Estimation of magnetic particle clustering in magnetic fluids from static magnetization experiments

The volume fraction dependence of the static magnetization of two magnetic fluids with different degrees of steric stabilization was measured at low field values (0-10 kA/m) and it was found to be nonlinear for both magnetic fluids. The nonlinearity is more pronounced in the case of the less stabilized magnetic fluid. The experimental data were processed by nonlinear regression using an analytical model for the formation of chain-like magnetic particle aggregates in magnetic fluids. The calculated dependence on the degree of steric stabilization, magnetic field, and sample concentration of the mean number of particles per chain was in the range (1-1.04).     

Phase behavior and particle size cutoff effects in polydisperse fluids

We report a joint simulation and theoretical study of the liquid-vapor phase behavior of a fluid in which polydispersity in the particle size couples to the strength of the interparticle interactions. Attention is focused on the case in which the particle diameters are distributed according to a fixed Schulz form with degree of polydispersity delta = 14%. The coexistence properties of this model are studied using grand canonical ensemble Monte Carlo simulations and moment free energy calculations. We obtain the cloud and shadow curves as well as the daughter phase density distributions and fractional volumes along selected isothermal dilution lines. In contrast to the case of size-independent interaction [N. B. Wilding et al., J. Chem. Phys. 121, 6887 (2004)], the cloud and shadow curves are found to be well separated, with the critical point lying significantly below the cloud curve maximum. For densities below the critical value, we observe that the phase behavior is highly sensitive to the choice of upper cutoff on the particle size distribution. We elucidate the origins of this effect in terms of extremely pronounced fractionation effects and discuss the likely appearance of new phases in the limit of very large values of the cutoff.     

Arrested chain growth during magnetic directed particle assembly in yield stress matrix fluids

The process of assembling particles into organized functional structures is influenced by the rheological properties of the matrix fluid in which the assembly takes place. Therefore, tuning these properties represents a viable and as yet unexplored approach for controlling particle assembly. In this Letter, we examine the effect of the matrix fluid yield stress on the directed assembly of polarizable particles into linear chains under a uniform external magnetic field. Using particle-level simulations with a simple yield stress model, we find that chain growth follows the same trajectory as in Newtonian matrix fluids up to a critical time that depends on the balance between the yield stress and the strength of magnetic interactions between particles; subsequently, the system undergoes structural arrest. Appropriate dimensionless groups for characterizing the arresting behavior are determined and relationships between these groups and the resulting structural properties are presented. Since field-induced structures can be indefinitely stabilized by the matrix fluid yield stress and "frozen" into place as desired, this approach may facilitate the assembly of more complex and sophisticated structures.     

Determination of crystallite particle size distribution of polymers from WAXS

A method for the calculation of crystallite size distributions from the profile of wide-angle x-ray reflections is developed. The influence of lattice distortions on the profile is taken into account. The information about the lattice distortions is obtained from the measurement of the integral widths of a number of reflections. The method is applied to samples of (ethylen-1 hexen) copolymers. The change of crystallite size distributions in lateral directions with increasing temperature (20–121°C) is measured. Recrystallization processes at temperatures near the melting point are observed. © 1996 John Wiley & Sons, Inc.     

On variations in size distributions of particles and aggregates upon dilution of magnetic fluids

Variations in size distributions of particles and aggregates upon dilution of kerosene-based magnetic fluids have been studied by dynamic light scattering. The data obtained on samples of magnetic fluids produced by three different manufacturers have shown that the dilution of an initial concentrated magnetic fluid leads to the formation of a system of unstable aggregates with sizes ranging from 70?100 nm to 1 μm. The aggregates peptize for 2?4 days to result in the establishment of stationary particle and aggregate size distributions.     

Determination of particle size distributions with angström resolution

An analytical ultracentrifugation technique for the determination of particle-size distributions is used which applies an ultracentrifuge with a scanning absorption optical system. Radial scans during a sedimentation velocity experiment yield the particle-size distribution. If the particles consist of several defined monodisperse species, we show that for dense inorganic colloids the resolution of the particle-size distribution is in the angström range. This is demonstrated for a Pt colloid (0.4-2 nm) and unstabilized ZnO (4-9 nm) during particle growth. Such highly resolved particle-size distributions show that the analytical ultracentrifuge is an excellent and rapid tool for the study of particle growth mechanisms as no other fractionating analytical technique with almost atomar resolution is known up to now. Some potential applications arising from the applied ultracentrifuge technique are suggested.     

Bidisperse electrorheological fluids using hydrolyzed styrene-acrylonitrile copolymer particles: synergistic effect of mixed particle size

Monodisperse micron-sized styrene-acrylonitrile copolymer (SAN) particles with three different sizes (about 5, 10, and 15 microm) were prepared by a two-step seeded polymerization and used for a study of bidisperse electrorheological (ER) suspensions. The effect of the particle size and the size-mixing fraction on ER properties was studied with varying the size of these monodisperse copolymer particles. When the two particle sizes were mixed, the suspension generally showed a decrease in the shear yield stress, reaching a minimum value. However, a bidisperse ER suspension of large particles containing a small fraction of fine particles showed an interesting synergy effect of size mixing on ER response, giving enhanced yield stresses over the other size-mixing fractions. This synergistic ER suspension also showed a great increase in the viscoelastic property. The current density of suspensions was maximum at the synergistic bidisperse suspension. This synergy effect in a particular bidisperse suspension was investigated in view of the structure model consideration and was concluded to be due to a close packing and a peculiar structural ordering at an optimum size ratio and mixing fraction.     

Determination of highly resolved particle size distributions in the submicron range by ultracentrifugation

Two methods, the H₂O/D₂O-analysis and the Coupling-Particle-Size-Distribution(PSD)-Technique, to determine the distribution of the density and the sire of sub-micron particles by means of an ultracentrifuge, are outlined. Either of them base only on Stokes' equations and on Mie's light scattering theory. Because of the possibility to measure seven samples simultaneously and to raise the rotor speed exponentially from 0 to 40,000 rpm, particle diameters from 10 to 3000 nm can be measured at high resolution. The H₂O/D₂O-analysis supplies a density distribution and also a size distribution, provided the sample is chemically homogeneous. The Coupling-PSD-Technique allows to determine highly resolved size distributions of extremely broad distributed dispersions by only one single run. Several examples applying either method are given.     

Single particle force distributions in simple fluids

The distribution function, W(F), of the magnitude of the net force, F, on particles in simple fluids is considered, which follows on from our previous publication [A. C. Bran?ka, D. M. Heyes, and G. Rickayzen, J. Chem. Phys. 135, 164507 (2011)] concerning the pair force, f, distribution function, P(f), which is expressible in terms of the radial distribution function. We begin by discussing the force on an impurity particle in an otherwise pure fluid but later specialize to the pure fluid, which is studied in more detail. An approximate formula, expected to be valid asymptotically, for W(F) referred to as, W(1)(F) is derived by taking into account only binary spatial correlations in the fluid. It is found that W(1)(F) = P(f). Molecular dynamics simulations of W for the inverse power (IP) and Lennard-Jones potential fluids show that, as expected, W(F) and P(f) agree well in the large force limit for a wide range of densities and potential forms. The force at which the maximum in W(F) occurs for the IP fluids follows a different algebraic dependence with density in low and high density domains of the equilibrium fluid. Other characteristic features in the force distribution functions also exhibit the same trends. An exact formula is derived relating W(F) to P(x)(F(x)), the distribution function of the x-cartesian components of the net force, F(x), on a particle. W(F) and P(x)(F(x)) have the same analytical forms (apart from constants) in the low and high force limits.     

Dipole interparticle interaction in magnetic fluids

The temperature dependence of the saturation magnetization of a magnetite-based magnetic fluid has been directly measured with a vibrating-coil magnetometer equipped with a superconducting solenoid. The magnetization varies in accordance with the 1 ? αT ² law. Coefficient α = 1.4 × 10^?6 is almost twice as high as that of monolithic magnetite. The results of measuring the susceptibility of magnetic fluids stabilized with oleic and linoleic acids have been analyzed using novel corrections to the temperature dependence of particle magnetization. The susceptibility of ultimately concentrated samples is in good agreement with the Ivanov-Huke-Lücke and Morozov theories. The susceptibility of samples with a medium concentration is adequately described by the Ivanov theory alone. The susceptibility of low-concentrated samples increases to the level predicted by the Morozov theory in the case of particle aggregation. The widening of the particle size distribution leads to a reduction in the level of the interparticle interactions.     

Physical properties of soft repulsive particle fluids

Molecular dynamics computer simulation has been applied to inverse power or soft-sphere fluids, in which the particles interact through the soft-sphere pair potential, phi(r) = epsilon(sigma/r)(n), where n measures the steepness or stiffness of the potential, and epsilon and sigma are a characteristic energy and distance, respectively. The focus of the study is on very soft particles with n values down to 4 considered, at densities up to and along the fluid-solid co-existence density. It is shown that in the soft-particle limit the local structure is dominated by the lengthscale associated with the average nearest neighbour distance of a random structure, which is proportional, variantrho(-1/3) and increasingly only very weakly dependent on n. This scaling is also manifest in the behaviour of the average energy per particle with density. The self-diffusion coefficient and shear viscosity are computed along the fluid-solid co-existence line as a function of n, for the first time. The product Deta(s) steadily increases with softness for n < 10, whereas the modified Stokes-Einstein relationship of Zwanzig, Deta(s)/rho(1/3), where rho is the number density, is within statistics constant over the same softness range. This is consistent with our observation that the static properties are determined by a characteristic lengthscale (i.e., l) which is proportional, variantrho(-1/3) in the soft-particle limit. The high frequency elastic moduli of these fluids are examined, which reveals that the mechanical properties become more 'rubbery' as the particles get softer.     

Determination of the latex particle size in emulsion polymerization of methyl methacrylate with low emulsifier concentrations

The mean size of the latex particles formed in emulsion polymerization of methyl methacrylate under definite conditions (water: monomer volume ratio 15: 1, 80°C, potassium persulfate concentration 0.07 wt %) decreases from 200 to 9–10 nm as the concentration of an ionic surfactant (anionic Disponil AES 60, SDS, cationic C₁₉H₄₂BrN) is increased from 0.0 to 1.0 wt %. The nonionic surfactants studied influence the size of the latex particles formed differently: with ALM-10, the particle size decreases from 200 to 150–190 nm, whereas with ALM-7 and ALM-2 it increases from 200 to 320 nm as the surfactant concentration is increased from 0.0 to 1.0 wt %. An increase in the concentration of F127 amphiphilic ternary block copolymer from 0.0 to 1.0 wt % leads to a monotonic decrease in the size of the poly(methyl methacrylate) latex particles formed from 200 to 53 nm.     

Low-temperature susceptibility of concentrated magnetic fluids

The initial susceptibility of concentrated magnetic fluids (ferrocolloids) has been experimentally investigated at low temperatures. The results obtained indicate that the interparticle dipole-dipole interactions can increase the susceptibility by several times as compared to the Langevin value. It is shown that good agreement between recent theoretical models and experimental observations can be achieved by introducing a correction for coefficients in the series expansion of susceptibility in powers of density and aggregation parameter. A modified equation for equilibrium susceptibility is offered to sum over corrections made by Kalikmanov (Statistical Physics of Fluids, Springer-Verlag, Berlin, 2001) and by B. Huke and M. Lucke (Phys. Rev. E 67, 051403, 2003). The equation gives good quantitative agreement with the experimental data in the wide range of temperature and magnetic particles concentration. It has been found that in some cases the magnetic fluid solidification occurs at temperature several tens of kelvins higher than the crystallization temperature of the carrier liquid. The solidification temperature of magnetic fluids is independent of particle concentration (i.e., magneto-dipole interparticle interactions) and dependent on the surfactant type and carrier liquid. This finding allows us to suggest that molecular interactions and generation of some large-scale structure from colloidal particles in magnetic fluids are responsible for magnetic fluid solidification. If the magnetic fluid contains the particles with the Brownian relaxation mechanism of the magnetic moment, the solidification manifests itself as the peak on the "susceptibility-temperature" curve. This fact proves the dynamic nature of the observed peak: it arises from blocking the Brownian mechanism of the magnetization relaxation.     

渣油中沥青质分子颗粒尺寸及其胶粒模型研究

分别以苯和硝基苯为溶剂测定了大庆、胜利、孤岛和辽河减压渣油沥青质、胶质和芳香分的分子量；依据球形分子模型计算了这些物质的分子尺寸；构筑了渣油中沥青质胶粒（胶团）模型，并依此计算了渣油中沥青质胶粒尺寸。结果表明，以硝基苯为溶剂所测沥青质分子量更能反应沥青质化学结构的实质；就原始沥青质来说，以苯为溶剂测得的沥青质分子直径为3.8 nm～5.0 nm,以氯代苯为溶剂测得的分子直径为3.2 nm～3.7 nm,以硝基苯为溶剂测得的分子直径为2.8 nm～3.2 nm；辽河、胜利与大庆减压渣油中沥青质的胶粒直径为10.0 nm～11.0 nm，孤岛减压渣油中沥青质的胶粒直径为9.0 nm～10.0 nm。     

Glassy arrest in colloidal fluids with size polydispersity

Short-range attraction between colloidal particles such as proteins can drive a glass-like structural arrest. For monodisperse systems, mode-coupling theory affords a simple asymptotic prediction of the transition. Here, using a depletion mapping framework, we extend this result to incorporate size polydispersity. For comparison, we also give an energy landscape formulation of the transition. We comment on the relevance to subcellular crowding, recombinant protein expression, and osmotic stress in microbial organisms.     

On the theory of birefringence in magnetic fluids

The influence of homogeneous correlations between the positions and orientations of ferroparticles on the effect of light birefringence in magnetic fluids has been studied. It has been demonstrated that, for typical magnetic fluids, the optical effects associated with the homogeneous correlations can be stronger than the effects caused by elongated primary aggregates formed at the stage of ferrofluid synthesis, as well as heterogeneous chains resulting from magnetic attraction between the largest particles of a magnetic fluid.     

Determination of particle size distribution by gravitational field-flow fractionation: Dimensional characterization of silica particles

Summary Gravitational field-flow fractionation (GFFF) is the simplest and cheapest of field-flow fractionation (FFF) techniques, although it is still at an early development stage. The application of GFFF to the determination of particle size distribution (PSD) of silica particles used as chromatographic supports is described. The accuracy of the method is evaluated by comparing PSDs obtained by GFFF with those obtained by laser diffraction, a non-separative technique widely applied to particle characterization. It is ultimately demonstrated that a low-cost GFFF channel can simply replace the column of a standard HPLC system, allowing laboratories that are not specialized in size analysis to perform accurate PSD studies with standard HPLC expertise.