Osmotic Attraction: A New Mechanism of Nanoparticle Aggregation.

Solvent-induced interactions of nanoparticles in colloidal solutions can substantially affect their physicochemical and transport properties. Predicting these interactions is challenging because the natural causes of the interactions are unclear. Here, we present a comprehensive experimental and theoretical study of the coagulation stability of the surfacted magnetic colloids. The magnetite nanoparticles stabilized by erucic acid were dispersed in 19 different good solvents. The colloidal stability was reduced by the gradual addition of a precipitant. As a precipitant, 19 other liquids were used. We show that coagulation is not associated with either dispersion or magnetic interactions. The coagulation mechanism is due to the osmotic attraction of nanoparticles induced by a specific local distribution of precipitant molecules. The precipitant molecules are repelled from the hydrophobic tails of the surfactant and form a depleted zone inside the surfactant layer leading to the appearance of the osmotic attraction between the nanoparticles and their subsequent coagulation when the critical concentration of the precipitant is reached. The quantitative description of the phenomenon is carried out within the framework of the generalized Asakura-Oosawa model of the attractive depletion forces between two adjacent particles and the Langmuir adsorption model for the equilibrium concentration of precipitant molecules in the surfactant layer of nanoparticles. The calculated precipitant critical concentrations, the coagulation curves of the polydisperse systems, and the variation of the coagulation criterion occurring upon changing the surfactant are in good agreement with the experimental data. The osmotic attraction mechanism is equally suitable for nanoparticles of any nature─plasmonic, semiconductor, or magnetic. This is determined by the surfactant-solvent interactions and is generic for many solvent-mediated systems taken at arbitrary concentrations of precipitant.

An Unreasonable Universality of the Thermophoretic Velocity.

Thermophoresis is the migration of dispersed molecules or particles in an inhomogeneous temperature field. It has been associated with various nonequilibrium phenomena ranging from stratified oil reservoirs to prebiotic evolution and the origin of life. The thermophoretic velocity is difficult to predict and appears almost random. We show that, in the case of strongly asymmetric mixtures with high molecular mass ratios of the solute to the solvent, it unexpectedly assumes a universal value once the trivial influence of the viscosity has been factored out. This asymptotic behavior is surprisingly universal and a general property of many highly asymmetric molecular mixtures ranging from organic molecules in n-alkanes to dilute solutions of high polymers. A quantitative explanation is provided on the basis of the asymmetric limit of the pseudoisotopic Soret effect.

The Soret effect of halobenzenes in n-alkanes: The pseudo-isotope effect and thermophobicities.

We have measured the Soret coefficients of three halobenzenes-fluoro-, chloro-, and bromobenzene-in n-alkanes ranging from hexane to hexadecane over the entire composition range at a temperature of 25 °C. With these new results, two semi-empirical models for the Soret effect, which are based on the pseudo-isotope effect and on the single-component thermophobicities, could significantly be expanded and put on a broader common experimental basis. In particular, for the longer alkanes, above decane, a simplified version of the pseudo-isotope effect yields a good description. In the dilute limit, the agreement of the chemical contributions to the Soret coefficient is perfect, but there are some unexplained systematic deviations at finite concentrations. We have used these Soret coefficients, together with the measurements of 1-bromonaphthalene in the n-alkanes, to expand the database for the thermophobicities of equimolar binary mixtures. Due to a vanishing mixing term in symmetric mixtures, the heats of transport computed from the Soret coefficients can be considered as differences in additive single component properties, the thermophobicities. This allows an ordering of the substances according to these numbers. In a binary mixture, the component with the higher thermophobicity migrates toward the cold side. With the new measurements, the database now contains 24 compounds with 107 out of 276 possible binary mixtures measured.

Optimal Length of Low Reynolds Number Nanopropellers.

Locomotion in fluids at the nanoscale is dominated by viscous drag. One efficient propulsion scheme is to use a weak rotating magnetic field that drives a chiral object. From bacterial flagella to artificial drills, the corkscrew is a universally useful chiral shape for propulsion in viscous environments. Externally powered magnetic micro- and nanomotors have been recently developed that allow for precise fuel-free propulsion in complex media. Here, we combine analytical and numerical theory with experiments on nanostructured screw-propellers to show that the optimal length is surprisingly short-only about one helical turn, which is shorter than most of the structures in use to date. The results have important implications for the design of artificial actuated nano- and micropropellers and can dramatically reduce fabrication times, while ensuring optimal performance.

Thermophobicity of liquids: heats of transport in mixtures as pure component properties--the case of arbitrary concentration.

We have measured Soret coefficients of a large number of binary mixtures of 23 different organic solvents. The present analysis is based on 77 equimolar mixtures and strongly supports the thermophobicity concept previously developed for the heats of transport of originally 10 different substances [S. Hartmann, G. Wittko, W. Köhler, K. I. Morozov, K. Albers, and G. Sadowski, Phys. Rev. Lett. 109, 065901 (2012)]. Among the investigated compounds, cis-decalin is the most thermophobic, hexane the most thermophilic one. In addition to the equimolar mixtures, we have also analyzed the composition dependence of the Soret coefficients and the heats of transport for 22 selected binary mixtures. Both the interpretation of the heats of transport in equimolar mixtures as pure component thermophobicities and the composition dependence of the Soret coefficient can be understood on the basis of the thermodiffusion theory developed by Morozov [Phys. Rev. E 79, 031204 (2009)], according to which the composition dependence is determined by the excess volume of mixing.

Thermophobicity of liquids: heats of transport in mixtures as pure component properties.

We have measured the Soret coefficients of 41 out of 45 possible equimolar binary mixtures of 10 different organic solvents and found an additive rule for the heats of transport. These can, except for an undetermined offset, uniquely be assigned to the pure components. Based on their heats of transport, the fluids can be arranged according to their thermophobicity, similar to the standard electrode potential. A qualitative explanation of this unexpected additivity is based on the work of Morozov [Phys. Rev. E 79, 031204 (2009)].

Nature of ferronematic alignment in a magnetic field.

Ferronematics are stable liquid crystal dispersions with high magnetic susceptibility. Although predicted many years ago (1970), they have been synthesized only recently. The experimental determination of the Fréedericksz transition critical field in ferronematics contradicts the earlier [Brochard and de Gennes, J. Phys. (Paris) 31, 691 (1970)] assumption of strong anchoring between liquid crystal molecules and magnetic grains. Here an explanation consistent with the experimental results of the coupling between liquid crystalline and magnetic degrees of freedom is given. We explain that this coupling is due to steric interactions between anisometric liquid crystal micelles and ferroparticle clusters.