Trends in sonochemistry and ultrasonic processing

Timothy J. Mason

Citation: AIP Conf. Proc. 1433, 21 (2012); doi: 10.1063/1.3703131

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 Trends in Sonochemistry and Ultrasonic Processing
Timothy J. Mason

Sonochemistry Centre, Faculty of Health and Life Sciences, Coventry University, Coventry CV1 5FB, UK

Abstract. It is always a valuable exercise to review the origins and developments of a technology before going on to
look at future prospects. Such an exercise allows one to judge both whether that technology has real long term
applications or is simply of transient interest on a laboratory scale. In the field of power ultrasound it is a fact that
many applications predated the advent of what is now known as sonochemistry by many years. A number of books
and articles were written that explored laboratory and industrial applications of ultrasonics from the 1920’s. With
such early applications in mind this paper will try and identify the early developments into a field that is now
encompassed by the term sonochemistry. Amongst the topics that will be highlighted are chemical synthesis,
electrochemistry, environmental protection, food technology and therapeutic ultrasound.
Keywords: ultrasound, processing, history, prospects

INTRODUCTION
This article has two aims the first being to review of the historical origins of ultrasound technology that has
become known as sonochemistry. The second is to illustrate some current developments of the technology in
chemical synthesis, electrochemistry, environmental protection, food technology and therapeutic ultrasound.
In science it is always important to appreciate and give credit to the contributions of those who were
pioneers of original research generally working with much poorer facilities than we have nowadays. In this way
we can make sure that in our own research we are not simply “re-inventing the wheel” but either developing a
new field or adding to existing knowledge. It is becoming more important that this should be done as a basic
part of any new project to avoid the trap fallen into by so many new research students of believing that all
knowledge is to be found in the search engines and files accessible using a computer.
Sonochemistry and ultrasonic processing are driven by cavitation which was first identified and
characterized in 1895 when Thornicroft found that it was the reason why there was inefficient drive from the
propellers of the high speed torpedo boat HMS Daring [1]. This and subsequent very early studies were all
linked to the type of cavitation produced by propellers driving through water i.e. hydrodynamic cavitation. A
key paper relating to cavitation was published in 1917 by Lord Rayleigh in which he developed a theoretical
investigation of the behaviour of the collapse of a “spherical void” in an incompressible fluid in a seminal
paper entitled “On the pressure developed in a liquid during the collapse of a spherical cavity” [2]. The research
was carried out because of the concern of hydraulic engineers with the problem of erosion. He was concerned
only with the collapse of existing cavities under a steady pressure but it has proved to be the basis of most
subsequent theoretical treatments of cavitation . Even today engineers will associate cavitation with surface
erosion and thus with damage to any surface in contact with a flowing liquid. However a s we will see later the
energy of cavitation is very high and when it is harnessed correctly it can be used to produce some remarkable
effects.
There are two types of cavitation the first has been mentioned above and is called hydrodynamic cavitation
and the second is acoustic cavitation which can be generated with power ultrasound. Like any sound wave
ultrasound is propagated via a series of compression and rarefaction waves induced in the molecules of the
medium through which it passes. At sufficiently high power the rarefaction cycle may exceed the attractive

International Congress on Ultrasonics

AIP Conf. Proc. 1433, 21-26 (2012); doi: 10.1063/1.3703131
© 2012 American Institute of Physics 978-0-7354-1019-0/$30.00

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forces of the molecules of the liquid and cavitation bubbles will form. Such bubbles grow by a process known
as rectified diffusion i.e. small amounts of vapour (or gas) from the medium enters the bubble during its
expansion phase and is not fully expelled during compression. It is the fate of these bubbles when they collapse
in succeeding compression cycles which generates energy. Some 30 or so years after the work of Rayleigh the
most significant advances in the development of mathematical treatment of acoustic cavitation came with the
work of Plesset in 1949 [3]. He developed an equation for the motion of a vapour-filled bubble in a changing
pressure field. Soon after this Noltingk and Neppiras developed equations describing the motion of a gas-filled
cavitation bubble in a liquid subjected to alternating pressure [4]. It was predicted from the latter work that as
the frequency of the acoustic wave was increased so the cavitation energy would decrease and at a certain
frequency all cavitation would finally disappear. By 1939 the effects of ultrasound were becoming more
familiar and the subject of many reports. These were reviewed by Richards in an excellent paper entitled
“Supersonic Phenomena“ that contained 348 references [5].
One of the effects of acoustic cavitation that gives an indication of the amount of instantaneous energy
involved in the collapse event is the generation of light. Frenzel and Schulze reported this effect for the first
time in 1934 [6]. The light produced during cavitation produced spots on a photographic film. Two years later
Chambers refered to this effect as sonic-luminescence [7] but today we know it as sonoluminescence and it is a
key tool in the investigation of cavitation. By 1939 the effects of ultrasound were becoming well known and the
subject of many reports. These were reviewed by Richards in an excellent paper entitled Supersonic
Phenomena containing 348 references [5].
Accompanying the development of the theory of cavitation and the observation of light emission was the
direct observation of cavitation bubble behaviour. Knapp & Hollander investigated hydrodynamic cavitation
induced by pressure drop over a blade using high-speed photography, and found the cavitation bubbles were
strongly deformed by the flow [8]. In more recent years the use of high speed photography was adopted and
developed by the Lauterborn group in Germany [9, 10].
Interest in acoustic cavitation continues and has now been refined into single bubble and multibubble
conditions and also the shape of bubble clusters [11] [12].

APPLICATIONS

Chemical Synthesis

The first report of the chemical effects of ultrasound was in 1927 which described the use of ulrasound for a
range of processes including emulsification and surface cleaning [13]. There were occasional references to
chemistry influenced by ultrasound after this and the two uses of ultrasound for chemists were considered to be
in analysis and synthesis [14]. In the 1950’s thought was being given to the reasons why acoustic cavitation
could induce chemical changes and this resulted in the concept of cavitation bubbles acting as “hot-spots” [15].
Primary ultrasonic reactions were seen as gas phase reactions, probably of a thermal nature, taking place inside
the bubbles themselves. Sonochemistry itself as a subject in its own right was not really recognised until the
1980’s when the first ever international conference was held at Warwick University in the UK in April 1986
[16]. This was followed by the first two major reviews of the subject divided into physical aspects [17] and
synthetic applications [18].
Recent reviews on those aspects of sonochemistry used in chemical synthesis have shown the breadth of
applications in this field [19, 20].

Electrochemistry

Nowadays we take it for granted that the effects of cavitation will strongly influence electrochemistry. It can
be readily appreciated that there are general benefits with the application of ultrasound which include keeping
the electrodes clean, degassing at the electrode surface, improved mass transport to the electrode and the
disturbance of the diffusion layer resulting in minimal ion depletion. In the 1930’s there were two types of
application that were initiated. The basic science of ultrasonic effects on electrode processes e.g. the work of
Moriguchi who showed that ultrasound reduced the decomposition voltage of water at platinum [21] and the
remarkable improvements reported by Young and Kersten when ultrasonic radiation was applied to
electrodeposition [22].

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 Some 20 years later Yeager reviewed these effects in a general survey of the applications of ultrasonic
waves in electrochemistry which were discussed in terms of (1) the effects of ultrasonic waves on electrode
processes (2) electrokinetic phenomena involving ultrasonic waves and (3) ultrasonic waves as a tool in the
study of the structure of electrolytic solutions [23]. In the same decade Rich published a paper which has
proved to be quite fundamental in subsequent studies leading to modern ultrasonically assisted plating [24].
Electrochemistry itself is a very broad subject and applications exist in most fields [25]. One aspect that
seems to be attracting increasing interest is the use of sonoelectrochemistry for the synthesis of nanoparticles
[26].

Environmental Protection

Biological
The biological effects of “supersound” were first reported by Wood and Loomis in 1927 who identified two
contrasting effects a stimulation or a lethal effects on unicellular organisms, tissues, small fish, and animals
[27]. Two years later Harvey and Loomis examined the reduction in light emission (a factor related to bacterial
kill) from a seawater suspension of rod shaped Bacillus Fisheri caused by sonication at 375kHz and 19 oC [28].
The final sentence of the paper predicted a poor future for the commercial exploitation of sonication (which
they referred to as “raying”) and this read: “In conclusion we can state that, under proper conditions of raying,
luminous bacteria can be broken up and killed by sound waves of approximately 400,000 cycles per second and
the solutions sterilized, but the method is not one of any practical or commercial importance because of the
expense of the process”. At the time this was written the conclusion was probably valid in that ultrasonic
equipment was specialist, large and expensive. Today that situation has changed, ultrasonic technology is more
commonplace, capital costs have been reduced and applications are more economic. In the following year
Harvey went on to suggest that the biological effects of these sound waves may be grouped in five
categories [29]:
(1) Whirling of the protoplasm.
(2) Displacement of small particles.
(3) Cytolysis of cells.
(4) Disintegration (emulsification?) of small bodies like chloroplasts.
(5) Stimulation of cells.
Ultrasound has certainly been found to be effective in removing microbiological contamination although it
would seem to be mainly applied in conjunction with other techniques e.g. chemical biocides, ozone, uv light
etc [30]. It has also been used for the treatment of algae contamination, particularly the harmful blue-green
type [31].

Chemical
The basis for the use of ultrasound to remove chemical contamination dates back almost as far as
investigations into the biological effects. In 1929 cavitation was found to induce oxidation when iodine was
liberated during sonication of aqueous potassium iodide [32]. The oxidation was thought to arise from the
formation of hydrogen peroxide and in 1964 Anbar and Pecht investigated the location of the sonochemical
formation of hydrogen peroxide and found that H2O2 was produced in cavitation bubbles and not in the liquid
phase [33].
It was in more recent years that the oxidation was found to be routed in the generation of the highly
oxidizing HO. free radical which was neatly demonstrated in 1994 in a study of the oxidative degradation of
phenol in water at 514kHz [34]. This report was significant in that it showed not only the complete destruction
of phenol in water but also the production of intermediate hydroxylated benzenes e.g. catechol which
themselves were further oxidized.
There is an active interest in the use of sonochemical methods in the presence of catalysts and chemical
additives for treatment of organic pollutants in wastewater [35]

Food Technology

The use of ultrasound to modify the properties of proteins is of considerable current interest in food
technology. It can be traced back to 1931 when solutions of egg albumin were exposed to sonication and

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became turbid as the albumin is precipitated out in fine shreds. The mechanism of this ultrasonic method of
protein coagulation was one of the first to be investigated [36].
One of the oldest applications of ultrasound in food processing is emulsification. For food processing the
development of the “Pohlmann whistle” or jet edge transducer proved to be an important new technology for
efficient emulsification [37]. It showed how hydrodynamic cavitation in liquids could be used for industrial
purposes. In 1960 a series of experiments was undertaken to compare four methods then in common usage for
the emulsification of mineral oil, peanut oil and safflower oil [38]. The results proved that a homogeniser,
which operated via a liquid whistle, was superior to three other types of apparatus, namely a colloidal mill and
two types of sonicator, one of which employed a quartz crystal and the other a barium titanate transducer.
Improvements in food preservation by drying and freezing using ultrasound has been the subject of
considerable research. Its use in freezing has two benefits (a) through a reduction in the ”dwell time” incurred
while the material remains at a steady low temperature while the whole mass freezes before the temperature
reduces further (due to latent heat considerations) and (b) a reduction in ice crystal size due to ultrasonic
seeding of crystallisation, a benefit when freezing soft fruit since smaller crystals rdeuce the problems of cell
wall damage. A patent was secured for ultrasonic freezing [39]. Some years earlier in 1959 ultrasound had been
investigated in terms of defrosting although at that time it was not found to be very efficient [40]. The origins of
ultrasonically assisted drying was suggested in the same year [41].
Current applications span a range of food technologies and provide many advantages over conventional
methods including more effective mixing and micro-mixing, faster energy and mass transfer, selective
extraction and in some cases a reduction in the number of processing steps [42] [43].

Materials

One of the first applications of power ultrasound for materials processing is derived from early studies of
the effects of ultrasound on colloids. In 1938 Freundlich pioneered work involving the influence of ultrasound
in this field with particular reference to the lowering in viscosity and liquefaction of gels [44]. The work
included the efficient formation of emulsions which combined the mechanical effects of acoustic cavitation in
terms of the mechanisms of dispersion and coagulation. At around the same time early studies of the effects of
sonication on polymers in solution. Schmid carried out the first experiments on the ultrasonic degradation of
synthetic polymers which also led to a reduction in viscosity [45]. He found that the rate of depolymerisation
was proportional to the difference, between the existing degree of polymerization, and the final polymer size. In
a reviewof the ultrasonic degradation of polymers in solution, Basedow and Ebert suggested that the particular
interest in this type of degradation was that unlike all known chemical and thermal decomposition reactions,
ultrasonic depolymerization was a nonrandom process that produces fragments of definite molecular size [46].
Research into the effects of ultrasound on polymers did not only involve degradation. In an early study of
the exposure of pure substituted benzenes to ultrasound where cavitation occurred Diedrich reported the
formation of a tar like residue [47]. The products had some of the characteristics of the char obtained from low
temperature pyrolysis of hydrocarbons, they were difficult to dissolve, melt above 300 °C. Within this material
were polymeric compounds thought to arise through thermal decomposition of the benzenes in a cavitation
bubble. In 1987 Kruus who had been an author on this paper presented a review of his work in ultrasonically
initiated polymerisation [48].
With an increasing effort being made to use nanomaterials it is not perhaps surprising to find sonochemistry
as a method of choice for their production [49]. It is also interesting to note the ways it has been incorporated
into the synthesis of polymer nanocomposites [50].

CONCLUSIONS

The origins of sonochemistry were in synthesis but there are many applications developing outside of this
field. One of the remarkable attributes of sonochemistry is that to begin work in this field there is no need to
purchase expensive or specialised apparatus, indeed some impressive results have been obtained using nothing
more complicated than an ultrasonic cleaning bath. As a topic it incorporates not only chemistry but also
physics, biology and medicine and so can be used to illustrate the benefits of true interdisciplinary research.

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