David Fernandez Rivas

Efficient Sonochemistry through Microbubbles Generated with Micromachined Surfaces

Sonochemical reactors are used in water treatment, the synthesis of fine chemicals, pharmaceutics and others. The low e ciency of sonoreactors have prevented its massive usage at industrial scales. Controlling the appearance of bubbles in place and time is the most limiting factor. A novel type of sonochemical reactor was designed making use of micro-fabrication techniques to control the nucleation sites of micro-bubbles. The e ciency was increased first by locating the nucleation sites in the most active region of a micro-chamber; additionally the desired chemical e ect was significantly higher at the same powers than when not controlled. Silicon substrates were micromachined with “artificial nucleation sites” or pits, and placed at the bottom of the micro-chamber. The pits entrap gas which, upon ultrasonic excitation, sheds o a stream of microbubbles. The gas content of the pits is not depleted but is replenished by di usion and the emission of microbubbles can continue for hours. Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/anie.201005533 Published in: Angewandte Chemie International Edition, 49:50, (2010), 9699-9701

Sonoluminescence and sonochemiluminescence from a microreactor

Micromachined pits on a substrate can be used to nucleate and stabilize microbubbles in a liquid exposed to an ultrasonic field. Under suitable conditions, the collapse of these bubbles can result in light emission (sonoluminescence, SL). Hydroxyl radicals (OH()) generated during bubble collapse can react with luminol to produce light (sonochemiluminescence, SCL). SL and SCL intensities were recorded for several regimes related to the pressure amplitude (low and high acoustic power levels) at a given ultrasonic frequency (200kHz) for pure water, and aqueous luminol and propanol solutions. Various arrangements of pits were studied, with the number of pits ranging from no pits (comparable to a classic ultrasound reactor), to three-pits. Where there was more than one pit present, in the high pressure regime the ejected microbubbles combined into linear (two-pits) or triangular (three-pits) bubble clouds (streamers). In all situations where a pit was present on the substrate, the SL was intensified and increased with the number of pits at both low and high power levels. For imaging SL emitting regions, Argon (Ar) saturated water was used under similar conditions. SL emission from aqueous propanol solution (50mM) provided evidence of transient bubble cavitation. Solutions containing 0.1mM luminol were also used to demonstrate the radical production by attaining the SCL emission regions.

Localized removal of layers of metal, polymer, or biomaterial by ultrasound cavitation bubbles

We present an ultrasonic device with the ability to locally remove deposited layers from a glass slide in a controlled and rapid manner. The cleaning takes place as the result of cavitating bubbles near the deposited layers and not due to acoustic streaming. The bubbles are ejected from air-filled cavities micromachined in a silicon surface, which, when vibrated ultrasonically at a frequency of 200 kHz, generate a stream of bubbles that travel to the layer deposited on an opposing glass slide. Depending on the pressure amplitude, the bubble clouds ejected from the micropits attain different shapes as a result of complex bubble interaction forces, leading to distinct shapes of the cleaned areas. We have determined the removal rates for several inorganic and organic materials and obtained an improved efficiency in cleaning when compared to conventional cleaning equipment. We also provide values of the force the bubbles are able to exert on an atomic force microscope tip.

Cavitation measurement during sonic and ultrasonic activated irrigation

INTRODUCTION The aims of this study were to quantify and to visualize the possible occurrence of transient cavitation (bubble formation and implosion) during sonic and ultrasonic (UAI) activated irrigation. METHODS The amount of cavitation generated around several endodontic instruments was measured by sonochemiluminescence dosimetry inside 4 root canal models of human dimensions and varying complexity. Furthermore, the spatial distribution of the sonochemiluminescence in the root canal was visualized with long-exposure photography. RESULTS Instrument oscillation frequency, ultrasonic power, and file taper influenced the occurrence and amount of cavitation. In UAI, cavitation was distributed between the file and the wall extending beyond the file and inside lateral canals/isthmuses. In sonic activated irrigation, no cavitation was detected. CONCLUSIONS Cavitation was shown to occur in UAI at clinically relevant ultrasonic power settings in both straight and curved canals but not around sonically oscillating instruments, driven at their highest frequency.

Synergy of Microfluidics and Ultrasound: Process Intensification Challenges and Opportunities

A compact snapshot of the current convergence of novel developments relevant to chemical engineering is given. Process intensification concepts are analysed through the lens of microfluidics and sonochemistry. Economical drivers and their influence on scientific activities are mentioned, including innovation opportunities towards deployment into society. We focus on the control of cavitation as a means to improve the energy efficiency of sonochemical reactors, as well as in the solids handling with ultrasound; both are considered the most difficult hurdles for its adoption in a practical and industrial sense. Particular examples for microfluidic clogging prevention, numbering-up and scaling-up strategies are given. To conclude, an outlook of possible new directions of this active and promising combination of technologies is hinted.

Enhancing acoustic cavitation using artificial crevice bubbles

We study the response of pre-defined cavitation nuclei driven continuously in the kHz regime (80, 100 and 200 kHz). The nuclei consist of stabilized gaspockets in cylindrical pits of 30 μm diameter etched in silicon or glass substrates. It is found that above an acoustic pressure threshold the dynamics of the liquid-gas meniscus switches from a stable drum-like vibration to expansion and deformation, frequently resulting in detachment of microbubbles. Just above this threshold small bubbles are continuously and intermittently ejected. At elevated input powers bubble detachment becomes more frequent and cavitation bubble clouds are formed and remain in the vicinity of the pit bubble. Surprisingly, the resulting loss of gas does not lead to deactivation of the pit which can be explained by a rectified gas diffusion process.

Emulsification in novel ultrasonic cavitation intensifying bag reactors

Cavitation Intensifying Bags (CIBs), a novel reactor type for use with ultrasound, have been recently proposed as a scaled-up microreactor with increased energy efficiencies. We now report on the use of the CIBs for the preparation of emulsions out of hexadecane and an SDS aqueous solution. The CIBs have been designed in such a way that cavitation effects created by the ultrasound are increased. It was found that the CIBs were 60 times more effective in breaking up droplets than conventional bags, therewith showing a proof of principle for the CIBs for the preparation of emulsions. Droplets of 0.2μm could easily be obtained. To our knowledge, no other technology results in the same droplet size more easily in terms of energy usage. Without depending on the wettability changes of the membrane, the CIBs score similarly as membrane emulsification, which is the most energy friendly emulsification method known in literature. Out of the frequencies used, 37kHz was found to require the lowest treatment time. The treatment time decreased at higher temperatures. While the energy usage in the current non-optimised experiments was on the order of 107-109J/m3, which is comparable to that of a high-pressure homogenizer, we expect that the use of CIBs for the preparation of fine emulsions can still be improved considerably. The process presented can be applied for other uses such as water treatment, synthesis of nanomaterials and food processing.

Electrolysis-Driven and Pressure-Controlled Diffusive Growth of Successive Bubbles on Microstructured Surfaces

Control over the bubble growth rates forming on the electrodes of water-splitting cells or chemical reactors is critical with respect to the attainment of higher energy efficiencies within these devices. This study focuses on the diffusion-driven growth dynamics of a succession of H2 bubbles generated at a flat silicon electrode substrate. Controlled nucleation is achieved by means of a single nucleation site consisting of a hydrophobic micropit etched within a micrometer-sized pillar. In our experimental configuration of constant-current electrolysis, we identify gas depletion from (i) previous bubbles in the succession, (ii) unwanted bubbles forming on the sidewalls, and (iii) the mere presence of the circular cavity where the electrode is being held. The impact of these effects on bubble growth is discussed with support from numerical simulations. The time evolution of the dimensionless bubble growth coefficient, which is a measure of the overall growth rate of a particular bubble, of electrolysis-generated bubbles is compared to that of CO2 bubbles growing on a similar surface in the presence of a supersaturated solution of carbonated water. For electrolytic bubbles and under the range of current densities considered here (5-15 A/m2), it is observed that H2 bubble successions at large gas-evolving substrates first experience a stagnation regime, followed by a fast increase in the growth coefficient before a steady state is reached. This clearly contradicts the common assumption that constant current densities must yield time-invariant growth rates. Conversely, for the case of CO2 bubbles, the growth coefficient successively decreases for every subsequent bubble as a result of the persistent depletion of dissolved CO2.

Taming acoustic cavitation

This thesis shows that through microfabrication techniques, an improved efficiency of sono-reactors can be achieved by the control of the nucleation sites of bubble streamers. It has been proofed that one order of magnitude improvement compared to the equivalent conventional sonoreactor is feasible. The characteristics of the light emitted (SL and SCL) from the reactor can give useful information on the type of bubbles generated. When more sophisticated techniques are available, more details on the nucleation of bubble streamers and its complex behavior can be addressed. The practical uses of these bubble streamers is shown for removing various types of layers and in different liquids other than water. The negative effects of cavitation erosion were studied for different types of silicon with important insight into future reactors design strategies. Nevertheless, the complexity of sonochemical reactors still remains, as bubbles generated in this way do not behave in a simpler way than in conventional reactors. What is clear is that there is enough room for improvement and challenging and new applications are around the corner to further tame acoustic cavitation.

Is reproducibility inside the bag? Special issue fundamentals and applications of sonochemistry ESS-15

In this paper we report our most recent attempts to tackle a notorious problem across several scientific activities from the ultrasonics sonochemical perspective: reproducibility of results. We provide experimental results carried out in three different laboratories, using the same ingredients: ultrasound and a novel cavitation reactor bag. The main difference between the experiments is that they are aimed at different applications, KI liberation and MB degradation; and exfoliation of two nanomaterials: graphene and molybdenum disulfide. Iodine liberation rates and methylene blue degradation were higher for the cases where a cavitation intensification bag was used. Similarly, improved dispersion and more polydisperse exfoliated layers of nanomaterials were observed in the intensified bags compared to plain ones. The reproducibility of these new experiments is compared to previous experimental results under similar conditions. Our main conclusion is that despite knowing and understanding most physicochemical phenomena related to the origins and effects of cavitation, there is still a long path towards reproducibility, both in one laboratory, and compared across different laboratories. As emphasized in the sonochemical literature, the latter clearly illustrates the complexity of cavitation as nonlinear phenomenon, whose quantitative estimation represents a challenging aspect. We also provide a list of procedural steps that can help improving reproducibility and scale-up efforts.