Experimental setup for measuring the dispersion forces by the adhered cantilever method.

Dispersion forces start to play role in modern micro/nanoelectromechanical devices, but the methods to measure these forces at distances close to contact (<50 nm) suffer from pull-in instability. The method of adhered cantilever proposed recently has no instability and is able to make measurements at short separations. To measure the force at the average distance between surfaces in contact, one has to know the shape of an elastic beam with one end fixed at a height of 1-10 µm and the other end adhered to the substrate. The maximum contribution to this shape from the dispersion forces is in a range of 30-100 nm, which is well measurable by the interferometric methods. This paper describes the instrument, measurements, and data processing that make possible the reconstruction of the beam shape with an accuracy of 1 nm in a height range of at least 5000 nm. Critical steps of the fabrication procedure of cantilevers that are 12 mm long, 200 µm wide, and 10 µm thick are described. The interferometer measures the shape based on the differential interference-contrast method; the scanning is realized by a stage with a step of 0.1 µm. The signal recorded from the adhered cantilever has a noise level of 0.33 nm at a maximum sensitivity in a frequency band of 20 MHz. It is concluded that the instrument and data processing algorithm can be used to measure the dispersion forces and adhesion energies between rough surfaces in unloaded contact.

Nanoreactors in action for a durable microactuator using spontaneous combustion of gases in nanobubbles.

A number of recent studies report enhancement of chemical reactions on water microdroplets or inside nanobubbles in water. This finding promises exciting applications, although the mechanism of the reaction acceleration is still not clear. Specifically, the spontaneous combustion of hydrogen and oxygen in nanobubbles opens the way to fabricate truly microscopic engines. An example is an electrochemical membrane actuator with all three dimensions in the micrometer range. The actuator is driven by short voltage pulses of alternating polarity, which generate only nanobubbles. The device operation is, however, restricted by a fast degradation of the electrodes related to a high current density. Here it is demonstrated that the actuator with ruthenium electrodes does not show signs of degradation in the long-term operation. It is the only material able to withstand the extreme conditions of the alternating polarity electrolysis. This property is due to combination of a high mechanical hardness and metallic conductivity of ruthenium oxide. The actuator combines two features considered impossible: on-water catalysis and combustion in a microscopic volume. It provides an exceptional opportunity to drive autonomous microdevices especially for medical or biological applications.

Fast Electrochemical Actuator with Ti Electrodes in the Current Stabilization Regime.

The actuators needed for autonomous microfluidic devices have to be compact, low-power-consuming, and compatible with microtechnology. The electrochemical actuators could be good candidates, but they suffer from a long response time due to slow gas termination. An actuator in which the gas is terminated orders of magnitude faster has been demonstrated recently. It uses water electrolysis performed by short voltage pulses of alternating polarity (AP). However, oxidation of Ti electrodes leads to a rapid decrease in the performance. In this paper, we demonstrate a special driving regime of the actuator, which is able to support a constant stroke for at least 105 cycles. The result is achieved using a new driving regime when a series of AP pulses are interspersed with a series of single-polarity (SP) pulses. The new regime is realized by a special pulse generator that automatically adjusts the amplitude of the SP pulses to keep the current flowing through the electrodes at a fixed level. The SP pulses increase the power consumption by 15-60% compared to the normal AP operation and make the membrane oscillate in a slightly lifted position.

Highly energetic impact of H2 and O2 nanobubbles on Pt surface.

Hypothesis Water electrolysis performed by short (≲5µs) voltage pulses of alternating polarity generates a dense cloud of H2 and O2 nanobubbles. Platinum electrodes turn black in this process, while they behave differently when the polarity is not altered. We prove that the modification of Pt is associated with highly energetic impact of nanobubbles rather than with any electrochemical process. Experiments Nanobubbles are generated by planar Pt or Ti microelectrodes. The process is driven by a series of alternating or single polarity pulses. In the case of Ti electrodes a Pt plate is separated by a gap from the electrodes. Nanoparticles on the surface of platinum are investigated with a scanning electron microscope and elemental composition is analysed using an energy-dispersive X-ray spectrometer. Findings Vigorous formation of Pt nanoparticles with a size of 10 nm is observed when the process is driven by the alternating polarity pulses. The effects of Pt corrosion have different character and cannot explain the phenomenon. Similar nanoparticles are observed when the Pt plate is exposed to a stream of nanobubbles. The process is explained by spontaneous combustion of hydrogen and oxygen nanobubbles on Pt surface. The phenomenon can be used to remove strongly adhered particles from solids.

Effect of Airborne Hydrocarbons on the Wettability of Phase Change Nanoparticle Decorated Surfaces.

We present here a detailed study of the wettability of surfaces nanostructured with amorphous and crystalline nanoparticles (NPs) derived from the phase-change material Ge2Sb2Te5 (GST). Particular attention was devoted to the effect of airborne surface hydrocarbons on surface wetting. Our analysis illustrates that a reversible hydrophilic-hydrophobic wettability switch is revealed by combined ultraviolet-ozone (UV-O3) treatments and exposure to hydrocarbon atmospheres. Indeed, the as-prepared surfaces exhibited a hydrophilic state after thermal annealing or UV-O3 treatment which can partially remove hydrocarbon contaminants, while a hydrophobic state was realized after exposure to hydrocarbon atmosphere. Using high-angle annular dark-field scanning transmission electron microscopy for the specially designed GST NP decorated graphene substrates, a network of hydrocarbon connecting GST NPs was observed. Our findings indicate that airborne hydrocarbons can significantly enhance the hydrophobicity of nanostructured surfaces. Finally, the experiments reveal that previously defined hydrophilic materials can be used for the design of hydrophobic surfaces even if the meniscus is highly adhered to a solid surface, which is in agreement with our qualitative model involving the contribution of the nanomeniscus formed between the substrate and a decorating NP.

Collective behavior of bulk nanobubbles produced by alternating polarity electrolysis.

Nanobubbles in liquids are mysterious gaseous objects with exceptional stability. They promise a wide range of applications, but their production is not well controlled and localized. Alternating polarity electrolysis of water is a tool that can control the production of bulk nanobubbles in space and time without generating larger bubbles. Using the schlieren technique, the detailed three-dimensional structure of a dense cloud of nanobubbles above the electrodes is visualized. It is demonstrated that the thermal effects produce a different schlieren pattern and have different dynamics. A localized volume enriched with nanobubbles can be separated from the parent cloud and exists on its own. This volume demonstrates buoyancy, from which the concentration of nanobubbles is estimated as 2 × 1018 m-3. This concentration is smaller than that in the parent cloud. Dynamic light scattering shows that the average size of nanobubbles during the process is 60-80 nm. The bubbles are observed 15 minutes after switching off the electrical pulses but their size is shifted to larger values of about 250 nm. Thus, an efficient way to generate and control nanobubbles is proposed.

Electrically controlled cloud of bulk nanobubbles in water solutions.

Using different experimental techniques we visualize a cloud of gas in water that is produced electrochemically by the alternating polarity process. Liquid enriched with gas does not contain bubbles strongly scattering visible light but its refractive index changes significantly near the electrodes. The change of the refractive index is a collective effect of bulk nanobubbles with a diameter smaller than 200 nm. Any alternative explanation fails to explain the magnitude of the effect. Spatial structure of the cloud is investigated with the optical lever method. Its dynamics is visualised observing optical distortion of the electrode images or using differential interference contrast method. The cloud covers concentric electrodes, in a steady state it is roughly hemispherical with a size two times larger than the size of the electrode structure. When the electrical pulses are switched off the cloud disappears in less than one second. The total concentration of gases can reach very high value estimated as 3.5 × 1020 cm-3 that corresponds to an effective supersaturation of 500 and 150 for hydrogen and oxygen, respectively.

Effect of Disjoining Pressure on Surface Nanobubbles.

In gas-oversaturated solutions, stable surface nanobubbles can exist thanks to a balance between the Laplace pressure and the gas overpressure, provided the contact line of the bubble is pinned. In this article, we analyze how the disjoining pressure originating from the van der Waals interactions of the liquid and the gas with the surface affects the properties of the surface nanobubbles. From a functional minimization of the Gibbs free energy in the sharp-interface approximation, we find the bubble shape that takes into account the attracting van der Waals potential and gas compressibility effects. Although the bubble shape slightly deviates from the classical one (defined by the Young contact angle), it preserves a nearly spherical-cap shape. We also find that the disjoining pressure restricts the aspect ratio (size/height) of the bubble and derive the maximal possible aspect ratio, which is expressed via the Young angle.

New type of microengine using internal combustion of hydrogen and oxygen.

Microsystems become part of everyday life but their application is restricted by lack of strong and fast motors (actuators) converting energy into motion. For example, widespread internal combustion engines cannot be scaled down because combustion reactions are quenched in a small space. Here we present an actuator with the dimensions 100 × 100 × 5 µm(3) that is using internal combustion of hydrogen and oxygen as part of its working cycle. Water electrolysis driven by short voltage pulses creates an extra pressure of 0.5-4 bar for a time of 100-400 µs in a chamber closed by a flexible membrane. When the pulses are switched off this pressure is released even faster allowing production of mechanical work in short cycles. We provide arguments that this unexpectedly fast pressure decrease is due to spontaneous combustion of the gases in the chamber. This actuator is the first step to truly microscopic combustion engines.

Transient nanobubbles in short-time electrolysis.

Water electrolysis in a microsystem is observed and analyzed on a short-time scale of ∼10 µs. The very unusual properties of the process are stressed. An extremely high current density is observed because the process is not limited by the diffusion of electroactive species. The high current is accompanied by a high relative supersaturation, S > 1000, that results in homogeneous nucleation of bubbles. On the short-time scale only nanobubbles can be formed. These nanobubbles densely cover the electrodes and aggregate at a later time to microbubbles. The effect is significantly intensified with a small increase of temperature. Application of alternating polarity voltage pulses produces bubbles containing a mixture of hydrogen and oxygen. Spontaneous reaction between gases is observed for stoichiometric bubbles with sizes smaller than ∼150 nm. Such bubbles disintegrate violently affecting the surfaces of the electrodes.

Combustion of hydrogen-oxygen mixture in electrochemically generated nanobubbles.

Ignition of exothermic chemical reactions in small volumes is considered as difficult or impossible due to the large surface-to-volume ratio. Here observation of the spontaneous reaction is reported between hydrogen and oxygen in bubbles whose diameter is smaller than a threshold value around 150 nm. The effect is attributed to high Laplace pressure and to fast dynamics in nanobubbles and is the first indication on combustion in the nanoscale. In this study the bubbles were produced by water electrolysis using successive generation of H(2) and O(2) above the same electrode with short voltage pulses in the microsecond range. The process was observed in a microsystem at current densities >1000 A/cm(2) and relative supersaturations >1000.

Application of the Lifshitz theory to poor conductors.

The Lifshitz formula for dispersive forces is generalized to the materials, which cannot be described with the local dielectric response. The principal nonlocality of poor conductors is related to the finite screening length of the penetrating field and collisional relaxation; at low temperatures the role of collisions plays the Landau damping. Spatial dispersion makes the theory self-consistent. Our predictions are compared with the recent experiment. It is demonstrated that at low temperatures Casimir-Lifshitz entropy disappears as T in the case of degenerate plasma and as T2 for the nondegenerate one.

Casimir-lifshitz force out of thermal equilibrium and asymptotic nonadditivity.

We investigate the force acting between two parallel plates held at different temperatures. The force reproduces, as limiting cases, the well-known Casimir-Lifshitz surface-surface force at thermal equilibrium and the surface-atom force out of thermal equilibrium recently derived by M. Antezza et al., Phys. Rev. Lett. 95, 113202 (2005)10.1103/PhysRevLett.95.113202. The asymptotic behavior of the force at large distances is explicitly discussed. In particular when one of the two bodies is a rarefied gas the force is not additive, being proportional to the square root of the density. Nontrivial crossover regions at large distances are also identified.