Biomedical subjects

A P Philipse

Publications and source records attributed to A P Philipse.

18 recordsLinked to original sources

PubMed2006

Preparation and properties of monodisperse latex spheres with controlled magnetic moment for field-induced colloidal crystallization and (dipolar) chain formation.

We report the preparation and properties of monodisperse magnetic poly(methyl methacrylate) latex spheres that exhibit field-induced colloidal crystallization to exotic morphologies controlled by the geometry of the gradient. The magnetic moment of the novel magnetic spheres is due to an inner core of magnetite particles. These particles, obtained from a conventional ferrofluid, first form a monodisperse emulsion with a silane coupling agent, after which they are directly incorporated in PMMA latex synthesized by standard emulsion polymerization. Scattering from the latex shell dominates over light absorption by the magnetic cores such that visible Bragg reflections of the magnetic crystals can be clearly observed. Concentrated nearly white latex fluids may exhibit near a magnet the warped equilibrium menisci known from the usually dark magnetite ferrofluids. Of the many possible applications, we briefly discuss the subsequent growth and melting of crystals by a slowly oscillating gradient, the formation of radial lattices, and the formation of ordered magnetic dots in PMMA latex films.

Journal Article↗

PubMed2006

Geometrical cluster ensemble analysis of random sphere packings.

We introduce a geometric analysis of random sphere packings based on the ensemble averaging of hard-sphere clusters generated via local rules including a nonoverlap constraint for hard spheres. Our cluster ensemble analysis matches well with computer simulations and experimental data on random hard-sphere packing with respect to volume fractions and radial distribution functions. To model loose as well as dense sphere packings various ensemble averages are investigated, obtained by varying the generation rules for clusters. Essential findings are a lower bound on volume fraction for random loose packing that is surprisingly close to the freezing volume fraction for hard spheres and, for random close packing, the observation of an unexpected split peak in the distribution of volume fractions for the local configurations. Our ensemble analysis highlights the importance of collective and global effects in random sphere packings by comparing clusters generated via local rules to random sphere packings and clusters that include collective effects.

Algorithms↗

PubMed2006

Fluorescent monodisperse silica ellipsoids for optical rotational diffusion studies.

We report on the preparation of monodisperse, fluorescent hematite-silica core-shell ellipsoids, with adjustable shapes ranging from spindles to nearly spheres, that are suitable for optical rotational diffusion studies. Hematite cores are grafted with poly(vinylpyrrolidone) which ensures colloidal stability during the silica coating provided by the base-catalyzed hydrolysis and polymerization of tetraethoxysilane. Using tetramethylammonium hydroxide as base instead of the volatile ammonia facilitates continuous seeded growth of silica to colloids with a desired aspect ratio. A convenient feature of the hematite-silica particles is the rapid dissolution of the iron oxide core by acid, producing hollow silica ellipsoids that can be optically matched to near transparency. The control of shape and size of the silica ellipsoids, their optical properties, and the fairly high yield in comparison to other preparation methods for nonspherical model colloids make the ellipsoids very suitable for quantitative studies. As a case in point, we have measured the rotational diffusion coefficient of fluorescent ellipsoids with rotational fluorescence recovery after photobleaching. Dye-labeled ellipsoids can be imaged with confocal microscopy.

Journal Article↗

PubMed2005

Stability of mixtures of charged silica, silica-alumina, and magnetite colloids.

We report experiments on the stability of aqueous mixtures of charged colloidal magnetite and charged silica and silica covered with alumina particles of similar size. First, positively charged magnetite dispersions were mixed with negatively charged silica dispersions at pH 4, at different volume ratios and low colloid volume fractions, producing mixtures which were stable over a period of weeks despite the expected electrostatic attraction between the oppositely charged particles. When magnetite particles were mixed with positively charged silica covered with alumina at pH 4 under exactly the same conditions, some of the systems separated to form a magnetite sediment. When the volume fraction of the initial dispersions was increased, the behavior of the mixtures was the opposite: positive magnetite/negative silica mixtures were unstable at intermediate volume ratios. The unexpected behavior of the mixtures was investigated by means of electrophoretic mobility, initial susceptibility, and dynamic light scattering measurements as well as sedimentation experiments.

Aluminum Oxide↗

PubMed2005

Monodisperse magnetizable composite silica spheres with tunable dipolar interactions.

We demonstrate that magnetic particles of maghemite (gamma-Fe(2)O(3)) and cobalt ferrite (CoFe(2)O(4)) can be irreversibly attached to colloidal silica that is grafted with 3-mercaptopropyl(trimethoxy)silane (followed by the controlled growth of a silica layer) to obtain stable dispersions of monodisperse colloidal silica spheres that contain a dense shell of ferrite particles at an adjustable distance from the sphere surface. Magnetization of the ferrite shell induces a large dipole moment, and adjusting the thickness of the outer silica layer enables one to tune the contact attraction. This novel type of magnetizable silica colloid exhibits structure formation in a homogeneous field that varies from isotropic distributions to elongated dipolar chains.

Journal Article↗

PubMed2005

On the caging number of two- and three-dimensional hard spheres.

Local structural arrest in random packings of colloidal or granular spheres is quantified by a caging number, defined as the average minimum number of randomly placed spheres on a single sphere that immobilize all its translations. We present an analytic solution for the caging number for two-dimensional hard disks immobilized by neighbor disks which are placed at random positions under the constraint of a nonoverlap condition. Immobilization of a disk with radius r = 1 by arbitrary larger neighbor disks with radius r > or = 1 is solved analytically, whereas for contacting neighbors with radius 0 < r < 1, the caging number can be evaluated accurately with an approximate excluded volume model that also applies to spheres in higher Euclidean dimension. Comparison of our exact two-dimensional caging number with studies on random disk packing indicates that it relates to the average coordination number of random loose packing, whereas the parking number is more indicative for coordination in random dense packing of disks.

Journal Article↗

PubMed2005

Preparation and properties of colloidal iron dispersions.

We systematically study the properties of dispersions of iron-based colloids synthesized in a broad size range by thermal decomposition of ironcarbonyl using different stabilizing surfactants. The synthesis results in stable dispersions of monodomain magnetic colloids. Our particles appear to consist of an amorphous Fe(0.75)C(0.25) alloy. Sizes of particles coated with modified polyisobutene or oleic acid can be easily controlled in the 2-10 nm range by varying the amounts of reactants. Extensive characterization with various techniques gives particle sizes that agree well with each other. In contrast to dispersions of small particles, which consist of single colloids, dynamic aggregates are present in dispersions of larger particles. On exposure to air, an oxide layer forms on the particle surface, consisting of a disordered Fe(III) oxide.

Journal Article↗

PubMed2004

Heteroaggregation, repeptization and stability in mixtures of oppositely charged colloids.

We report a study of mixtures of initially oppositely charged particles with similar size. Dispersions of silica spheres (negatively charged) and alumina-coated silica spheres (positively charged) at low ionic strength, mixed at various volume ratios, exhibited a surprising stability up to compositions of 50% negative colloids as well as spontaneous repeptization of particles from the early-stage formed aggregates. The other mixtures were found to contain large heteroaggregates, which were imaged using cryogenic electron microscopy. Electrophoretic mobility, electrical conductivity, static and dynamic light scattering and sedimentation were studied as a function of volume fraction of the mixed dispersions to investigate particle interactions and elucidate the repeptization phenomenon.

Journal Article↗

PubMed2004

Rotational dynamics of colloidal spheres probed with fluorescence recovery after photobleaching.

We report a polarized fluorescence recovery after photobleaching (pFRAP) method to measure the rotational dynamics of fluorescent colloids over a wide dynamic range. The method is based on the polarization anisotropy in the fluorescence intensity, generated by bleaching of fluorescently labeled particles with an intense pulse of linearly polarized laser light. The rotational mobilities of the fluorescent particles can be extracted from the relaxation kinetics of the postbleach fluorescence polarization anisotropy. Our pFRAP setup has access to correlation times over a range of time scales from tens of microseconds to tens of seconds, and is highly sensitive, so very low concentrations of labeled particles can be probed. We present a detailed description of the theoretical background of pFRAP. The performance of the equipment is demonstrated for fluorescent colloidal silica spheres, dispersed in pure solvents as well as in fd-virus suspensions.

Biomechanical Phenomena↗

PubMed2004

Rotational and translational diffusion of fluorocarbon tracer spheres in semidilute xanthan solutions.

We report an experimental study of rotational and translational diffusion and sedimentation of colloidal tracer spheres in semidilute solutions of the nonadsorbing semiflexible polymer xanthan. The tracers are optically anisotropic, permitting depolarized dynamic light scattering measurements without interference from the polymer background. The xanthan solutions behave rheologically like model semidilute polymeric solutions with long-lived entanglements. On the time scale of tracer motion the xanthan solutions are predominantly elastic. The generalized Stokes-Einstein relation describing the polymer solution as a continuous viscous fluid therefore severely overestimates the tracer hindrance. Instead, effective medium theory, describing the polymer solution as a homogeneous Brinkman fluid with a hydrodynamic screening length equal to the concentration-dependent static correlation length, is in excellent agreement with the tracer sedimentation and rotational diffusion coefficients. Rotational diffusion, however, is at the same time in good agreement with a simple model of a rotating sphere in a concentric spherical depletion cavity. Translational diffusion is faster than predicted for a Brinkman fluid, likely due to polymer depletion.

Colloids↗

PubMed2003

Initial susceptibility, flow curves, and magneto-optics of inverse magnetic fluids.

We introduce inverse magnetic fluids, consisting of gibbsite [Al(OH)(3)] platelets and alumina (Al2O3) spheres dispersed in a magnetic fluid, studied together with silica (SiO2) dispersions based on the same magnetic fluid matrix. Atomic force microscopy, optical microscopy, and alternate gradient magnetometry confirm the remarkable stability of the samples. Optical microscopy shows aggregation of nonmagnetic spheres, which, surprisingly, strongly depends on the concentration of the magnetic fluid rather than the concentration of nonmagnetic particles. Our model for the initial susceptibility of inverse magnetic fluids agrees very well with experimental data for systems containing spherical particles. The flow curves in an external magnetic field are strongly influenced by the aggregation of nonmagnetic particles or preformed nonmagnetic particle clusters, and by their disruption due to the shear flow. Static linear magnetobirefringence and magnetodichroism of all samples are investigated both experimentally and theoretically. These effects, which occur in all magnetic fluids, can be enhanced by the additional anisotropy due to the magnetic holes. The experiments we performed showed that, at a wavelength of 820 nm, the magnetodichroism is increased while the magneto-birefringence decreases when nonmagnetic particles were dispersed in the magnetic fluid. Magneto-birefringence is expected to be increased at large enough wavelengths only.

Journal Article↗

PubMed2003

Random packings of spheres and spherocylinders simulated by mechanical contraction.

We introduce a simulation technique for creating dense random packings of hard particles. The technique is particularly suited to handle particles of different shapes. Dense amorphous packings of spheres have been formed, which are consistent with the existing work on random sphere packings. Packings of spherocylinders have also been simulated out to the large aspect ratio of alpha=160.0. Our method packs randomly oriented spherocylinders to densities that reproduce experimental results on anisotropic powders and colloids very well. Interestingly, the highest packing density of phi=0.70 is achieved for very short spherocylinders rather than spheres. This suggests that slightly changing the shapes of the particles forming a hard sphere glass could cause it to melt. Comparisons between the equilibrium phase diagram for hard spherocylinders and the densest possible amorphous packings have interesting implications on the crystallization of spherocylinders as a function of aspect ratio.

Journal Article↗

PubMed2003

Direct observation of dipolar chains in iron ferrofluids by cryogenic electron microscopy.

A key issue in research on ferrofluids (dispersions of magnetic colloids) is the effect of dipolar interactions on their structure and phase behaviour, which is not only important for practical applications but gives fundamental insight in dipolar fluids in general. In 1970, de Gennes and Pincus predicted a Van der Waals-like phase diagram and the presence of linear chains of particles in ferrofluids in zero magnetic field. Despite many experimental studies, no direct evidence of the existence of linear chains of dipoles has been reported in the absence of magnetic field, although simulations clearly show the presence of chain-like structures. Here, we show in situ linear dipolar structures in ferrofluids in zero field, visualized on the particle level by electron cryo-microscopy on thin, vitrified films of organic dispersions of monodisperse metallic iron particles. On systematically increasing the particle size, we find an abrupt transition from separate particles to randomly oriented linear aggregates and branched chains or networks. When vitrified in a permanent magnetic field, these chains align and form thick elongated structures, indicating lateral attraction between parallel dipole chains. These findings show that the experimental model used is well suited to study the structural properties of dipolar particle systems.

Cryoelectron Microscopy↗

PubMed2002

Atomic force microscopy and magnetic force microscopy study of model colloids.

Atomic force microscopy (AFM) is used to study the size, shape, and polydispersity of a variety of magnetic and nonmagnetic model colloids, previously imaged by transmission electron microscopy (TEM) only. Both height and phase images are analyzed and special attention is given to 3D morphology and softness of particles, as well as structures and presence of secondary components in the colloid, difficult to investigate with TEM. Several methods of tip characterization followed by deconvolution were applied in order to improve the accuracy of lateral diameter determination. In the case of magnetite particles dispersed in conventional ferrofluids, we explore both experimentally and theoretically the possibility of using magnetic force microscopy (MFM). We propose and discuss several models which allow to estimate the magnetic moment of a single domain superparamagnetic sphere using MFM, which cannot be done with other techniques; alternatively the tip magnetization can be determined.

Journal Article↗

PubMed2002

The synthesis and magnetic properties of nanosized hematite (alpha-Fe2O3) particles.

The synthesis of nanosized superparamagnetic hematite particles by dissolving ferric salts in hydrochloric acid and heating at 100 degrees C is described. A hydrolysis reaction causes the formation of hematite particles. The influence of the sequence of additions on the resulting precipitates was studied using TEM and XRD. The magnetic behavior was characterized by magnetization measurements. It was found that small changes in the reaction conditions led to remarkable changes in final size and shape of the hematite crystallites. A well-defined subrounded morphology and an average diameter of 41 nm were obtained for superparamagnetic hematite particles. This is the largest size reported thus far for superpara-magnetic hematite particles.

Journal Article↗

PubMed2001

Rotational tracer diffusion in binary colloidal sphere mixtures.

We demonstrate that tracer/host size asymmetry and electrostatic interactions strongly affect rotational self-diffusion in binary mixtures of charged colloidal tracer and host spheres. Tracer diffusion coefficients, measured with time-resolved phosphorescence anisotropy, are compared with calculations of rotational diffusion including two- and three-particle hydrodynamic interactions. We also show that the inverse dependence of the rotational diffusion coefficient on the suspension viscosity is approached only at large size ratios.

Journal Article↗

PubMed2001

Caging of a d-dimensional sphere and its relevance for the random dense sphere packing.

We analyze the caging of a hard sphere (i.e., the complete arrest of all translational motions) by randomly distributed static contact points on the sphere surface for arbitrary dimension d>/=1, and prove that the average number of uncorrelated contacts required to cage a sphere is (d)=2d+1. Computer simulations, which confirm this analytical result, are also used to model the effect of correlations between contacts that occur in real hard-sphere systems. Our analysis predicts an average coordination number of 4.79 (+/-0.02) for caged spheres, which agrees surprisingly well with the experimental coordination number for random sphere packings reported by Mason [Nature 217, 733 (1968)]. This result supports the physical picture that the coordination number in random dense sphere packings is primarily determined by caging effects. It also suggests that it should be possible to construct such packings from a local caging rule.

Journal Article↗

PubMed1999

Linear viscoelasticity of an inverse ferrofluid.

A magnetorheological fluid consisting of colloidal silica spheres suspended in an organic ferrofluid is described. Its linear viscoelastic behavior as a function of frequency, magnetic field strength, and silica volume fraction was investigated with a specially designed magnetorheometer. The storage modulus G' is at least an order of magnitude larger than the loss modulus G" at all magnetic field strengths investigated. G' does depend only weakly on frequency, and linearly on volume fraction. A model is presented for the high frequency limit of the storage modulus G'(infinity). In the model our system is treated as a collection of single noninteracting chains of particles. Assuming a dipolar magnetic interaction, theory and experiment show reasonable agreement at high frequencies.

Journal Article↗