Self-assembled monolayers on mercury probed with a modified surface force apparatus

Self-assembled monolayers (SAMs) of three thiol compounds formed on mercury are investigated by a combination of cyclic voltammetry, electrocapillary curves, and a novel method of measuring electrical doublelayer properties. The last method involves a modified surface force apparatus in which a flat mica surface is pressed down toward a fixed mercury drop held beneath it, while both are immersed in aqueous electrolyte solution. Optical interference measurements are made of the mica-mercury separation as a function of electrical potential applied to the mercury, which yields information on the double-layer interaction between the two surfaces. Mercury is decorated by SAMs of 11-mercapto-1-undecanoic acid, which is shown to bring negative charge to the mercury/aqueous interface due to dissociation of the carboxylic acid groups; 11-mercapto-1- undecanol, which although it is uncharged changes the dipole potential of the interface; and 1-undecanethiol, which likewise changes the dipole potential, but by a different amount. The difference between the changes in dipole potential (90 mV) can be related to the different terminal groups of these two SAMs, -CH3 compared to -OH, that are in contact with the aqueous phase.

Direct measurement of surface forces between sapphire crystals in aqueous solutions

Measurements are presented of the electrical double layer and van der Waals forces between the (0001) surfaces of two single-crystal sapphire platelets immersed in an aqueous solution of NaCl at pH values from 6.7 to 11. The results fit the standard Deryaguin-Landau-Verwey-Overbeek (DLVO) theory, with a Hamaker constant of 6.7 × 10−20 J. These are the first measurements made using the Israelachvili surface forces apparatus without mica as a substrate material, and they demonstrate the possibility of using this technique to explore the surface chemistry of a wider range of materials.

Measurement of the deformation and adhesion of solids in contact

Two curved surfaces of molecularly smooth mica are brought into contact under a controlled load, and their deformed shape is measured using optical interference fringes of equal chromatic order. This technique allows exceptionally accurate measurements of surface profiles at separations down to a molecular scale. Contact between the surfaces can be made either adhesive or nonadhesive by suitable choice of the medium between them. Results have been obtained in both cases and compared with the theories of Hertz (nonadhesive contact) and Johnson, Kendall, and Roberts (adhesive contact).

Analytic solution for the three-layer multiple beam interferometer

We present a simple analytic solution for the condition of constructive interference for light transmitted through an interferometer incorporating three ideally transparent layers of arbitrary thickness and refractive index. We also consider the effect of adding two metallic coatings to the outer surfaces of the interferometer and give empirical expressions for the associated phase changes for silver coatings on silica, sapphire, and mica substrates. A particular application to fringes of equal chromatic order can be utilized to obtain precise measurements of the thickness of extremely thin films sandwiched between two substrates.

Contact electrification and adhesion between dissimilar materials

Simultaneous measurements of surface force and surface charge demonstrate strong attraction due to the spontaneous transfer of electrical charge from one smooth insulator (mica) to another (silica) as a result of simple, nonsliding contact in dry nitrogen. The measured surface charge densities are 5 to 20 millicoulombs per square meter after contact. The work required to separate the charged surfaces is typically 6 to 9 joules per square meter, comparable to the fracture energies of ionic-covalent materials. Observation of partial gas discharges when the surfaces are approximately 1 micrometer apart gives valuable insight into the charge separation processes underlying static electrical phenomena in general.

Attractive forces between surfaces : what can and cannot be learned from a jump-in study with the surface forces apparatus?

We study theoretically the dynamics of film thinning under the action of an attractive surface force near the point of a jump instability. Our approach is illustrated by modeling van der Waals and hydrophobic attractive forces. The main result is that with the hydrophobic force law reported previously it is often impossible to establish the jump separation with any certainty. The surfaces instead approach slowly from a distance which is much larger than the point where an actual jump is expected. We conclude that an attractive force measured by the static jump technique is overestimated, and we formulate principles of a new dynamic jump method. The use of this new technique would permit direct measurements of attractive forces at separations below the static jump distance down to contact of the surfaces.

Interfacial energy states of moisture-exposed cracks in mica

Results of crack growth observations on mica in water-containing environments are described. The study focuses on equilibrium crack states for reversed loading cycles, i.e., for initial propagation through virgin solid and subsequent retraction-repropagation through healed or misoriented-healed interfaces. Departures from these equilibrium states are manifest as steady-state forward or backward crack velocities at specific applied loads. The equilibria are thereby interpreted as quiescent, threshold configurations G = W_E, with G the Griffith mechanical-energy-release rate and W_E the Dupré work of adhesion, on crack velocity (v-G) diagrams. Generally, W_E is found to decrease with concentration of water, in accordance with a Gibbs formalism. Hysteresis is observed in the forward-backward-forward crack propagation cycle, signifying a reduction in the adhesion energy on exposure of the open interface to environmental species prior to healing. This hysteresis is especially marked for those interfaces that are misoriented before healing, indicating that the structure of the underlying solid substrate as well as of the intervening fluid is an important consideration in the interface energetics. The equilibrium states for different environments can be represented on a simple energy-level diagram, as differences between thermodynamic end-point states: initial, closed-interface states refer to crystallographic bonding configurations ahead of the crack-tip adhesion zone; final, open interface states refer to configurations behind the crack-tip zone. The significance of this diagram in relation to the fundamental atomic structure of interfaces in fracture and other adhesion geometries, including implications concerning kinetics, is discussed.

Pressurized internal lenticular cracks at healed mica interfaces

The equilibrium states of internal penny cracks at interfaces in thin-sheet bodies are investigated. Consideration is given to cracks held open by a center-loading force from an entrapped particle in combination with a uniform pressure from a fixed mass of entrapped gas. A fracture mechanics analysis indicates that under these conditions the cracks are stable, but are amenable to growth from an enhancement in net pressure (increase in internal pressure or decrease in external pressure) or effective particle size. Essential details of the theory are confirmed by experiments on lenticular cracks at healed interfaces in muscovite mica. The results are pertinent to flaw responses in brittle ceramic systems where structural integrity is an issue.

How honeybees make grazing landings on flat surfaces

Freely flying bees were filmed as they landed on a flat, horizontal surface, to investigate the underlying visuomotor control strategies. The results reveal that (1) landing bees approach the surface at a relatively shallow descent angle; (2) they tend to hold the angular velocity of the image of the surface constant as they approach it; and (3) the instantaneous speed of descent is proportional to the instantaneous forward speed. These characteristics reflect a surprisingly simple and effective strategy for achieving a smooth landing, by which the forward and descent speeds are automatically reduced as the surface is approached and are both close to zero at touchdown. No explicit knowledge of flight speed or height above the ground is necessary. A model of the control scheme is developed and its predictions are verified. It is also shown that, during landing, the bee decelerates continuously and in such a way as to keep the projected time to touchdown constant as the surface is approached. The feasibility of this landing strategy is demonstrated by implementation in a robotic gantry equipped with vision.