Structure factor of ferrofluids with chain aggregates: Influence of an external magnetic field

In this paper we present the structure factor of ferrofluid with chain aggregates under the influence of an externally applied magnetic field. On the basis of the equilibrium chains distribution the structure factor is calculated as Fourier transform of the radial distribution function. An extensive comparison of the theoretical model to the results of computer simulations showed a qualitative agreement of the data. The existence of the chains leads to strong anisotropy of the structure factor for the cases parallel and perpendicular to the external magnetic field.     

Study of the structure factor anisotropy and long range correlations of ferrofluids in the dilute low-coupling regime

Dipolar soft-sphere (DSS) fluids in the dilute low-coupling regime are studied via Molecular Dynamic simulations and the extension of a theoretical formalism previously used for dipolar hard spheres in which new terms for the virial expansion of the radial distribution function corresponding to the three-particle contribution are presented and tested for the zero and non-zero magnetic field case. A thorough comparison with simulations shows that the extended formalism is able to account for the structure factors of DSS with and without externally applied magnetic fields in the dilute low-coupling regime: quantitative agreement between theory and simulations is found for dipolar coupling parameters λ?2, and volume fraction φ?0.25. When λ>1 the new added term to the virial expansion is observed to play a crucial role in order to match quantitatively theory and simulations at zero field. In the presence of an external magnetic field our tests show that further improvements are needed and only new terms with Langevin function dependences can significatively contribute to improve the predictions for the dilute low-coupling regime. Numerical simulations show that despite that the ferrofluids considered here are in the dilute low-coupling regime, when an external field is applied, important correlations along the parallel direction to the field and depletion phenomena along the perpendicular direction are observed in the averaged density surrounding a particle.     

Inertial deposition of nanoparticle chain aggregates: Theory and comparison with impactor data for ultrafine atmospheric aerosols

Nanoparticle chain aggregates (NCAs) are often sized and collected using instruments that rely on inertial transport mechanisms. The instruments size segregate aggregates according to the diameter of a sphere with the same aerodynamic behavior in a mechanical force field. A new method of interpreting the aerodynamic diameter of NCAs is described. The method can be used to calculate aggregate surface area or volume. This is useful since inertial instruments are normally calibrated for spheres, and the calibrations cannot be directly used to calculate aggregate properties. A linear relationship between aggregate aerodynamic diameter and primary particle diameter based on published Monte-Carlo drag calculations is derived. The relationship shows that the aggregate aerodynamic diameter is independent of the number of primary particles that compose an aggregate, hence the aggregate mass. The analysis applies to aggregates with low fractal dimension and uniform primary particle diameter. This is often a reasonable approximation for the morphology of nanoparticles generated in high temperature gases. An analogy is the use of the sphere as an approximation for compact particles. The analysis is applied to the collection of NCAs by a low-pressure impactor. Our results indicate the low-pressure impactor collects aggregates with a known surface area per unit volume on each stage. Combustion processes often produce particles with aggregate structure. For diesel exhaust aggregates, the surface area per unit volume calculated by our method was about twice that of spheres with diameter equal to the aerodynamic diameter. Measurements of aggregates collected near a major freeway and at Los Angeles International Airport (LAX) were made for two aerodynamic cutoff diameter diameters (d _a,50), 50 and 75 nm. (Aerodynamic cutoff diameter refers to the diameter of particles collected with 50% efficiency on a low-pressure impactor stage.) Near-freeway aggregates were probably primarily a mixture of diesel and internal combustion engine emissions. Aggregates collected at LAX were most likely present as a result of aircraft emissions. In both measurements, the aggregate aerodynamic diameters calculated from the primary particle diameter were fairly close to the stage cutoff diameter. The number of primary particles per aggregate varied one order of magnitude for particles depositing on the same stage. The average aggregate surface area per unit volume was 2.41 × 10⁶ cm⁻¹ and 2.59 × 10⁶ cm⁻¹ (50 nm d _a,50) and 1.81 × 10⁶ cm⁻¹ and 1.68 × 10⁶ cm⁻¹ (75 nm d _a,50) for near-freeway and LAX measurements, respectively. These preliminary measurements are consistent with values calculated from theory.     

Extinction of polarized light in ferrofluids with different magnetic particle concentrations

The magnetic field intensity and nanoparticle concentration dependence of the polarized light extinction in a ferrofluid made of magnetite particles stabilized with technical grade oleic acid dispersed in transformer oil was experimentally investigated. The magnetically induced optical anisotropy, i.e. the dichroism divided by concentration, was found to decrease with increasing sample concentration from 2% to 8%. The magnetically induced change in the optical extinction of light polarized at 54.74° with respect to the magnetic field direction was found to be positive for the less concentrated sample (2%) and negative for the samples with 4% and 8% magnetic nanoparticle concentrations, the more negative the higher the concentration and field intensity. Based on the theoretically proven fact [11] that the particle orientation mechanism has no effect on the extinction of light polarized at 54.74° with respect to the field direction, we analyzed the experimental findings in the frames of the agglomeration and long-range pair correlations theories for the magnetically induced optical anisotropy in ferrofluids. We developed a theoretical model in the approximation of single scattering for the optical extinction coefficient of a ferrofluid with magnetically induced particle agglomeration. The model predicts the existence of a polarization independent component of the optical extinction coefficient that is experimentally measurable at 54.74° polarization angle. The change in the optical extinction of light polarized at 54.74° is positive if only the formation of straight n-particle chains is considered and may become negative in the hypothesis that the longer chains degenerate to more isotropic structures (polymer-like coils, globules or bundles of chains). The model for the influence on the light absorption of the long-range pair correlations, published elsewhere, predicts that the change in the optical extinction of light polarized at 54.74° is always negative, the more negative the higher the magnetic field intensity and particle concentration.     

The quasi-magnetic-hysteresis behavior of polydisperse ferrofluids with small coupling constant

The magnetization behaviors of ferrofluids based on γ-Fe₂O₃/Ni₂O₃ composite nanoparticles of size about 11 nm have been investigated. The dipole coupling constant λ of these particles is so small (0.43) that they cannot form aggregates through magnetic interaction alone. Experimental results have shown that for a polydisperse ferrofluid with a particle volume fraction of ?_V=2.4%, the magnetization curve exhibits quasi-magnetic-hysteresis behavior, i.e., the demagnetization curve lies above the magnetization curve in a high field. However, for a more dilute γ-Fe₂O₃/Ni₂O₃ ferrofluid with ?_V=0.94%, the magnetization curve does not show such behavior. According to the bidisperse model for polydisperse ferrofluids, these magnetization behaviors may be attributed to field-induced effects of self-assembled pre-existing chain-like aggregates. For such pre-existing chain-like aggregates, the orientation of the moments inside the particles is not co-linear, so that during the magnetization and demagnetization processes, their apparent magnetizations at the high-field limit are different. As a consequence, the magnetization curve of the ferrofluid with ?_V=2.4% displays quasi-magnetic-hysteresis.     

Study of magnetic and structural properties of ferrofluids based on cobalt-zinc ferrite nanoparticles

Ferrofluids are colloidal systems composed of a single domain of magnetic nanoparticles with a mean diameter around 30 nm, dispersed in a liquid carrier. Magnetic Co_(1−x)Zn_xFe₂O₄ (x=0.25, 0.50, 0.75) ferrite nanoparticles were prepared via co-precipitation method from aqueous salt solutions in an alkaline medium. The composition and structure of the samples were characterized through Energy Dispersive X-ray Spectroscopy and X-ray diffraction, respectively. Transmission Electron Microscopy (TEM) studies permitted determining nanoparticle size; grain size of nanoparticle conglomerates was established via Atomic Force Microscopy. The magnetic behavior of ferrofluids was characterized by Vibrating Sample Magnetometer (VSM); and finally, a magnetic force microscope was used to visualize the magnetic domains of Co_(1−x)Zn_xFe₂O₄ nanoparticles. X-ray diffraction patterns of Co_(1−x)Zn_xFe₂O₄ show the presence of the most intense peak corresponding to the (311) crystallographic orientation of the spinel phase of CoFe₂O₄. Fourier Transform Infrared Spectroscopy confirmed the presence of the bonds associated to the spinel structures; particularly for ferrites. The mean size of the crystallite of nanoparticles determined from the full-width at half maximum of the strongest reflection of the (311) peak by using the Scherrer approximation diminished from (9.5±0.3) nm to (5.4±0.2) nm when the Zn concentration increases from 0.21 to 0.75. The size of the Co-Zn ferrite nanoparticles obtained by TEM is in good agreement with the crystallite size calculated from X-ray diffraction patterns, using Scherer's formula. The magnetic properties investigated with the aid of a VSM at room temperature presented super-paramagnetic behavior, determined by the shape of the hysteresis loop. In this study, we established that the coercive field of Co_(1−x)Zn_xFe₂O₄ magnetic nanoparticles, the crystal and nanoparticle sizes determined by X-ray Diffraction and TEM, respectively, decrease with the increase of the Zn at%. Finally, our magnetic nanoparticles are not very hard magnetic materials given that the hysteresis loop is small and for this reason Co_(1−x)Zn_xFe₂O₄ nanoparticles are considered as soft magnetic material.     

Field-induced motion of ferrofluids through immiscible viscous media: Testbed for restorative treatment of retinal detachment

Biocompatible, hydrophobic ferrofluids comprised of magnetite nanoparticles dispersed in polydimethylsiloxane show promise as materials for the treatment of retinal detachment. This paper focuses on the motion of hydrophobic ferrofluid droplets traveling through viscous aqueous media, whereby the movement is induced by gradients in external fields generated by small permanent magnets. A numerical method was utilized to predict the force on a spherical droplet, and then the calculated force was used to estimate the time required for the droplet to reach the permanent magnet. The calculated forces and travel times were verified experimentally.     

Structure factor of a hard-core fluid with short-range Yukawa attraction: analytical FMSA theory against Monte Carlo simulations

ABSTRACT

Analytical solution of the first-order Ornstein–Zernike equation known as the first-order mean spherical approximation (FMSA) theory due to Tang and Lu [J. Chem. Phys. 99, 9828 (1993)] is used to write down a closed equation for the static structure factor of the hard-sphere fluid with a short-range Yukawa attraction. Calculations are performed for a Yukawa decay exponent that corresponds to a range of attraction that does not exceed the first coordination shell of Lennard-Jones-like simple fluids. By comparison with Monte Carlo simulation data it is shown that the analytical FMSA equation for the static structure factor is of the same or even of superior accuracy as that within the seminumerical mean spherical approximation theory.     

Magnetic and optical response of tuning the magnetocrystalline anisotropy in Fe3O4 nanoparticle ferrofluids by Co doping

Co_xFe_3−xO₄ (0?x?0.10) nanoparticles coated with tetramethyl ammonium hydroxide as a surfactant were synthesized by a co-precipitation technique. The Fe:Co ratio was tuned up to x=0.10 by controlling the Co²⁺ concentration during synthesis. The mean particle size, determined by transmission electron microscopy, ranged between 15±4 and 18±4 nm. The superparamagnetic blocking temperature and the magnetocrystalline anisotropy constant of the ferrofluids, determined using ac and dc magnetic measurements, scale approximately linearly with cobalt concentration. We also find distinct differences in the optical response of different samples under an applied magnetic field. We attribute changes in field-induced optical relaxation for the x=0 and 0.05 samples to differences in the anisotropic microstructure under an applied magnetic field.     

Extended calculation of polarization and intensity of fractal aggregates based on rigorous method for light scattering simulations with numerical orientation averaging

The intensity and polarization of fractal aggregates have been investigated using both rigorous and approximate methods for light scattering simulations. However, previous studies using the analytical orientation averaging version of the rigorous method were generally limited to a few hundred monomers when the monomer size parameter was around 1.7. In this study, we propose using numerical orientation averaging instead of analytical orientation averaging. The numerical averaging is performed together with a fixed orientation version of the rigorous T-matrix method for clusters of spheres. This approach enables increasing the number of monomers by a factor of 2-7 or the size of monomers by a factor of 8-10 compared to the analytical orientation averaging version.We investigated the influence of monomer size and the number of monomers on the light scattering of silicate aggregates (refractive index m=1.68+0.03i) for incident light with a wavelength of . We considered ballistic particle-cluster aggregates (BPCA) and ballistic cluster-cluster aggregates (BCCA) composed of 128, 256, 512, and 1024 monomers with radii between 0.11 and .Our results show that the size of monomers plays an important role in reproducing the negative polarization branch for all the BPCA and BCCA. Silicate aggregates with the monomer radius of less than contribute to reproducing the negative polarization branch, while aggregates with monomers larger than do not have the negative polarization branch. Polarization oscillation with scattering angle occurs for larger monomers (i.e., monomer radius ).The maximum polarization decreases for increasing monomer radius between 0.11 and . However, the negative polarization branch is generally enhanced for monomer radii up to around , and reduced for further increase of monomer size.The number of monomers also has a large influence on the negative polarization branch in the case of BPCA. The increase in the number of monomers from 128 to 1024 shifts the scattering angle of minimum polarization to larger angles for BPCA. In addition, the increase in the number of monomers reduces the values of negative polarization for BPCA while the variation with the number of monomers for BCCA is small and is not monotonic.     

Structure of Co-Zn ferrite ferrofluid: A small angle neutron scattering analysis

A hydrothermal synthesis route is used to synthesize nanomagnetic particles of Co_0.3Zn_0.7Fe₂O₄ ferrite ferrofluids with particle diameter ranging from 5.5–9 nm. XRD analysis shows the formation of a single phase spinel structure. EDX results confirm the stoichiometric composition of the cations. Small angle neutron scattering technique is used to determine the size and size distribution of Co_0.3Zn_0.7Fe₂O₄ ferrofluid. The sizes thus obtained are in the range of 5.4 to 8.4 nm. These results are in agreement with magnetic measurements.      

First-principles molecular dynamics simulations of the structure of germanium dioxide under pressures

We have carried out first-principles molecular dynamics simulations of glass and liquid germanium dioxide (GeO₂) over a wide range of pressure. Our results show that in the glass GeO₂ system nearly all Ge–O coordination environments are fourfold at low compression, whereas at high compression five- and sixfold coordination types coexist. In the liquid GeO₂ system although most Ge–O coordination environments are fourfold, some threefold coordination types exist at low compression. Pentahedral units also exist in the liquid state while less than that in the glass state. At high compression, pentahedral units disappear and GeO₆ octahedron is dominant in the liquid state going with some sevenfold coordination.     

Rescaled mean spherical approximation structure factor for an aqueous suspension of polystyrene spheres

Rescaled mean spherical approximation (RMSA) has been used to calculate the structure factor for the aqueous suspension of polystyrene macroions with the interaction potential taken according to Derjaguin and Landau (1941) and Verwey and Overbeek (1948) (DLVO) model. The effects of charge over the macroion and size on the surface potential and therefore, the structure factor have been studied. The breakdown of the DLVO potential with an excess charge over the macroion (⩾800e) has been reported. The oscillation in the first peak height of structure factor versus wave vector curve with size has been correlated with the Debye length.     

Molecular dynamics in solid n-nonadecane: Experiments and computer simulations

We have undertaken a collaborative study on the molecular dynamics and the phase transition mechanisms in low-dimensional molecular crystals by combining incoherent quasielastic neutron scattering, deuterium NMR and computer simulation techniques. In this paper, we summarize the method used for deriving a dynamical model for the reorientations of n-nonadecane molecules in the rotator phase R _I of the crystal. This model has been applied successfully to interpret experimental and computational data.     

Structural and magnetic properties of self-assembled Sm-Co spherical aggregates

Self-assembled Sm-Co nanoparticles in the form of spherical aggregates (referred as nanospheres) with diameter ranging from 50 to 180 nm were achieved by means of polyol technique. The size distribution of the Sm-Co nanospheres can be regulated close to ∼100 nm by controlling the molar ratio of Sm:Co precursor. The spherical aggregates exhibited Sm₂Co₇ phase as a major constituent; while the aggregates obtained at higher Co concentration showed co-existence of Co-phase with Sm₂Co₇ phase. Upon annealing, the biphasic nature of nanospheres (Sm₂Co₇/Co) transformed into Sm₂Co₁₇ structure. By varying the Sm:Co precursor ratio from 1:5 to 1:9, the coercivity (H_c) and magnetization (M_s) values of the as-synthesized nanospheres can be tuned from 336 to 140 Oe and from 63.7 to 108 emu/g, respectively, and these values significantly improved after annealing. Maximum values of H_c (1050 Oe) at the Sm:Co molar ratio of 1:5 and M_s of 184.6 emu/g at the Sm:Co molar ratio of 1:9 were achieved in the annealed samples.     

Kinetics of a first-order phase transition: computer simulations and theory

We make a quantitative comparison between the predictions of the Becker-Döring equations and computer simulations on a model of a quenched binary A-B alloy. The atoms are confined to the vertices of a simple cubic lattice, interact through attractive nearest neighbor interactions, and move by interchanges of nearest neighbor pairs (Kawasaki dynamics). We study in particular the time evolution of the number of clusters of A atoms of each size, at four different concentrations: _A=0.035, 0.05, 0.075, and 0.1 atoms per lattice site. The temperature is 0.59 times the critical temperature. At this temperature the equilibrium concentration of A atoms in the B-rich phase is _A ^eq =0.0145 atoms/lattice site. The coefficients entering the Becker-Döring equations are obtained by extrapolation from previously published low-density calculations, leaving the time scale as the only adjustable parameter. We find good agreement at the three lower densities. At 10% density the agreement is, as might be expected, less satisfactory but still fairly good-indicating a quite wide range of utility for the Becker-Döring equations.Supported in part by NSF Grant DMR81-14726 and DOE Contract DE-AC02-76ERO3077.     

Structure and properties of the bronze laser alloyed with titanium

The paper describes the microstructure and properties (microhardness and wear resistance) of the bronze laser alloyed with titanium. The laser alloying was done using a pulsed Nd:YAG laser with a generated beam energy of 25-35 J. A very fine microstructure was formed under such rapid solidification conditions like laser treatment. The high chemical homogeneity and fine structure of the melted zone were attributed to high cooling rates due to the short interaction time with Nd:YAG pulsed laser radiation and relatively small volume of the melted material. The structure obtained in the surface layer after laser alloying permits to get a high level of hardness and an improved wear resistance.     

Quasi-2D Monte Carlo simulations of the regime change in the aggregates of magnetic cubic particles on a material surface

We have investigated the aggregate structure of a suspension composed of magnetic particles with a cubic geometry by means of Monte Carlo simulations. From the viewpoint of application to the technology of surface modification, we have considered a quasi-two-dimensional suspension in thermodynamic equilibrium. As the magnetic interaction strength is increased, the effects of the thermal energy are reduced and the particles tend to aggregate together. These aggregates of cubic particles are not chain-like, but are designated as closely packed clusters. An applied magnetic field tends to enhance the formation of clusters along the field direction but does not significantly regularise the internal structure of the cluster. This is mainly due to the preference of a face-to-face contact configuration for the alignment of particles with cubic geometry. The regime of the internal structure of aggregates has a significant effect on the characteristics of the alignment of the magnetic moments with regard to the external magnetic field direction. Our simulations indicate that larger closely packed clusters are formed with increasing volumetric fraction, whereas the internal structure of the closely packed clusters is not found to be significantly influenced by the change in the volumetric fraction.     

二元液态金属Cu-Ni和Ag-Cu凝固过程的分子动力学模拟研究

用Quantum Sutton-Chen多体势对Ag6Cu4和CuNi液态金属凝固过程进行了分子动力学模拟研究.在冷却速率2×1012到2×1014K/s范围内,CuNi总是形成fcc晶体结构,而Ag6Cu4总是形成非晶态结构.考虑到CuNi及AgCu中原子半径之比分别为1.025和1.13,那么模拟结果证实了原子的尺寸差别是非晶态合金形成的一个主要影响因素.此外采用键对及原子多面体类型指数法对凝固过程中微观结构组态变化的分析,不但能说明二十面体结构在非晶态合金形成和稳定性中所起的关键作用,又有助于对液态金属的凝固过程、非晶态结构特征的深入理解.