Probing the mechanisms of enhanced crystallisation of APS in the presence of ultrasound.

Understanding the origins of the enhancement of crystallisation of a lipid (all-purpose shortening, APS) through the application of ultrasound is a fundamental pre-requisite for the exploitation of this technique in a wider context. To this end, we show here a number of measurements designed to probe the mechanisms responsible for this effect. For example, we show how the type of bubble cluster, produced at the sound source, alters the bubble population and residency time. In addition, to probe the various contributions to the enhanced crystallisation rate, isolation of the cluster environment below the piston like emitter (PLE) used as the ultrasonic source was shown to reduce the enhancement observed, but did not remove it entirely. This implied that the exposure of the liquid to pressure shocks and the environment around the cluster has a positive effect on the crystallisation kinetics. In turn the addition of extra seed crystals and mechanical agitation also enhances the rate of crystallisation. Finally, the time at which ultrasonic irradiation of the fluid is applied is shown to alter the kinetics observed. These observations suggest that two components are important: large bubble populations and mechanical effects on pre-existing crystals. These findings suggest that maximising these effects could be an eloquent way to enhance and control the material characteristics of materials produced in this manner.

Development of an optical flow through detector for bubbles, crystals and particles in oils.

The characterisation of bubbles or particles in an oil poses some unique challenges. In contrast to water solutions, the use of electrochemical detection approaches is more difficult in an oil. However, optical sensing systems have considerable potential in this area. Here we use a flow through channel approach and monitor the light propagation through this structure in an optical transmission sensor arrangement (OTS). This simple approach is demonstrated to be useful at detecting bubbles produced in the oil as a result of cavitation induced by high intensity ultrasound (HIU). The optical technique is shown to have an analytical basis. Bubble detection from an operating HIU source is shown to depend on position of the sensor with respect to the source. Critically, the bubble population can be followed for extended time periods after the ultrasonic source has been terminated. The detection of crystals is also demonstrated. Hence, this technique is ideal for the study of the effects of HIU on oils as they crystallise over extended time periods.

Enhanced crystallisation kinetics of edible lipids through the action of a bifurcated streamer.

The processing of healthy foods remains a challenge and any technology with the ability to tailor the physical properties of new materials is in demand. High-intensity ultrasound (HIU) has been identified as a useful processing technique for such activities particularly for edible lipids. HIU has been known to alter the crystallisation kinetics and in turn the resultant physicochemical properties for specific food applications. The role of cavitation dynamics during treatment of oils with HIU is of interest, with the knowledge gained allowing for insight into the complex and still undefined mechanism of action. To this end, the crystallisation kinetics of an edible lipid were investigated in the presence of several distinctly different cavitation conditions. Several cavitation clusters, including a bifurcated streamer (BiS), located on the surface of a piston-like emitter (PLE) were studied, each generated by a specific ultrasonic power level. Only samples crystallised at a low supercooling (ΔTSC) value display significant differences in induction time for each of the selected HIU powers, at least 5 minutes earlier than without exposure to HIU. Substantially better energy efficiencies were seen for the BiS regime (ΔTSC = 5 °C) which coincided with maximal crystal growth rates. An increase in melting enthalpy and elastic modulus is reported in the presence of HIU for all crystallisation temperatures, this effect is larger overall with increasing ultrasonic power. In addition, sonicated samples in the presence of the BiS event were composed of fewer smaller crystals compared to higher HIU powers after 60 minutes at 30 °C. Bubble dynamics recorded during a 10 s sonication period exhibited a greater acoustic attenuation effect for the highest ultrasonic power (75 W). The results suggest that the dynamics of the cluster and the presence of the BiS event are important in terms of energy efficiency and the physical properties of the crystallised lipid material.

The in situ electrochemical detection of microbubble oscillations during motion through a channel.

Bubble oscillation has many applications, from driving local fluid motion to cleaning. However, in order to exploit their action, a full understanding of this motion, particularly in confined spaces (such as crevices etc. which are important in ultrasonic decontamination) is important. To this end, here we show how a Coulter counter can be used to characterize microbubbles produced through the ultrasonication of electrolytes. These microbubbles are shown to exist in relatively high concentrations while bubble activity is driven by ultrasound. Detection of these microbubbles, and their oscillatory behaviour, is achieved via translocation through a cylindrical glass microchannel (GMC). The microbubbles oscillate within the 40 µm channel employed and this behaviour is observed to change over the translocation period. This is attributed to the acoustic environment present or changes to the physical conditions in the interior of the chamber compared to the exterior. High-speed imaging confirms the presence of microbubbles as they move or 'skate' across the surface of the structures present before translocating through the channel. The observations are useful as they show that microbubble oscillation occurs within small structures, is preceded by surface confined bubbles and could be enhanced through pressure driven flow through a structure.

An electrochemical and high-speed imaging study of micropore decontamination by acoustic bubble entrapment.

Electrochemical and high-speed imaging techniques are used to study the abilities of ultrasonically-activated bubbles to clean out micropores. Cylindrical pores with dimensions (diameter × depth) of 500 µm × 400 µm (aspect ratio 0.8), 125 µm × 350 µm (aspect ratio 2.8) and 50 µm × 200 µm (aspect ratio 4.0) are fabricated in glass substrates. Each pore is contaminated by filling it with an electrochemically inactive blocking organic material (thickened methyl salicylate) before the substrate is placed in a solution containing an electroactive species (Fe(CN)6(3-)). An electrode is fabricated at the base of each pore and the Faradaic current is used to monitor the decontamination as a function of time. For the largest pore, decontamination driven by ultrasound (generated by a horn type transducer) and bulk fluid flow are compared. It is shown that ultrasound is much more effective than flow alone, and that bulk fluid flow at the rates used cannot decontaminate the pore completely, but that ultrasound can. In the case of the 125 µm pore, high-speed imaging is used to elucidate the cleaning mechanisms involved in ultrasonic decontamination and reveals that acoustic bubble entrapment is a key feature. The smallest pore is used to explore the limits of decontamination and it is found that ultrasound is still effective at this size under the conditions employed.

Multiple observations of cavitation cluster dynamics close to an ultrasonic horn tip.

Bubble dynamics in water close to the tip of an ultrasonic horn (∼23 kHz, 3 mm diameter) have been studied using electrochemistry, luminescence, acoustics, light scattering, and high-speed imaging. It is found that, under the conditions employed, a large bubble cluster (∼1.5 mm radius) exists at the tip of the horn. This cluster collapses periodically every three to four cycles of the fundamental frequency of the horn. Following the collapse of the cluster, a short-lived cloud of small bubbles (each tens of microns in diameter) was observed in the solution. Large amplitude pressure emissions are also recorded, which correlate temporally with the cluster collapse. Bursts of surface erosion (measured in real time using an electrochemical technique) and multibubble sonoluminescence emission both also occur at a subharmonic of the fundamental frequency of the horn and are temporally correlated with the bubble cluster collapse and the associated pressure wave emission.

Investigation of noninertial cavitation produced by an ultrasonic horn.

This paper reports on noninertial cavitation that occurs beyond the zone close to the horn tip to which the inertial cavitation is confined. The noninertial cavitation is characterized by collating the data from a range of measurements of bubbles trapped on a solid surface in this noninertial zone. Specifically, the electrochemical measurement of mass transfer to an electrode is compared with high-speed video of the bubble oscillation. This gas bubble is shown to be a "noninertial" event by electrochemical surface erosion measurements and "ring-down" experiments showing the activity and motion of the bubble as the sound excitation was terminated. These measurements enable characterization of the complex environment produced below an operating ultrasonic horn outside of the region where inertial collapse can be detected. The extent to which solid boundaries in the liquid cause the frequencies and shapes of oscillatory modes on the bubble wall to differ from their free field values is discussed.

Opto-isolation of electrochemical systems in cavitation environments.

An electrochemical technique that can detect inertial cavitation within an ultrasonic reactor is reported. The technique relies on the erosion and repassivation of an oxide covered electrode (specifically aluminum). The sensitivity of the technique (<46 fg per erosion event) is significantly greater than normal weight loss measurements. A novel opto-isolation system is discussed which enables the electrochemical measurements to be undertaken within an earthed metallic container. Events detected in this manner are reported and compared to the noise in the absence of appropriate isolation. This system is combined with a multichannel analyzer to map the erosion/corrosion activity within an operating ultrasonic bath.

An Analytical Differential Resistance Pulse System Relying on a Time Shift Signal Analysis-Applications in Coulter Counting.

Improving the sensitivity and ultimately the range of particle sizes that can be detected with a single pore extends the versatility of the Coulter counting technique. Here, to enable a pore to have greater sensitivity, we have developed and tested a novel differential resistive pulse sensing (DiS) system for sizing particles. To do this, the response was generated through a time shift approach utilizing a "self-servoing regime" to enable the final signal to operate with a zero background in the absence of particle translocation. The detection and characterization of a series of polystyrene particles, forced to translocate through a cylindrical glass microchannel (GMC) by a suitable static pressure difference using this approach, is demonstrated. An analytical response, which scales with the size of the particles employed, was verified. Parasitic capacitive effects are discussed; however, translocations on the millisecond time scale can be detected with high sensitivity and accuracy using the approach described.

An activated fluid stream--New techniques for cold water cleaning.

Electrochemical, acoustic and imaging techniques are used to characterise surface cleaning with particular emphasis on the understanding of the key phenomena relevant to surface cleaning. A range of novel techniques designed to enhance and monitor the effective cleaning of a solid/liquid interface is presented. Among the techniques presented, mass transfer of material to a sensor embedded in a surface is demonstrated to be useful in the further exploration of ultrasonic cleaning of high aspect ratio micropores. In addition the effect of micropore size on the cleaning efficacy is demonstrated. The design and performance of a new cleaning system reliant on the activation of bubbles within a free flowing stream is presented. This device utilised acoustic activation of bubbles within the stream and at a variety of substrates. Finally, a controlled bubble swarm is generated in the stream using electrolysis, and its effect on both acoustic output and cleaning performance are compared to the case when no bubbles are added. This will demonstrate the active role that the electrochemically generated bubble swarm can have in extending the spatial zone over which cleaning is achieved.

Cavitation, shock waves and the invasive nature of sonoelectrochemistry.

The invasive nature of electrodes placed into sound fields is examined. In particular, perturbations of the sound field due to the presence of the electrode support are explored. The effect of an electrode on the drive sound field (at approximately 23 kHz) is shown to be negligible under the conditions investigated in this paper. However, scattering of shock waves produced by cavity collapse is shown to exhibit a significant effect. To demonstrate this, multibubble sonoluminescence (MBSL) and electrochemical erosion measurements are employed. These measurements show an enhancement, due to the reflection by the solid/liquid boundary at the electrode support, of pressure pulses emitted when cavitation bubbles collapse. To first order, this effect can be accounted for by a correction factor. However, this factor requires accurate knowledge of the acoustic impedance of the interface and the electrolyte media. These are measured for two commonly employed substrates (soda glass and epoxy resin, specifically Epofix). A scattering model is developed which is able to predict the acoustic pressure as a function of position over a disk-like electrode substrate. The effects of shock wave reflection and materials employed in the electrode construction are used to clarify the interpretation of the results obtained from different sonoelectrochemical experiments. Given the widespread experimentation involving the insertion of electrodes (or other sensors) into ultrasonic fields, this work represents a significant development to aid the interpretation of the results obtained.

Electrochemical detection of bubble oscillation.

The interaction of a tethered bubble with sound is demonstrated using novel electrochemical characterisation technology. A 25 microm diameter microelectrode, positioned close to the gas/liquid interface is used to monitor the motion of the bubble wall as a function of time in the presence and absence of sonic irradiation. Evidence for 'breathing' mode oscillation of the bubble and its effect on mass transfer to the microelectrode is presented.

The use of acoustoelectrochemistry to investigate rectified diffusion.

This paper describes the approach to bubble related phenomena using a novel 'acoustoelectrochemical' technique designed to investigate the physical and chemical effects of the acoustically induced motion of the bubble wall. In particular it describes the behaviour of a suspended gas bubble irradiated with sound of an appropriate frequency and pressure to induce bubble wall oscillation. The first electrochemical measurement of the growth of a bubble through rectified diffusion is demonstrated. The technique employed relies on the sensitivity of a scanning electrochemical microscope (SECM) deployed close to the gas/liquid interface of a bubble. The growth rate of the bubble (<0.1 microms(-1)) is reported. It will be also demonstrated that gas exchange across the phase boundary at the bubble wall, can be successfully probed when the bubble is stationary.

Electrochemical, luminescent and photographic characterisation of cavitation.

The characterisation of a small sonochemical reactor has been performed using electrochemical, luminescent and photographic techniques. The electrochemical experiments have employed a novel flow system to determine the formation of sonochemical products (in this case hydrogen peroxide) in semi-real time with high sensitivity. The rate of production of hydrogen peroxide is reported as a function of driving pressure amplitude. The degradation of an organic molecule, specifically the organic dye amaranth, within the sonochemical cell is also reported.

TEMPO-mediated electrooxidation of primary and secondary alcohols in a microfluidic electrolytic cell.

A general procedure for the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated electrooxidation of primary and secondary alcohols modified for application in a microfluidic electrolytic cell is described. The electrocatalytic system utilises a buffered aqueous tert-butanol reaction medium, which operates effectively without the requirement for additional electrolyte, providing a mild protocol for the oxidation of alcohols to aldehydes and ketones at ambient temperature on a laboratory scale. Optimisation of the process is discussed along with the oxidation of 15 representative alcohols.

Experimental and theoretical characterisation of sonochemical cells. Part 2: cell disruptors (Ultrasonic horns) and cavity cluster collapse.

Cavitation theory is used to predict the acoustic pressure at the boundary of the inertial/non inertial threshold for a range of bubble sizes. The sound field generated from a commonly employed sonoelectrochemical cell is modelled. The model is tested with a calibrated hydrophone far from the transducer to avoid spatial averaging. This allows the model to provide the absolute pressure amplitude as a function of axial distance from the source. An electrochemical technique for detecting both inertial and non-inertial cavitation within the solution is employed. This technique uses a dual microelectrode to map the boundary between the regions where inertial cavitation occurs (associated with surface erosion), and where it does not. This zone occurs close to the transducer for the microelectrode employed (<1.5 mm). Further characterisation of the inertial cavitation zone is achieved by imaging of multibubble sonoluminescence (MBSL). The pressures at the boundary between inertial and non inertial cavitation that are determined from the electrochemical and imaging experiments are compared to a sound field model and cavitation theory. Qualitative arguments for the invasive nature of the electrode into the sound field are proposed. Evidence for cavity cluster collapse and shock wave emission is presented and discussed in relation to luminescence, the electrochemical experiments and cavitation theory.

Cathodic electrochemical detection of sonochemical radical products.

This paper reports on an electrochemical technique for the detection of oxidizing radical species, produced as the result of cavitation induced by ultrasound. A study of two example reactions is reported: the Weissler reaction and the Fricke reaction. In both cases, redox-active materials trap oxidative radicals. Electrochemical detection within a flow cell system is then used to sense redox-active products of the reactions between a chosen trapping agent and radicals produced within an ultrasonically irradiated aqueous solution. A demonstration of the sensitivity of electrochemical detection of radical products is presented. An equivalent dose of the ultrasonic reactor is reported.