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Alfons van Blaaderen

Publications and source records attributed to Alfons van Blaaderen.

13 recordsLinked to original sources
PubMed2006

Surface molecular view of colloidal gelation.

We investigate the phase behavior of surface-functionalized silica colloids at both the molecular and macroscopic levels. This investigation allows us to relate collective properties such as aggregation, gelation, and aging directly to molecular interfacial behavior. By using surface-specific vibrational spectroscopy, we reveal dramatic changes in the conformation of alkyl chains terminating submicrometer silica particles. In fluid suspension at high temperatures, the interfacial molecules are in a liquid-like state of conformational disorder. As the temperature is lowered, the onset of gelation is identified by macroscopic phenomena, including changes in turbidity, heat release, and diverging viscosity. At the molecular level, the onset of this transition coincides with straightening of the carbon-carbon backbones of the interfacial molecules. In later stages, their intermolecular crystalline packing improves. It is the increased density of this ordered boundary layer that increases the van der Waals attraction between particles, causing the colloidal gas to aggregate. The approach presented here can provide insights into phase transitions that occur through surface modifications in a variety of colloidal systems.

Colloids↗
PubMed2006

Re-entrant melting and freezing in a model system of charged colloids.

We studied the phase behavior of charged and sterically stabilized colloids using confocal microscopy in a low polarity solvent (dielectric constant 5.4). Upon increasing the colloid volume fraction we found a transition from a fluid to a body centered cubic crystal at 0.0415+/-0.0005, followed by reentrant melting at 0.1165+/-0.0015. A second crystal of different symmetry, random hexagonal close packed, was formed at a volume fraction around 0.5, similar to that of hard spheres. We attribute the intriguing phase behavior to the particle interactions that depend strongly on volume fraction, mainly due to the changes in the colloid charge. In this low polarity system the colloids acquire charge through ion adsorption. The low ionic strength leads to fewer ions per colloid at elevated volume fractions and consequently a density-dependent colloid charge.

Journal Article↗
PubMed2005

Synthesis of colloidal silica dumbbells.

We describe the synthesis and characterization of stable suspensions of monodisperse fluorescently labeled silica dumbbell particles. Pure dispersions of silica dumbbells with center-to-center lengths from 174 nm to 2.3 microm were produced with a variety of aspect ratios. Individual particles in concentrated dispersions of these particles could be imaged with confocal microscopy. These particles can be used as a colloidal model system for addressing fundamental questions about crystal and glass formation of low-aspect-ratio anisotropic particles. They also have potential in photonic applications and electro-optical devices.

Journal Article↗
PubMed2005

Ionic colloidal crystals of oppositely charged particles.

Colloidal suspensions are widely used to study processes such as melting, freezing and glass transitions. This is because they display the same phase behaviour as atoms or molecules, with the nano- to micrometre size of the colloidal particles making it possible to observe them directly in real space. Another attractive feature is that different types of colloidal interactions, such as long-range repulsive, short-range attractive, hard-sphere-like and dipolar, can be realized and give rise to equilibrium phases. However, spherically symmetric, long-range attractions (that is, ionic interactions) have so far always resulted in irreversible colloidal aggregation. Here we show that the electrostatic interaction between oppositely charged particles can be tuned such that large ionic colloidal crystals form readily, with our theory and simulations confirming the stability of these structures. We find that in contrast to atomic systems, the stoichiometry of our colloidal crystals is not dictated by charge neutrality; this allows us to obtain a remarkable diversity of new binary structures. An external electric field melts the crystals, confirming that the constituent particles are indeed oppositely charged. Colloidal model systems can thus be used to study the phase behaviour of ionic species. We also expect that our approach to controlling opposite-charge interactions will facilitate the production of binary crystals of micrometre-sized particles, which could find use as advanced materials for photonic applications.

Journal Article↗
PubMed2005

Combined optical tweezers/ion beam technique to tune colloidal masks for nanolithography.

A method is presented to control the in-plane ordering, size, and interparticle distance of nanoparticles fabricated by evaporation through a mask of colloidal particles. The use of optical tweezers combined with critical point drying gives single-particle position control over the colloidal particles in the mask. This extends the geometry of the colloidal masks from (self-organized) hexagonal to any desired symmetry and spacing. Control over the mask's hole size is achieved by MeV ion irradiation, which causes the colloids to expand in the in-plane direction, thus shrinking the size of the holes. After modification of the mask, evaporation at different angles with respect to the mask gives additional control over structure and interparticle distance, allowing nanoparticles of different materials to be deposited next to each other. We demonstrate large arrays of metal nanoparticles with dimensions in the 15-30 nm range, with control over the interparticle distance and in-plane ordering.

Colloids↗
PubMed2004

Synthesis of monodisperse high-aspect-ratio colloidal silicon and silica rods.

We describe the synthesis and the physical properties of suspensions of colloidal silicon and silica rodlike particles. In addition to pure silicon and pure silica rods, we have also synthesized silicon rods with a silica shell and silica rods with a fluorescent silica layer. Pre-patterned p-type (100) silicon wafers were electrochemically etched in electrolyte solutions containing hydrogen fluoride. By the current density being varied while etching, macropores were etched with controllable modulated pore diameters. These silicon structures were transformed into rods with indentations 5.5 mum apart and with lengths up to 100 mum using iterative oxidation in air and dissolution of the silica by HF. Complete oxidation of these rods was also achieved. Sonication of the modulated rods resulted in monodisperse particles of 5.5 mum length and 300 nm width. A high yield of 10(12) particles, or more, is possible with this method. At high concentrations, these particles show nematic ordering in charge-stabilized suspensions. The oxidized silica outer layer of the silicon rods makes the further growth of silica in solution or on a wafer possible. This allows for control of the particles' interaction potential. Labeling with a fluorescent dye and index matching of the complete silica rods enable the study of concentrated dispersions quantitatively, on a single particle level, with confocal microscopy. Because of their high refractive index in the near-IR, the nematic phases of rods with a silica core are also interesting for photonic applications.

Colloids↗
PubMed2004

Nature of an electric-field-induced colloidal martensitic transition.

We study the properties of a solid-solid close-packed to body-centered tetragonal transition in a colloidal suspension via fluorescence confocal laser scanning microscopy, in three dimensions and in real space. This structural transformation is driven by a subtle competition between gravitational and electric dipolar field energy, the latter being systematically varied via an external electric field. The transition threshold depends on the local depth in the colloidal sediment. Structures with order intermediate between close-packed and body-centered tetragonal were observed, with these intermediate structures also being stable and long lived. This is essentially a colloidal analogue of an "atomic-level" interfacial structure. We find qualitative agreement with theory (based purely on energetics). Quantitative differences can be attributed to the importance of entropic effects.

Journal Article↗
PubMed2003

A colloidal model system with an interaction tunable from hard sphere to soft and dipolar.

Monodisperse colloidal suspensions of micrometre-sized spheres are playing an increasingly important role as model systems to study, in real space, a variety of phenomena in condensed matter physics--such as glass transitions and crystal nucleation. But to date, no quantitative real-space studies have been performed on crystal melting, or have investigated systems with long-range repulsive potentials. Here we demonstrate a charge- and sterically stabilized colloidal suspension--poly(methyl methacrylate) spheres in a mixture of cycloheptyl (or cyclohexyl) bromide and decalin--where both the repulsive range and the anisotropy of the interparticle interaction potential can be controlled. This combination of two independent tuning parameters gives rise to a rich phase behaviour, with several unusual colloidal (liquid) crystalline phases, which we explore in real space by confocal microscopy. The softness of the interaction is tuned in this colloidal suspension by varying the solvent salt concentration; the anisotropic (dipolar) contribution to the interaction potential can be independently controlled with an external electric field ranging from a small perturbation to the point where it completely determines the phase behaviour. We also demonstrate that the electric field can be used as a pseudo-thermodynamic temperature switch to enable real-space studies of melting transitions. We expect studies of this colloidal model system to contribute to our understanding of, for example, electro- and magneto-rheological fluids.

Journal Article↗
PubMed2003

Colloidal epitaxy: playing with the boundary conditions of colloidal crystallization.

We have studied, with quantitative confocal microscopy, epitaxial colloidal crystal growth of particles interacting with an almost hard-sphere (HS) potential in a gravitational field and density matched colloids interacting with a long-range (LR) repulsive potential with a body-centred cubic (BCC) equilibrium crystal phase. We show that in both cases it is possible to grow thick, stacking fault-free metastable crystals: close-packed crystals with any stacking sequence, including hexagonal close packed (HCP), for the HS particles and face-centred cubic (FCC) in the case of the LR colloids. In accordance with recent computer simulations done for HS particles it was found that the optimal lattice constant to grow HS HCP crystals was larger than that of equilibrium FCC crystals. In addition, because of the absence of gravity, pre-freezing could be observed for the particles with the LR potential on a template of charged lines. We also argue that the ability to manipulate colloids with highly focused light, optical traps or tweezers, will become an important tool in both the study of colloidal crystallization and in making new structures. We show how cheap 2D and 3D templates can be made with optical tweezers and demonstrate, in proof of principle experiments with core-shell colloids, how light fields can generate crystal nuclei and other structures in the bulk of concentrated dispersions and how the effect of these structures on the rest of a dispersion can be studied quantitatively in 3D.

Journal Article↗
PubMed2002

Layer-by-layer growth of binary colloidal crystals.

We report the growth of binary colloidal crystals with control over the crystal orientation through a simple layer-by-layer process. Well-ordered single binary colloidal crystals with a stoichiometry of large (L) and small (S) particles of LS2 and LS were generated. In addition, we observed the formation of an LS3 superstructure. The structures formed as a result of the templating effect of the first layer and the forces exerted by the surface tension of the drying liquid. By using spheres of different composition, one component can be selectively removed, as is demonstrated in the growth of a hexagonal non-close-packed colloidal crystal.

Journal Article↗
PubMed2002

Preparation of monodisperse, fluorescent PMMA-latex colloids by dispersion polymerization.

We report a single step procedure to prepare monodisperse colloidal poly(methyl)methacrylate (PMMA) particles where fluorescent dyes are incorporated into the polymer network. The particles are sterically stabilized against flocculation by poly(12-hydroxystearic acid). The fluorescent dyes are RITC (rhodamine isothiocyanate)-aminostyrene (RAS) and 4-methylaminoethylmethacrylate-7-nitrobenzo-2-oxa-1,3-diazol (NBD-MAEM), which are prepared from (commercially available) RITC and 4-chloro-7-nitrobenzo-2-oxa-1,3-diazol (NBD-Cl), respectively, as starting materials. The particles can be grown larger with nonfluorescent PMMA. Examples of the usefulness of these model particles in colloid science are given.

Journal Article↗