherical nanoparticles. The analysis of the effective potential revealed that in an electrolyte solution, even a neutral nanoparticle feels an important repulsive force in the presence of a charged nanoparticle, with a typical range similar to the Debye length. When the two nanoparticles carry charges of opposite sign, we have shown that this repulsion can reverse the effect of the direct attractive electrostatic potential at short distances. This also yields the change of sign of the effective potential as a function of the relative orientations of two anisotropic nanoparticles. Moreover, we found that the 3-body terms of the effective potentials can overcome the 2-body terms, which is not observed in the case of symmetrically charged nanoparticles.     

Voronoi neighbor statistics of hard-disks and hard-spheres

The neighbor distribution in hard-sphere and hard-disk fluids is analyzed using Voronoi tessellation. The statistical measures analyzed are the nth neighbor coordination number (Cn), the nth neighbor distance distribution [fn(r)], and the distribution of the number of Voronoi faces (Pn). These statistics are sensitive indicators of microstructure, and they distinguish thermodynamic and annealed structures. A sharp rise in the hexagon population marks the onset of hard-disk freezing transition, and Cn decreases sharply to the hexagonal lattice values. In hard-disk random structures the pentagon and heptagon populations remain significant even at high volume fraction. In dense hard-sphere (three-dimensional) structures at the freezing transition, C1 is close to 14, instead of the value of 12 expected for a face-centered-cubic lattice. This is found to be because of a topological instability, where a slight perturbation of the positions in the centers of a pair of particles transforms a vertex in the Voronoi polyhedron into a Voronoi surface. We demonstrate that the pair distribution function and the equation-of-state obtained from Voronoi tessellation are equal to those obtained from thermodynamic calculations. In hard-sphere random structures, the dodecahedron population decreases with increasing density. To demonstrate the utility of the neighbor analysis, we estimate the effective hard-sphere diameter of the Lennard-Jones fluid by identifying the diameter of the spheres in the hard-sphere fluid which has C1 equal to that for the Lennard-Jones fluid. The estimates are within 2% deviation from the theoretical results of Barker-Henderson and Weeks-Chandler-Andersen.     

Spontaneous formation of core/shell bimetallic nanoparticles: a calorimetric study

We showed recently that low entropy core/shell structured nanoparticles form spontaneously from the physical mixture of a dispersion of Ag nanoparticles and that of another noble metal (Rh, Pd, or Pt) at room temperature. Here we use isothermal titration calorimetry (ITC) and show that the initial step of such a spontaneous process is strongly exothermic. When the alcohol dispersion of poly(N-vinyl-2-pyrrolidone) (PVP)-protected Rh nanoparticles (average diameter 2.3 nm) was titrated into the alcoholic dispersion of PVP-protected Ag nanoparticles, a strong exothermic enthalpy change, DeltaH, was observed: DeltaH = -908 kJ/mol for Ag(S) nanoparticle (average diameter 10.8 nm) and -963 kJ/mol for Ag(L) nanoparticles (average diameter 22.5 nm). The strength of interaction increases in the order of Rh/Ag > Pd/Ag > Pt/Ag. This strong exothermic interaction is considered as a driving force to from low entropy bimetallic nanoparticles by simple mixing of two kinds of monometallic nanoparticles. We show also that exothermic interactions occur between a pair of noble metal nanoparticles themselves by using ITC.     

Size ratio effects on interparticle interactions and phase behavior of microsphere-nanoparticle mixtures

We investigate the interparticle interactions and phase behavior of microsphere-nanoparticle mixtures of high charge asymmetry and varying size ratio. In the absence of nanoparticles, negligibly charged microspheres flocculate as a result of van der Waals interactions. Upon addition of a lower critical nanoparticle volume fraction, the microspheres are stabilized by the formation of nanoparticle halos around each microsphere. , A weak attraction between the two species leads to a pronounced enhancement of the effective nanoparticle concentration near the microsphere surface relative to the bulk solution. Above an upper critical nanoparticle volume fraction, the microspheres undergo reentrant gelation. Binary mixtures, in which the effective nanoparticle size is reduced at a fixed microsphere diameter, exhibit a narrow window of stability that ultimately disappears with increasing ionic strength. By contrast, binary mixtures of varying microsphere diameter are stabilized at similar nanoparticle volume fractions and exhibit a broader window of stability with decreasing size ratio. This unexpected observation may arise from the reduced attraction between smaller microspheres because negligible differences in nanoparticle halo formation are observed in these mixtures.     

Aging investigation of cobalt ferrite nanoparticles in low pH magnetic fluid

In this study, we report on how surface-passivated and nonpassivated cobalt ferrite nanoparticles (8 nm diameter), suspended as ionic magnetic fluids and aged under low pH conditions, revealed different behavior as far as the time evolution of the iron/cobalt cation distribution, crystal quality, coercivity, and saturation magnetization are concerned. Different techniques were used to perform a detailed study regarding the chemical stability, structural stability, and surface and magnetic properties of the suspended nanoparticles as a function of the aging time. Properties of surface-passivated and nonpassivated nanoparticles were investigated by transmission electron microscopy, X-ray diffraction, atomic absorption spectrometry, magnetic measurements, Raman spectroscopy, and M?ssbauer spectroscopy. Our data showed that the employed nanoparticle surface passivation process, besides the formation of an iron-rich surface layer, modifies the nanoparticle core as well, improving the crystal quality while modifying the Fe/Co cation distribution and the nanoparticle dissolution rate profile. Magnetic data showed that the saturation magnetization increases for surface-passivated nanoparticles in comparison to the nonpassivated ones, though coercivity decreases after passivation. These two observations were associated to changes in the cation distribution among the available tetrahedral and octahedral sites.     

Preparation and surface characterization of polymer nanoparticles designed for incorporation into hybrid materials

We prepared water dispersions of poly(n-butyl methacrylate-st-butyl acrylate) crosslinked core-shell nanoparticles functionalized with different amounts of trimethoxisilane (TMS) groups in the outer shell. The purpose of the TMS groups is to chemically bind the rubbery particles to a nanostructured silica network, using sol-gel copolymerization. Here, we present nanoparticles containing 13 mol % and 30 mol % of TMS groups in the outer shell and compare their surface morphology with particles that do not contain TMS. The particles are prepared by a two-step seeded emulsion polymerization technique at neutral pH. In the first step, we obtained crosslinked seed particles (44 nm in diameter) by a batch process. In the second step, we used a semi-continuous emulsion polymerization technique under starved feed conditions to obtain monodispersed particles of controlled composition and size (ca. 100 nm in diameter). Fluorescence decay measurements were performed in situ on the dispersions, using a pair of cationic dyes adsorbed onto the surface of the nanoparticles: rhodamine 6G as the energy transfer donor and malachite green carbinol hydrochloride as the acceptor. The kinetics of F?rster resonance energy transfer (FRET) between the dyes is sensitive to the donor-acceptor distance, allowing us to obtain the binding distribution of the dyes at the nanoparticle surface. For the unmodified nanoparticles, we found a dye distribution that corresponds to an average interface thickness of delta = (5.2 +/- 0.2) nm. For the samples containing 13 mol % and 30 mol % of TMS groups in the outer shell we obtained broader interfaces, with widths of delta = (6.2 +/- 0.2) nm and delta = (6.5 +/- 0.1) nm respectively. This broadening of the distribution with the surface modification is interpreted in terms of the increase in free volume of the shell caused by the TMS groups. Finally, we studied the effect of temperature on the water-polymer interface fuzziness, in order to evaluate the accessibility of the TMS groups during the sol-gel synthesis of nanostructured hybrid materials.     

Refractive index of sparse layers of adsorbed gold nanoparticles

Measurements are presented of the effective complex refractive index of a layer of gold nanoparticles adsorbed to a silicon wafer at low coverages. The measurements were made by means of variable-angle ellipsometry, and correlated with nanoparticle coverage determined from atomic force microscope images. The analysis establishes the effective refractive index of a uniform layer whose thickness equals the nanoparticle diameter. A simple empirical relationship is obtained for real component of refractive index as a function of the fractional nanoparticle coverage regardless of the nanoparticle size. The imaginary component also follows a simple relationship but only up to a certain coverage, above which it increases rapidly. These relationships may be useful in other contexts such as chemical or biosensors in which the nanoparticle coverage could be inferred from optical measurements such as ellipsometry, surface plasmon resonance spectroscopy, reflectometry, or interferometry.     

Diffusion of nanoparticles in dense fluids

The diffusion process of a single spherical nanoparticle immersed in a fluid solvent is studied by molecular dynamics simulations. When the nanoparticle mass stays constant, it is shown that, at short times, the decay of the nanoparticle velocity autocorrelation function is strongly modified when the particle diameter increases. It is also shown that, at large times, the characteristic algebraic decay induced by the hydrodynamic correlations between the solvated particle and the solvent presents a scaling behavior depending on the particle diameter.