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Kenneth J Rosenberg

Publications and source records attributed to Kenneth J Rosenberg.

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Recent progress in understanding hydrophobic interactions.

We present here a brief review of direct force measurements between hydrophobic surfaces in aqueous solutions. For almost 70 years, researchers have attempted to understand the hydrophobic effect (the low solubility of hydrophobic solutes in water) and the hydrophobic interaction or force (the unusually strong attraction of hydrophobic surfaces and groups in water). After many years of research into how hydrophobic interactions affect the thermodynamic properties of processes such as micelle formation (self-assembly) and protein folding, the results of direct force measurements between macroscopic surfaces began to appear in the 1980s. Reported ranges of the attraction between variously prepared hydrophobic surfaces in water grew from the initially reported value of 80-100 Angstrom to values as large as 3,000 Angstrom. Recent improved surface preparation techniques and the combination of surface force apparatus measurements with atomic force microscopy imaging have made it possible to explain the long-range part of this interaction (at separations >200 Angstrom) that is observed between certain surfaces. We tentatively conclude that only the short-range part of the attraction (<100 Angstrom) represents the true hydrophobic interaction, although a quantitative explanation for this interaction will require additional research. Although our force-measuring technique did not allow collection of reliable data at separations <10 Angstrom, it is clear that some stronger force must act in this regime if the measured interaction energy curve is to extrapolate to the measured adhesion energy as the surface separation approaches zero (i.e., as the surfaces come into molecular contact).

Hydrophobic and Hydrophilic Interactions↗

The deformation and adhesion of randomly rough and patterned surfaces.

Using a surface forces apparatus (SFA) and an atomic force microscope (AFM) we have studied the effects of surface roughness (root-mean-square (RMS) roughness between 0.3 and 220 nm) on the "contact mechanics", which describes the deformations and loading and unloading adhesion forces, of various polymeric surfaces. For randomly rough, moderately stiff, elastomeric surfaces, the force-distance curves on approach and separation are nearly reversible and almost perfectly exponentially repulsive, with an adhesion on separation that decreases only slightly with increasing RMS. Additionally, the magnitude of the preload force is seen to play a large role in determining the measured adhesion. The exponential repulsion likely arises from the local compressions (fine-grained nano- or submicron-scale deformations) of the surface asperities. The resulting characteristic decay lengths of the repulsion scale with the RMS roughness and correlate very well with a simple finite element method (FEM) analysis based on actual AFM topographical images of the surfaces. For "patterned" surfaces, with a nonrandom terraced structure, no similar exponential repulsion is observed, suggesting that asperity height variability or random roughness is required for the exponential behavior. However, the adhesion force or energy between two "patterned" surfaces fell off dramatically and roughly exponentially as the RMS increased, likely owing to a significant decrease in the contact area which in turn determines their adhesion. For both types of rough surfaces, random and patterned, the coarse-grained (global, meso- or macroscopic) deformations of the initially curved surfaces appear to be Hertzian.

Journal Article↗

Further studies on the effect of degassing on the dispersion and stability of surfactant-free emulsions.

Recently reported results indicate that the formation of surfactant-free, oil-in-water emulsions can be significantly enhanced by the almost complete removal of dissolved gases and that the reintroduction of dissolved gases does not immediately destabilize the already-formed emulsions. These initial experiments have been repeated and extended to include a wider range of organic liquids and the application of light scattering to determine droplet size and distribution. The earlier observations have been confirmed. In addition, a systematic trend was found between the solubility of the oil in water and the stability (lifetime) of the degassed oil droplets in water. The lower the solubility, the more stable the emulsion, and for oils that are sparingly soluble in water such as squalane, the small droplets remain stable for several weeks, with buoyancy separation being the main cause of instability of the large droplets with time. The addition of electrolytes, up to molar concentrations, substantially reduces the enhancement of the dispersions on degassing but appears to have little effect on the stability of the already-formed emulsions. The reduction of pH to about 2 significantly reduces both the enhancement of the dispersions on degassing and the stability of the already-formed emulsions. In contrast, the increase of pH to about 11 hardly affects the enhancement of the dispersions on degassing or the stability of the already-formed emulsions. We have confirmed the importance of dissolved gas and its association with the electrostatic effects, but we still cannot provide a complete explanation for the effect of degassing on the hydrophobic dispersions.

Journal Article↗