On-line determination of Förster resonance energy transfer efficiency in drying latex films: correlation of interdiffusion and particle deformation.

An instrument is described, which measures the efficiency of Förster resonance energy transfer (FRET) in parallel to the sample's turbidity. The instrument was used to study the film formation from polymer latex dispersions. In this context, the FRET efficiency reflects the diffusion of polymer chains across the interparticle boundaries, while the loss of turbidity reflects the progress of particle deformation. Particle deformation causes tensile in-plane stress, while polymer interdiffusion creates cohesion and thereby helps to prevent cracking. The relative timing between the two therefore is of fundamental importance for successful film formation. The on-line determination of FRET efficiency while the film dries is complicated by the fact that the fluorescence lifetime of the donor, τ(D), depends on the water content in the vicinity of the donor. In the established procedure for data analysis, drifts in τ(D) induce corresponding artifical drifts in the values of the FRET efficiency. A novel algorithm for the analysis of fluorescence decay profiles is proposed, which makes use of the method of moments. The FRET efficiency is quantified by the upward curvature of the fluorescence decay curve in log-linear display. In the application example, interdiffusion is delayed relative to particle deformation by about 10 min. For successful film formation, this delay should be as small as possible.

Quartz crystal microbalance based on torsional piezoelectric resonators.

A quartz crystal microbalance (QCM) is described, which is based on a torsional resonator, rather than a conventional thickness-shear resonator. Typical applications are measurements of film thickness in the coating industry and monitoring of biofouling. The torsional QCM is about a factor of 100 less sensitive than the conventional QCM. On the other hand, it can probe film thicknesses in the range of hundreds of microns, which is impossible with the conventional QCM due to viscoelastic artifacts. Data acquisition and data analysis proceed in analogy to the conventional QCM. An indicator of the material's softness can be extracted from the bandwidth of the resonance. Within the small-load approximation, the frequency shift is independent of whether the sample is applied to the face or to the side of the cylinder. Details of the geometry matter if the viscoelastic properties of the sample are of interest.

Capillary aging of the contacts between glass spheres and a quartz resonator surface.

The strength of the contacts between small glass spheres and the surface of a quartz crystal resonator has been probed based on the increase of resonance frequency induced upon sphere contact. The acoustic interaction between the sphere and the plate is modeled as a low-frequency coupled resonance; the dependence of the resonant parameters on overtone order lends support to this model. After exposing the sample to humid air and drying it again, the contact strength increases at least tenfold due to capillary forces--we observe a hysteretic form of the sand-castle effect. Repeated wet-dry cycles reveal logarithmic capillary aging with time. The experiments suggest that the drying of the liquid bridges leads to a contraction of small voids in the contact zone, subsequently increasing cohesion.

Electrolyte-induced collapse of a polyelectrolyte brush.

We have investigated the electrolyte-induced collapse of a polyelectrolyte brush covalently attached to a planar solid surface. Positively charged poly-4-vinyl [N-methyl-pyridinium] (MePVP) brushes were prepared in situ at the surface by free radical chain polymerization using a surface-immobilized initiator monolayer ("grafting from" technique) and 4-vinylpyridine as the monomer, followed by a polymer-analogous quaternization reaction. The height of the brushes was measured as a function of the external salt concentration via multiple-angle null ellipsometry. As predicted by mean-field theory, the height of the MePVP brushes remains unaffected by the addition of low amounts of external salt. At higher salt concentrations the brush height decreases. The extent to which the brush shrinks strongly depends on the nature of the salt present in the environment. MePVP brushes collapse to almost the dry layer thickness upon the addition of potassium iodide to a contacting aqueous medium. In contrast, the collapse of MePVP brushes having bromide or chloride counterions is much less pronounced. These brushes remain in a highly swollen state even after large amounts of salt have been added to the solution.

High speed microtribology with quartz crystal resonators.

Quartz resonators in contact with metal-covered spheres have been used to study the tribology of micron-sized metal-metal contacts at high speed (1 m/sec and high frequency (12 MHz), while maintaining a shear amplitude in the nanometer range. The data aquisition is based on ring-down experiments, where the electrical excitation is periodically interrupted and the free decay of the oscillation is analyzed. At contact, an amplitude-dependent frequency and decay rate are found, indicative of an underlying nonlinear equation of motion. Using perturbation theory and the two-timing approximation, a nonlinear spring constant kappa(1)(x) and a nonlinear drag coefficient xi(1)(x) are explicitly derived. We find a local slip-to-stick-transition at a shear amplitude of 0.5 nm. Coating the gold sufaces with a self-assembled thiol monolayer removes the stick.

Hydrodynamic interaction of AFM cantilevers with solid walls: an investigation based on AFM noise analysis.

The noise power spectrum of the thermally activated motion of an AFM cantilever has been analyzed with respect to viscoelastic and hydrodynamic coupling between the cantilever and a substrate surface. Spheres with radii between 5 and 25 microm were glued to the cantilever to provide a well-defined geometry. The cantilever is modeled as a harmonic resonator with a frequency-dependent complex drag coefficient xi(omega). The variation of the drag coefficient xi(omega) with the tip-sample distance, D, and the sphere radius, R, can be expressed as a function of the single dimensionless parameter D/ R. However, this scaling breaks down close to the surface. There are two sources of a frequency dependence of xi(omega), which are viscoelastic memory and hydrodynamics. Viscoelastic relaxation is observed when the surface is covered with a soft polymer layer. In the absence of such a soft layer one still finds a frequency dependence of xi(omega) which is caused by hydrodynamics. At large substrate-cantilever distances, the drag coefficient increases with frequency because of inertial effects. At small distances, on the other hand, the drag coefficient decreases with increasing frequency, which is explained by the reflection of shear waves from the substrate surface. In liquids, inertial effects can be important when performing dynamic AFM experiments.

Long-range attraction between colloidal spheres at the air-water interface: the consequence of an irregular meniscus

Recent observations of charged colloidal particles trapped at the air-water interface revealed long-range interparticle attractive forces, not accounted for by the standard theories of colloidal interactions. We propose a mechanism for attraction which is based on nonuniform wetting causing an irregular shape of the particle meniscus. The excess water surface area created by these distortions can be minimized when two adjacent particles assume an optimum relative orientation and distance. Typically, for spheres with diameter of 1 &mgr;m at an interparticle distance of 2 &mgr;m, deviations from the ideal contact line by as little as 50 nm result in an interaction energy of the order of 10(4)kT. Roughness-induced capillarity explains the experimental findings, including the cluster dissolution caused by addition of detergent to the subphase and the formation of linear aggregates. This kind of interaction should also be of importance in particle-stabilized foams and emulsions.