Chemical Engineering and Processing 49 (2010) 885–900

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Review

Microwave and ultrasonic processing: Now a realistic option for industry

Cristina Leonelli a,∗ , Timothy J. Mason b
a
M.A.G. – Microwave Application Group Dipartimento di Ingegneria dei Materiali e dell’Ambiente, Università di Modena e Reggio Emilia, Via Vignolese 905, 41125 Modena, Italy
b
Sonochemistry Centre, Faculty of Health and Life Sciences, Coventry University, CV1 5FB, UK

a r t i c l e i n f o a b s t r a c t

Article history: Environmentally friendlier preparations of chemical compounds and organic or inorganic materials are
Received 5 February 2010 generally accompanied by the concept of saving resources by optimizing reaction conditions and/or
Received in revised form 1 May 2010 introducing new process technologies. The use of ionic liquids and a solvent-free approach are among
Accepted 23 May 2010
these technologies, but in terms of the minimisation of energy and optimization of reaction control both
Available online 4 June 2010
microwave and ultrasound irradiation have now proved to be real options. This review starts from the
basic considerations on the separate interaction of microwaves and ultrasound with matter and goes on
Keywords:
to explore some laboratory and industrial applications of each type of activation. It is also possible to
Ultrasound
Microwaves
enhance the effects of high frequency electromagnetic fields, typical of microwaves, or the cavitational
Sonochemistry energy associated with sonochemistry by combining them with other extreme conditions such as plas-
Dielectric heating mas, high pressure and UV. Finally the simultaneous use of microwaves and ultrasound in a single reactor
Processing is described. This novel mixing of technologies has been implemented in order to combine the effects of
Equipment enhanced energy with improved matter transportation.
Scale up © 2010 Elsevier B.V. All rights reserved.

Contents

1. Microwave chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 886

1.1. Introduction to microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 886
1.1.1. Dielectric heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 886
1.1.2. Peculiarities of microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 887
1.2. The scale up of microwave chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 887
1.2.1. Microwave applicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
1.2.2. Microwave and pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
1.2.3. Microwave and photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
1.2.4. Microwave and SHS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
1.2.5. Microwave and plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
1.2.6. Microwave and vacuum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
2. Sonochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 891
2.1. Introduction to sonochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 891
2.1.1. Ultrasound in synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
2.1.2. Ultrasound in electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
2.1.3. Ultrasound in environmental protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
2.1.4. Ultrasound in food technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
2.1.5. Ultrasound in material science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 892
2.1.6. Ultrasound in therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 893
2.2. The scale up of sonochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 894
2.2.1. Methods of measuring cavitation zones in a sonochemical reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 894
2.2.2. Large scale ultrasonic reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 895
2.2.3. Some recent examples of pilot and industrial applications of sonochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 896

∗ Corresponding author. Tel.: +39 059 205 6247; fax: +39 059 205 6243.
E-mail address: cristina.leonelli@unimore.it (C. Leonelli).

0255-2701/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2010.05.006
886 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900

3. Combining ultrasound and microwaves as a hybrid technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 897

4. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 899

1. Microwave chemistry Table 1

Dielectric constant (ε ), tangent loss (tan ı), and dielectric loss (␧  ) for commonly
used solvents at 2450 MHz and room temperature (after data from Ref. [4]).
1.1. Introduction to microwave heating
Solvent Dielectric Tangent loss Dielectric loss
constant (ε ) (tan ı) (ε  )
As many researchers have already stated in numerous pub-
lished papers [1,2] microwave irradiation (usually at the ISM – Water 80.4 9.889 0.123
Industrial Scientific and Medical – frequency of 2.45 GHz) produces DMSOa 45.0 0.825 37.125
DMFb 37.7 0.161 6.079
efficient internal heating for most chemical reactions, delivering
Ethylene glycol 37.0 1.35 49.950
energy exactly where it is needed, even under exothermic condi- Methanol 32.6 0.856 21.483
tions. Another valuable advantage of using controlled microwave Ethanol 24.3 0.941 22.866
dielectric heating for chemical synthesis is the dramatic reduction Chloroform 4.8 0.091 0.437
Toluene 2.4 0.040 0.096
in reaction times: from days and hours to minutes and seconds.
Hexane 1.9 0.020 0.038
These two properties are sufficient motivation to promote the use
a
of microwaves in “greener chemical processes” [3], but many others Dimethyl sulfoxide.
b
Dimethylformamide.
are listed in the following pages.

tan ı, which is the ratio between the dissipative (including electri-

1.1.1. Dielectric heating
cal conductivity losses) and capacitive behavior of the materials,
The interaction of an electric field with condensed matter is
according to the simplified equation below [8,9]:
most often considered in terms of a dielectric response. The usual
theories model the macroscopic properties of matter based on the ε
tanı = (3)
individual behavior of dipoles or charges in an electric field. Many ε
authors have contributed to the dielectric theories [see Ref [4] and The value of tan ı is then easily related to the capacity of the mate-
quotations therein]. A macroscopic and quantitative description of rials to be heated, the higher the better.
microwave-matter interactions is given through a consideration If we now consider some examples of applications in chemical
of the permittivity (accounting for electric losses) and perme- processes, chemists are reasonably familiar with the relative dielec-
ability (accounting for magnetic losses) of the materials under tric constants which is used to distinguish between polar and apolar
study, measured at the applied microwave frequency. An adequate solvents (Table 1).
description of the permittivity has been given for many systems In most cases the values reported in the literature for dielectric
including pure liquids, mixtures of liquids, emulsions, heteroge- constant refer to room temperature conditions and to a frequency
neous solids, crystals, and so on. The frequency and temperature of 1 kHz, while microwave high power heating is occurring at
dependence of the permittivity are known for these systems [5–7] 2.45 GHz. In fact since the beginning of the 1980s [10], it has
and the results agree well with theorical predictions. These con- become possible to produce high electric field strengths within the
siderations are however restricted to a spectroscopic view of the microwave domain of common microwave ovens at this frequency.
interaction: the strength of the electric field is always consid- Excitation with microwave radiation results in the molecules align-
ered to be small enough so that it does not cause any breakdown ing their dipoles within the external field, so most of the chemicals
phenomena. are heated at microwave frequency mainly by dielectric interac-
Microwaves are oscillating electromagnetic energy with fre- tions and rarely to magnetic ones. When reactions are carried out
quencies in the 300 MHz to 300 GHz range with the most effective in solvents with high tangent losses, the heating will be more rapid
range for dielectric heating between 0.915 and 2.45 GHz. Most of than when “non-absorbing” solvents are used (Fig. 1).
the interactions between microwaves and matter that are of chem- When microwaves are used to supply a large amount of energy
ical relevance are due to electric field-induced polarization and this will be proportional to the material’s dielectric and magnetic
re-orientation phenomena. The degree of conversion of electro- properties as well as the electric and magnetic fields intensities
magnetic energy into heat can be considered to be dependent in [8]. However it has to be taken into account that there are some
practical terms on the permittivity, ε*, which is a complex number, inconveniences such as the variation of dielectric properties with
i.e. having real and imaginary parts, as described by the Eq. (1):

ε∗ = ε + iε (1)

ε , the dielectric constant, represents the ability of a material to be

polarised by an external electric field and so it is a relative measure
of the microwave energy density. This is often expressed relative
to the permittivity of free space, ε0 , by Eq. (2) [8,9]:

ε = εr ε0 (2)

ε ,
the loss factor, quantifies the efficiency with which the electro-
magnetic energy is converted to heat [4]. Usually the losses due to
the induction of real currents, i.e. the contribution of the electri-
cal conductivity to heat generation, is included in the effective loss
Fig. 1. Heating curves of 4 different solvents: distilled water, ethanol, acetone and
factor. Sometimes a linear combination of dielectric constant and dioxane (from top to bottom) in a multi-mode cavity at 150 W microwave irradia-
loss factor is used to account for the losses, using the loss tangent, tion.
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 2. Loss tangent variations at 2.45 GHz, as a function of temperature for a glass
powder mixture undergoing drying (tan ı decreasing from room temperature to
100 ◦ C) and subsequent heating (tan ı increasing above the glass transition temper-
ature) [11].
temperature and changes in the chemistry of the system. (Fig. 2)
[11].
Moreover the modification of the dielectric properties that
occurs can affect the depth at which the power is dissipated, i.e.
the thickness of the layer being heated, the penetration depth.
Because of the dependences on the dielectric and magnetic
properties of the material being treated, microwave irradiation can
be described as selective, volumetric and localized. In the case of
a composite material, or a biphasic system for instance the pres-
ence of different permittivity values will induce a differential power
density, and thus temperature increase, for a given electromagnetic
field intensity in the material (Fig. 3) [12].
1.1.2. Peculiarities of microwave heating
The peculiarities of the microwave heating derive form the gen-
eration of the heat due to energy transfer during the interaction
between the electromagnetic radiation and chemical compounds.
Very often scientists have suggested so-called “non-thermal”
effects as responsible for improved kinetics or increased selectivity
in chemical reactions [2]. However discussion of this is far from the
aim of this paper, so readers are asked to consult more specialized
literature for more information on this.
However there are other aspects of microwave activation which
are sometimes neglected by chemists but are important for process
engineers when designing new MW reactors. These will be briefly
summarized and described with some recent examples.
Heating at the interface: In the case of interfaces such as sur-
face/gas or others that are often found in heterogeneous syntheses,
the temperature at the surface where sorption occurs is “effec-
tively” greater than the measured solid or gas temperature. In
Fig. 3. Features of the selective microwave heating due to different permittivity in a biphasic material (yellow to red indicate the heating of the phase with higher losses). On
the right: lossy matrix with low loss particles; on the right: lossy particles embedded in a low-loss matrix. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of the article.)
887
their studies, Vallee and Conner [13] reported of measurements
of the amounts of adsorption as functions of the partial pressures
of a specific adsorbate in the presence of microwave irradiation,
related to the conventional adsorption isotherms. It was found that
the effective surface temperature increased when using adsorbates
having a higher permittivity or when increasing the microwave
power.
Localised plasma: Along with the “microwave effect” observa-
tion at interfaces, there are also micro-discharges and localised
plasma that occur between metallic spheres or particles [14]. In
the presence of a sufficiently high electric field intensity, the shape
and distribution of conductive particles can lead to electric field
concentration in the dielectric (air, for instance), with electric field
values surpassing the dielectric strength of the interposed medium,
which favours breakdown phenomena. Fig. 4 shows the numeri-
cal simulation results of the electric field envelope in the case of
four micrometric metallic spheres initially spaced and separated
by air (left), then after necking (right), exposed to a planar wave
at 2.45 GHz, with a forward power of 300 W. It is evident that the
dielectric strength of air at atmospheric pressure is surpassed in
the space between the particles, where necking occurs.
Homogeneous crystal growth: In recent years researchers have
found that during hydrothermal and solvothermal treatments [15]
as well as in some gas phase preparations [16] is it possible
to produce particles with an extremely narrow size distribution.
Independent of the shape and the size of the particles produced,
microwave irradiation allows the solution or the reaction fluid
to heat up homogeneously (with a narrower temperature distri-
bution) thus allowing all the nuclei formed to grow at the same
heating rate (Fig. 5). This peculiarity of microwave heating is par-
ticularly interesting for powder drug preparation in the sense that
the dissolution rate of the powder can be designed dependent upon
the particle size.
1.2. The scale up of microwave chemistry
Since the beginning of the 80s [10], we have been involved in
the development of the industrial applications of MW heating in
activating physical or chemical reactions such as drying, defrosting,
food lyophilization, or devulcanization of rubber, i.e. endothermic
reactions.
Over the years many efficient industrial production plants can
be found in a number of industries including:
Food industry: For the tempering of large or small blocks of food
from −20 ◦ C to −2 ◦ C a very compact installation of 60 kW can be
888 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 4. Simulation results of electric field envelope before (left) and after (right) sintering of metallic powders. The color scale indicates the electric field density (V/m). The
maximum of 3106 V/m is the value of dielectric strength of air [13].
used often occupying a sixth of the space of conventional equip-
ment. Baking and cooking are carried out in systems that apply
microwaves to conventional fuel fired baking ovens, which com-
bines the advantages of traditional baking with the volumetric
and selective heating effect of microwave energy. The distinc-
tive flavour, colour and texture of the baking process is retained,
whilst the introduction of microwaves enables throughputs to be
increased and cracking can be eliminated. Pasteurization is also
possible in MW ovens where closed food packages can be safely
treated to appropriate temperature in a reduced time with respect
to conventional vapour process. A major application entails the
puffing or dry frying of snack foods, which are brought rapidly to
100 ◦ C and the subsequent boiling of the water produces steam
which causes the required expansion within about 10 s.
Rubber industry: MW used to heat blocks of rubber of up to
several hundred kilograms in weight replaces conventional vul-
canisation that uses hot air or salt baths which suffer from the
usual limitation of heating via thermal conduction. Better working
conditions also apply to personnel around the MW kiln.
Wood industry: In timber manufacturing the MW process creates
an evenly heated product with extremely consistent properties,
such as density and dimensions. The strength of the finished prod-
uct is higher than available from conventional wood-based building
materials. Wood paint drying is specially efficient using MW since
the residual water of the paint can be reduce to 2% so allowing an
optimum UV–vis polymerization with no undesired white spots.
Processing of wastes: A concerted effort has been made in a num-
ber of areas which includes the processing of automotive tyres,
treatment of hospital and municipal wastes, vitrification of nuclear
wastes, treatment of highly toxic substances, waste recovery of
plastics, heating of resins, polymerisation, heating of oil sands and
soil remediation. In the case of hospital waste sterilization a 50%
saving can be achieved in disposal costs.
Fig. 5. Scanning electron microscopy (left) and transmission electron microscopy images (right) of submicrometric and nanometric particles produced with microwave-
assisted hydrothermal methods [17,18].
General drying: Drying of parsnips, quick-cooking noodles, sea-
weeds, snack foods, fabrics, leather, ceramic cores and moulds and
ceramic wares can be easily reduced from hours to minutes when
MW are used in combination of hot air. Another example of a com-
bination system uses the combination of microwave and infra-red
energies to dry/roast green tea with the added advantage of stop-
ping discolouration during storing.
The advantages of microwave heating over conventional sys-
tems are:
- Rapid energy transfer
- Volumetric and selective heating
- Uniformity of heating
- Faster throughputs
- Fast on and off switching
- Compact equipment
- Clean environment at the point of use
- Very high power densities developed in the processing zone
- Superior moisture levelling
In the field of fine chemical processes MW heating has been
used over the last 10 years for extraction and synthetic organic
chemistry, and also for inorganic synthesis to a smaller extent. In
terms of process intensification approach MW are very useful to
efficiently deliver energy into the reaction vessel once the following
requirement have been dealt with:
1. homogenization of the electric field profile, either by mode stir-
rers or by rotation of the reaction vessel itself;
2. optimum design of reactor geometry taking into account the
penetration depth of the microwaves as described in Section
1.1.1;
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 6. Picture of a multi-mode applicator (top left), single mode applicator (top right), radiant plate (bottom left) and slotted waveguide (bottom right).
3. temperature and pressure control within the reaction chamber
for continuous monitoring of process parameters;
4. cost of reactor and spare parts;
5. safety issue and MW leakage.
The continuous flow reactor seems to positively answer require-
ments 1, 2 and partially 5, while most of the devices have rapid
temperature measurement devices. Working with the frequency
ISM of 2.45 GHz drastically reduces the cost, point 4, even though
allowing. The issue of MW leakage and safety is really important
in continuous flow reactors where the fluid in the reactor could be
responsible of taking microwave radiation outside the vessel for
some distance [8].
More recently microwaves have been successfully applied to
high energy chemical environments with a proliferation of reactor
geometry some aspects of which are illustrated below.
1.2.1. Microwave applicators
It order to better evaluate the most recent developments in
chemical reactors adapted to microwave heating we are now
describing the most simple geometries.
Magnetron are the most commonly used microwave sources,
they are connected with transmission lines (waveguides, coaxial
cables,. . .) to the cavity for single mode and multi-mode applica-
tors, while for radiant geometry also antennas can be used [as a
reference text see Ref. [3]]. Fig. 6 illustrates the most commonly
used commercial geometries. The choice of the best applicator,
where to locate the materials to be heated depends upon many
different factors. Domestic ovens that are the most used laboratory
kilns belong to the multi-mode applicators type. The advantages
of these applicators are: ease of construction, the possibility to
homogenise the electromagnetic field with rotating devices (mov-
ing the load or perturbing the electromagnetic filed with mode
stirrers), large dimensions, the possibility of installing multiple
microwave inlet ports, and finally they are relatively cheap. Some
of the drawbacks are undoubtedly the absence of an analytical solu-
889
tion of the Maxwell equations describing the electromagnetic field
in the case of partially loaded applicators and the need for thermal
insulation over large areas.
The single mode applicators advantages when compared to the
multi-mode applicators, include the availability of analytical solu-
tions, more easy to design, and a relatively simple construction;
moreover they can present higher electromagnetic field homo-
geneity in precise zones of the applicator. Some drawbacks are the
small dimensions, the ease with which arcing and plasma are gen-
erated, as a consequence of high field density and finally the high
cost per load volume.
There is also a large number of radiant structures which can
operate with very different output power, depending on the final
application. Their advantages are a good heating homogeneity,
large dimensions, open termination and the fact that they are
less affected by load variations with respect to closed applica-
tors. The drawbacks are the difficulties in design and in preventing
microwave leakage.
1.2.2. Microwave and pressure
When pressurised reaction vessels are transparent to
microwaves, the volumetric dielectric heating of the reac-
tants can be extremely rapid (few minutes) (Fig. 7) [15]. Usually
these applicators involve pressures from 2–3 to 8–10 MPa and
temperatures from 150 to 250 ◦ C. They are used for hydrothermal
and solvothermal preparation, staining, sterilization and so on.
The combination of microwave and vapour pressure have been
already applied successfully to polymers-composite reticulation in
huge (7500 l) multi-mode cavities (Fig. 8) [21].
1.2.3. Microwave and photochemistry
The possibility to light up a gas lamp by microwave irra-
diation within a microwave photocatalytic reactor was proved
around the year 2000 and used to promote photochemical organic
reactions [22]. Recent papers have demonstrated outstanding
improvement of the degradative efficiency by coupling of the
890 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900

Fig. 7. On the right the superfast microwave reactor, RAMO (Réacteur Autoclave Micro-Onde), designed by the group of Prof. D. Stuerga at Nanosciences-GERM (Groupe
d’Etudes et de Recherches en Microondes), UMR 5209 CNRS, Université de Bourgogne, Dijon, France (multicolor candy represents the position of the solution) [19]. On the
left the sketch of autoclave developed by milestone, Bergamo, Italy, featuring a stainless steel reactor with a volume of 4.2 l and the inner PTFE liner with a volume of 3.5 l at
a maximum pressure of 20 MPa at 280 ◦ C. [20].

propagating high-temperature synthesis (SHS) in which a reactant

compact is typically ignited at one end, and thermal explosion,
in which the whole volume of the compact is heated to ignition
temperature. Thus these syntheses usually present an inversion of
the heat flow, which, before the synthesis occurs, is directed from
the external environment to the reacting products, and during and
after synthesis is directed from the reactants, towards the external
environment, due to the pronounced exothermicity of the reaction.
Microwave heating has been used for years at a laboratory scale to
start RS or SHS, providing a rapid, volumetric and energy efficient
ignition of loose or compacted metal powders [24].

1.2.5. Microwave and plasma

Fig. 8. HEPHAISTOS system developed by the group of Dr. L. Feher at the HEC Exper-
imental Center, Institut für Hochleistungsimpuls und Mikrowellentechnik–IHM
Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany [21].
microwave (MW) radiation with electrodeless discharge lamps for
the photocatalytic degradation of various compounds (Rhodamine
B, brilliant red X-3B, methylene blue, 4-chlorophenol, and 2,4-
dichlorophenoxyacetic acid) [23].
1.2.4. Microwave and SHS
Combustion synthesis (CS) or reaction synthesis (RS) is a process
which uses the exothermic reaction of starting compounds, prop-
erly ignited to spontaneously transform into products. Depending
on the mode of ignition, the process can be subdivided into self-
Microwave induced plasmas present some important benefits,
such as the high efficiency in generating chemically active species,
relatively high electron density, fast and nearly contamination-
free processes and the capability of operating over a wide pressure
range [25]. One of the main drawbacks of this technique, however,
is the need of a proper matching to compensate the impedance
variations of the load seen by the microwave generator, induced
by small changes in the plasma characteristics. Applications are in
the field of thick film preparation, even 3D geometry (Fig. 9) [26],
ablation, and exhaust gas combustion.
1.2.6. Microwave and vacuum
One of the most diffused applications of microwave heating
under vacuum is for drying food or pharmaceutical slurries at very
low temperatures. For these kinds of products there is the require-

Fig. 9. (a) Plasma source; (b) normalised E-field distribution; (c) power density in the plasma after [26].
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 10. Batch chemical reactor for vacuum drying of pharmaceutical compounds
[27].
ment to maintain the whole batch at a temperature low enough
to avoid deterioration. Compared to other equipment, dedicated to
drying only, filter dryers are very efficient in term of water/solvent
evaporation or extraction, but require long drying time. Tentative
studies have been done to couple filter dryers with fast microwave
heating, and compact equipment has been developed capable of
standing from full vacuum to 1.03 MPa, and from 30 to 200 ◦ C [27]
(Fig. 10).
2. Sonochemistry
2.1. Introduction to sonochemistry
We normally associate sound with communication and music
but seldom think of it as an energy source. It is therefore some-
thing of a surprise to find that sound can be used to sterilize
water, improve electroplating, produce better face creams, treat
cancer and much more. These remarkable effects come from the
energy released by cavitation bubbles generated in a liquid by
sound waves. These acoustic cavitation bubbles are very different
and much more energetic than soap bubbles blown by children or
the bubbles fizzing in a glass of champagne. Sonochemistry is based
upon harnessing the energy of such bubbles to create changes in
a medium and is generally associated with the use of ultrasonic
sound frequencies.
Ultrasound is most simply defined as sound with a frequency
that is too high for the human ear to detect and this is generally
considered to be above 20 kHz (20,000 Hz, Hertz = cycle per second).
The ultrasound frequency range can then be divided into two parts
(Fig. 11):
Power ultrasound which is capable of influencing chemistry and
processing and is mainly in the frequency range between 20 and
100 kHz.
Fig. 11. General classification of sound frequencies.
891
Fig. 12. Formation and collapse of an acoustic cavitation bubble.
Diagnostic ultrasound which does not have enough power to pro-
duce cavitation, is at very high frequencies (above 5 MHz) and is
used in for example in foetal scanning.
The potential of using acoustic cavitation to create changes in
materials was identified in the USA in the late 1920s [28–30].
Over the succeeding years after a great deal of pioneering work
in sonochemistry, two reviews on the applications of ultrasound
in polymer and chemical processing were published in the 1940s
[31,32]. Yet there are very few references to ultrasound in chem-
istry from about 1955 to 1970 when a major renaissance in the
subject began to occur which then accelerated. This revival of
interest is undoubtedly due to the more general availability of com-
mercial ultrasonic equipment. In the 1960s the ultrasonic cleaning
bath began to make its appearance in metallurgy and chemical lab-
oratories and in this period biology and biochemistry laboratories
also began using ultrasonic cell disruptors on a regular basis. The
next major reviews came some 40 years later [33,34] and now there
are many publications and texts on a wide variety of applications
[35–37].
Cavitation bubbles are generated by the ultrasound wave as it
passes through the liquid. Like any sound wave it is transmitted as a
series of compression and rarefaction cycles affecting the molecules
of the liquid. When the negative pressure of the rarefaction cycle
exceeds the attractive forces between the molecules of the liquid
a void is formed. This void or cavity in the structure takes in a
small amount of vapour from the solution so that on compression
it does not totally collapse but instead continues to grow in size in
successive cycles to form an acoustic cavitation bubble. There are
many thousands of such bubbles in the liquid some of which are
relatively stable but others expand further to an unstable size and
undergo violent collapse to generate temperatures of about 5000 K
and pressures of the order of 2000 atm (Fig. 12).
These tiny hotspots provide the energy for some remarkable
chemical and mechanical effects. If the bubble collapses close to
or on a solid surface the collapse is not symmetrical and results
in a microjet of liquid being directed towards the surface of the
material at speeds of up to 200 m/s. These jets are of course the
underlying reason why ultrasonic cleaning baths are so effective in
surface cleaning.
The current major areas for sonochemistry research and devel-
opment include:
• Synthesis
• Electrochemistry
• Environmental protection
• Food technology
• Materials
• Therapy
892 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
2.1.1. Ultrasound in synthesis
Even from the early days of sonochemistry it was clear that
acoustic cavitation would provide faster and cleaner syntheses and
that this linked well with what was then an emerging interest in
so-called “Green Chemistry”. If we look at the following objectives
that were set out for sonochemical synthesis and compare them
with those for green chemistry then the similarity becomes clear
and sonochemistry can certainly be looked upon as potentially a
major contributor to green science [38,39]:
• The use of less hazardous chemicals and environmentally friendly
solvents.
• Developing reaction conditions to increase the selectivity for the
product.
• Minimizing the energy consumption for chemical transforma-
tions.
• The use of alternative or renewable feedstocks e.g. biomaterials.
The future contribution of sonochemistry to green and sus-
tainable science is dependent upon the possibility of scaling up
excellent laboratory results for industrial use. There are currently
several systems commercially available with configurations to suit
most applications and these will be discussed later.
2.1.2. Ultrasound in electrochemistry
There are many aspects of sonochemistry which recommend
its use in conjunction with electrochemical processes. The benefits
include:
• continuous cleaning and activation of the electrode surfaces
• degassing which limits gas bubble accumulation on the electrode
surface
• agitation (via cavitation) which disturbs and reduces the thick-
ness of the diffusion layer
• agitation which also stops the depletion of electroactive species
in the immediate vicinity of the electrode.
The benefits of sonoelectrochemistry have been reported for
a number of processes including electrosynthesis, electroanalysis,
bioelectrochemistry, synthesis of conducting polymers, electro-
plating, nanomaterial preparation and electrocatalysis [40,41].
There is particular interest in the applications of ultrasound
in electrochemistry to make such processes more environmental
friendly such as the minimisation of waste and the replacement
of toxic components including mercury electrodes and chemi-
cal additives. Sonoelectrochemistry can also be used for pollutant
degradation and remediation, and to provide more efficient sensors
for the detection of various species in water and in the atmosphere.
2.1.3. Ultrasound in environmental protection
In water treatment, the destruction/transformation of organic
compounds is the prime objective of fundamental and applied
investigations involving ultrasound. The degradation of chemical
pollutants is possible through the effects of acoustic cavitation [42].
The reaction rate is a function of the physico-chemical properties
of the target compounds. Volatile and hydrophobic pollutants are
degraded by thermal reactions in the “hot spot” of the cavitation
bubble. Compounds which are more hydrophilic are decomposed
in the bulk liquid by hydroxyl radicals produced in the cavitation
bubble. Depending on the pollutants to be eliminated, the com-
bination of Advanced Oxidation Processes such as ozonation with
ultrasound or an integrated ultrasonic/biological treatment can sig-
nificantly improve process efficiency and economy.
In sewage sludge treatment, ultrasound is applied as a pre-
treatment to improve anaerobic sludge stabilisation. The high shear
forces created in the advent of cavitation can be used to improve
process efficiency in sludge dewatering and to achieve sludge disin-
tegration. Due to the ultrasonic disruption of putrescible biomass in
the sludge, subsequent microbial degradation occurs up to 4 times
faster than in the conventional treatment.
The violent collapse of cavitation bubbles in water produces
shear forces that can disrupt cell membranes and kill bacteria
[43]. At lower acoustic intensities these forces weaken the mem-
branes rendering the bacteria more susceptible to the effect of
biocides. The hydroxyl radical produced during cavitation can also
assist disinfection. Sonochemistry also has applications in chemical
decontamination and in particular as an adjunct to Advanced Oxi-
dation Processes (AOP) such as ultraviolet radiation or ozonation.
2.1.4. Ultrasound in food technology
Long standing applications of ultrasound in the food industry
can be divided into two categories; low power ultrasound at high
frequencies (in the MHz range) for non-destructive testing and high
power ultrasound at low frequencies (in the 20–40 kHz range) for
cutting and processing [44,45]. Applications of the latter in food
processing are broad and amongst these are to be found ultrasonic
improvements in:
• Cooking and frying: improved heat transfer gives shorter cooking
times and more even cooking.
• Cutting: can be achieved rapidly with reduced pressure using
ultrasonic vibrations on the edge of a cutting tool. The method
can be used for frozen or soft foods.
• Dispersal, mixing and homogenization: turbulent mixing is a fea-
ture of cavitation at liquid/liquid interfaces and can be used for
many years in the production of sauces and mayonnaise.
• Brining, pickling and marination: involving the penetration of liq-
uids into food material that can be applied to both vegetable and
meat products.
• Drying and filtration: air drying benefits from improved heat
transfer and ultrasound has applications in filtration because it
improves water flow through the filter cake.
• Tenderising meat: this is normally achieved by pounding and
ultrasound provides a mechanical vibration that can achieve sim-
ilar results with less drastic mechanical damage.
• Extraction: the break down of cell walls in plants together with
improved solvent penetration results in better and sometimes
more targeted extract yields of flavourings and nutriceuticals
from plants, herbs and seeds.
• Freezing and crystallization: can be improved through cavitation
initiating crystallisation without seeding and also providing effi-
cient heat transfer.
• Sterilization and pasteurization: conventional pasteurization and
sterilization involves heating but this can result in nutrient loss
and the development of undesirable flavours. Sonication reduces
these problems by using lower temperatures and accelerating the
process.
• Degassing and defoaming: is an important process for beverages
before they are canned or bottled.
Nowadays, when minimal processing is a driver for food prepa-
ration, power ultrasound can provide useful possibilities for the
food technologist. It has several positive aspects which can provide
a range of applications in processing as above but perhaps more
significantly it can provide concurrent combinations that include
mixing with sterilization, controlled crystallisation with improved
heat transfer and many more.
2.1.5. Ultrasound in material science
There are many areas of materials science where ultrasound has
been employed. Among the most general applications are:
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900 893

Fig. 13. (a) Printed circuit board; (b) circuit board substrate as supplied; (c) circuit board substrate after ultrasonic treatment.

Preparation and modification of nanoparticles: There are many
features of power ultrasound that make its use effective and dif-
ferent from other methods for the fabrication of nanomaterials
[46]. These include: (a) The ability to produce the nanomateri-
als in the amorphous state which is due to the very high cooling
rates (>1011 K/s) obtained in the collapsing cavitation bubble during
sonochemistry. The amorphous nature of the products is of impor-
tance in fields like catalysis, magnetism, coatings and others. (b)
Sonication generally results in shorter reaction times. (c) The shock
waves and microjets which follow the collapse of a bubble near a
solid surface is unique to sonochemistry, and is of great impor-
tance for the insertion and coating processes. These forces can be
used for the insertion of nanoparticles into the pores of mesoporous
materials MSPM. The nanoparticles form a homogeneous mono-
layer on the inner walls of the MSPM and do not block the pores.
The same effect is responsible for the formation of a smooth coating
monolayer of nanoparticles on ceramic or polymeric surfaces.
Surface modification of materials used in electronics manufactur-
ing: To ensure effective adhesion of a coating to its substrate it
is essential to form strong physical and chemical bonds between
them. To achieve this, the substrate is often roughened or tex-
tured in a process frequently referred to as surface modification.
One major user of surface modification is the electronics indus-
try where conducting metal tracks need to be laid down on epoxy,
plastic and ceramic substrates to produce printed circuit boards or
Wi-Fi aerials. Traditional manufacturing techniques for such sur-
face modification often use hazardous chemicals e.g. hot alkaline
permanganate for polymer composites and hydrofluoric acid for
ceramics. We are exploring the use of power ultrasound and water
with no added chemicals to produce similar surface modifications
(Fig. 13) [47,48].
Sonochemical surface modification also helps in the encap-
sulation of polymer beads (mean diameter 0.6 mm) with copper
particles (see Fig. 14). Metal coated beads of this type are under
investigation to improve the performance of solder joints used to
attach chip carriers to printed circuit boards.
2.1.6. Ultrasound in therapy
The use of high frequency ultrasound (around 5 MHz) in med-
ical imaging is a routine part of antenatal medicine to obtain an

Fig. 14. Polymer beads coated with copper in the absence and presence of ultrasound.
894 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900

Fig. 15. High-Intensity Focused Ultrasound equipment currently used for the treat-
ment of cancer (photograph courtesy of Chongqing HAIFU, P.R. China).

ultrasonic scan of the foetus in the womb. Such “diagnostic” ultra-

sound uses a refined pulse echo technique based upon the fact that
sound waves are reflected to varying degrees from the interfaces
between different tissue, blood and bone in the body. The reflec-
tions are processed to give a visual image and the energies involved
are so low that the ultrasound can have no effect on the tissues
themselves.
At lower ultrasonic frequencies energy inputs can be increased
to a level where chemical effects become possible and this has given
rise to a new field of medicine called therapeutic ultrasound [49,50].
There are a number of active research areas in this domain some of
which are being developed into clinical practise including:

• Sono-Dynamic Therapy (SDT): Some chemicals e.g. porphyrins

give out free radicals on treatment with light and so cancers
which absorb the chemical can be treated with light to activate
them (Photo Dynamic Therapy, PDT). Ultrasound can do a similar
job with the advantage that ultrasound can penetrate the body
and so reach tumours without the need for them to be exposed
directly to light (SDT).
• Transdermal drug delivery: Physiotherapists use ultrasound at fre-
quencies of between 1 and 3 MHz to treat muscle injury because
applying ultrasound to the skin surface provides a localised heat-
ing/massage effect to the injury site. However the accompanying
vibration also causes a temporary weakening of the skin bar-
rier and this permits the administration of drugs not normally
permeable through the skin layer.
• High-Intensity Focused Ultrasound (HIFU): The use of a focused
array of transducers for use in cancer therapy has been under
investigation for many years. The array is constructed to produce
an accurately targeted focus on the cancerous tissue within the
body. The focus is small so the system is designed to give sequen-
tial pulses during a traverse of the tumour thus treating larger
volumes. Clinical trials are well advanced in the use of HIFU for
the treatment of patients with liver and other soft tissue cancers
(Fig. 15).
2.2. The scale up of sonochemistry
Since the 1960s when the industrial uses of power ultrasound
were mainly in cleaning and plastic welding a much wider range
of activities involving the uses of ultrasound have evolved (see
above).
One extremely important aspect for the development of any of
these fields is that laboratory scale experiments must be able to be
up-scaled for industry and this is an aspect of sonochemistry that
has been of interest for many years [51–53]. Ideally this requires an
understanding of the appropriate design parameters for an ultra-
sound reactor and some of these are still under development.
Several models are available from the very fundamental involving
Fig. 16. Perforation of foil as a result of immersion in an ultrasonic cleaning bath.
cavitation bubble dynamics and its chemical effects through rad-
ical formation, to more empirical ways of trying to reproduce the
same acoustic pressure field on larger scale. Convenient measure-
ment and modelling of the pressure and cavitation bubble fields
are the central problem. Complete models are extremely complex
due to the fact that high acoustic intensities generate cavitation and
thus oscillating bubbles. Such bubbles will modify pressure wave
propagation through the sonicated fluid and also cause damping.
With a heterogeneous system, e.g. one involving suspended solid
particles, the acoustic field is even more complex. Despite these dif-
ficulties a number of larger scale sonochemical reactors have been
developed.
2.2.1. Methods of measuring cavitation zones in a sonochemical
reactor
One of the first methods that was used to locate active zones in
an ultrasonic cleaning bath, probably the simplest form of reactor,
was by placing aluminium foil in the cavitating liquid and observing
the degree of perforation (Fig. 16) This is still a quick and easy way
to determine whether a cavitating system is operating efficiently
but is not very quantitative [36,54].
In many publications the routine and established method of
assessing acoustic power input to a reaction medium is by calorime-
try i.e. the estimation of the initial heating effect of acoustic
cavitation which can then be converted to intensity (e.g. W/cm3 ).
Ideally this should be carried out in an insulated container to avoid
losses to the environment but it has been adapted for use in reg-
ular laboratory systems. This is a measure of overall heat energy
dissipated by sonication but does not take into account any of the
chemical effects that occur as a result of free radical production
on collapse of the cavitation bubbles [55]. For this type of dosime-
try the liberation of iodine by oxidation of iodide ion is often used
[56].
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 17. Bubble flare from a transducer (photograph courtesy of Robert Mettin).
An alternative method is based on the chemiluminescence of
luminol (which reacts specifically with OH radicals to emit a blue
light) and is applied to visualize the zones where the sonochemical
reactions are the most active. The spatial distribution of the light
intensity emitted by these reactions can be measured inside the
reactor with an optical fibre fitted on a photomultiplier. To deter-
mine the relative ultrasonic energy distribution, the temperature
is measured at different points of the reactor with a thermocouple
probe embedded in an absorbing material. The zones where the
energy density is the highest were shown not to correspond with
those where chemiluminescence reactions are the most efficient
[57].
With the advent of high speed photography and advanced math-
ematical modelling there has been significant progress in the study
of acoustic cavitation fields. Several different cavitation bubble
cloud structures in the low frequency ultrasound range (20–50 kHz)
have been investigated and summarized by Mettin [58]. In standing
wave fields these include patterns categorised as streamers, fila-
ments, bows, rings, jellyfish and starfish whilst in travelling wave
fields there are conical and flare type structures (Fig. 17).
2.2.2. Large scale ultrasonic reactors
Large scale processing using power ultrasound is not a new con-
cept and the industrial uses of power ultrasound were recognized
some 50 years ago [59]. There are many examples in the litera-
ture which show early examples of the implementation of large
scale power ultrasonics, for example a series of papers appeared in
the journal Ultrasonics back in the 1970s, entitled ‘Macrosonics in
Industry’ [60]. Progress over the last few years has been more rapid
[61–63]. This is probably for two reasons: firstly the greater general
awareness of the possibilities for ultrasonic processing, and sec-
ondly the ever-widening span of applications which has attracted
the attention and investment of more companies.
There are two types of ultrasonic processing for liquid systems
either batch or flow. The former is appropriate where lower power
treatment is required but for high power sonication it is necessary
to use a flow system through an intense sonication zone. An exam-
ple of a batch industrial ultrasonic reactor was designed and built
in Romania for the extraction and preparation of tinctures from
various herbs (Fig. 18) [64]. Using this reactor the solvent extrac-
tion time of medicinal compounds from various plant sources could
be shortened from 28 days to around 10 h with similar or better
outputs.
There are a number of examples of flow reactors that are com-
mercially available on the market and four of these are shown
in Fig. 19. Each has a different configuration to illustrate a vari-
ety of approaches. Ideally an ultrasonic flow processor should
be a module with the potential to be retrofitted into existing
pipework in the plant. This is particularly important in fine chem-
ical/pharmaceutical production but will also be significant in
materials processing and waste water treatment.
The Prosonitron P500 system developed by Prosonix
(http://www.prosonix.co.uk/) (Fig. 19(a)) uses piezoelectric trans-
ducers attached to the outside surface of a metal tube through
895
Fig. 18. Ultrasonic 1000 l batch extractor (courtesy of Plafar Company, Romania).
which the process liquid flows. The system has the advantage that
the tube itself resonates thus delivering sound energy towards
a focus in the centre of the flow. It has been used in commercial
crystallisation processes (see below). A different approach is the
Nearfield Acoustic Processor or NAP reactor made by Advanced
Sonic Processing Systems (http://www.advancedsonics.com/). It is
produced in variety of sizes but the system as shown (Fig. 19(b))
is a typical configuration and consists of two parallel vertical
plates through which the fluid to be processed is pumped (from
the bottom). It uses magnetostrictive transducers with each plate
operating at different frequencies (20 and 16 kHz) to produce high
cavitational activity in the fluid flowing through. The gap between
the plates can be adjusted. There are many applications for such a
system one of which is in the removal of chemical contaminants
from water [65]. Hielscher have produced what they claim to be
currently the most powerful ultrasonic processor in the world
the UIP16000 operating at 16,000 W (http://www.hielscher.com/).
This can be made part of a flow system (Fig. 19(c)). It is designed to
work in clusters of three or more units, for large volume processing,
such as to homogenization, dispersion and deagglomeration at up
to 50 m3 /h.
Power ultrasound has been found to improve the digestion of
sewage sludge. This is because it can break down biological cells
and cell lysis is known to be the rate-limiting step of anaero-
bic biosolids degradation. Two examples of systems developed
for sludge processing are shown in Fig. 19(d) and (e). The for-
mer is the V5 Reactor from Enpure (http://www.enpure.co.uk/)
and employs 5 horns in shape of discs inserted into a tube. The
reactor is driven by a 3 kW generator operating at 20 kHz [66].
The latter employs standard 20 kHz horns inserted into the mate-
rial flow (http://www.ultrawaves.eu/ultrawaves/home.htm) [67].
In both cases these have been developed for continuous operation
under real life conditions on sewage treatment plants.
896 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 19. Ultrasonic flow treatment modules: (a) prosonitron from Prosonix, UK; (b) Nearfield Acoustic Processor (NAP reactor) from Advanced Sonic Processing Systems,
USA; (c) UIP16000 from Hielscher, Germany; (d) V5 reactor from Enpure (UK); (e)sludge disruptor from Ultrawaves, Germany.
2.2.3. Some recent examples of pilot and industrial applications
of sonochemistry
Simultaneous generation and coating of fabric with nanoparti-
cles: Laboratory studies have reported that the deposition of some
metal nanoparticles onto fabrics to give them excellent antibacte-
rial properties (Fig. 20) [68]. The design of sonochemical devices for
the scale up of such processes could provide bandages and hospi-
tal clothing for the future. An instrument has been developed that
will simultaneously generate antibacterial nanoparticles and drive
them into a fabric fed through a gap between two flat ultrason-
ically vibrating plates [69]. This work demonstrated for the first
time the potential for the scale up of a sonochemical system for the
production of biocidal cotton bandages coated with metal oxide
nanoparticles. Cotton bandages containing 0.65 and 1.50 wt% CuO
demonstrated activity for killing E. coli microorganisms.
Fig. 20. Pilot scale system for the ultrasonic impregnation of nanoparticles in fabric.
Ultrasonic crystallisation: The application of power ultrasound
to the crystallization of organic molecules has been the subject
of research for many years but has now become a real option for
industry [70]. New equipment has been developed and the field
has widened to well beyond initial ideas of inducing crystallisation
without seeds and controlling crystal size.
Drug delivery by inhalation offers significant potential for
administering drugs and avoiding injection. Pharmaceuticals for
drug inhalation are traditionally manufactured by very primitive
pharmaceutical technologies such as micronisation, a destructive
and energy inefficient technique to turn large, regular crystals into
irregular 1–5 ␮m. Such particles can also be highly charged, which
affects the flow-rates essential for aerosolised and dry powder
inhalers. A new type of application of ultrasound in crystallization
has been put into place to achieve some remarkable morphology
changes in drug powders. Termed Solution Atomisation and Crys-
tallization by Sonication (SAXTM ) (Fig. 21(a)) it has been applied to
the production of corticosteroids, including Budesonide a synthetic
anti-inflammatory drug administered by inhalation [71]. It is used
for the treatment of asthma and hay fever amongst a range of other
conditions.
The more industrially oriented development of SAX, named
Ultrasound Mediated Amorphous to Crystalline transition
(UMAX® ), incorporating spray drying and ultrasonication is
now used to manufacture a wide range of drug materials for
asthma and chronic obstructive pulmonary disease (COPD) [72].
The normal synthetic drug powder (Fig. 21(b)) when micronized
(Fig. 21(c)) is suitable for use in inhaler but it has a slight problem
in that the powder can agglommerate and the shape is not ideal.
Through the UMAX process the powder has a different morphology
and is much better for use in an inhaler (Fig. 21(d)).
Stimulation of oil well production: The oil industry is forever
searching for more effective ways of getting crude oil from the
bottom of wells. Sometimes the oil itself is very heavy and dif-
ficult to pump or the well begins to slow output as the well
bottom becomes blocked. A traditional solution to the latter is
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 21. Ultrasonic crystallisation (courtesy of Prosonix, UK): (a) schematic SAX process; (b) cortecosteroid prepared normally; (c) cortecosteroid prepared normally then
micronised; (d) cortecosteroid prepared by the UMAX system.
to set off a small explosive device at the well bottom to break
apart the substrata and release the blockage but this is a costly
solution in terms of down-time and therefore loss of produc-
tion. A solution to this is to use high power ultrasound at the oil
well bottom through a device lowered down the shaft (Fig. 22)
[73,74].
Increasing alcohol content in beverages without distilling: Ultra-
sonic atomisation, sometimes known as nebulization, is the
production of a fine mist above the surface of a liquid when high fre-
quency ultrasound is applied beneath the surface. It is very different
from boiling as the process can take place at ambient temperatures.
The mist is of use in medicine as an inhalant because the parti-
cle size is so small. Research has shown that the vapour produced
from ultrasonic atomisation of an aqueous solution of organic is
different from that of the bulk liquid and this has been utilised
as a possible means of separation of materials [75]. For aqueous
ethanol mixture the atomised vapour is enriched in alcohol and this
has been used to produce a stronger form of the popular Japanese
drink sake without recourse to distillation [76]. An enhanced sake
recently produced by Honda Electronics carried the name “Sono
Sake” (Fig. 23).
3. Combining ultrasound and microwaves as a hybrid
technology
I suppose that the first question that should be asked about
attempting to combine ultrasound with microwaves is why
bother? Certainly we know that the two techniques are com-
plementary in that acoustic cavitation provides a large amount
of concentrated energy that is released by hotspots and that
897
microwaves provide dielectric heating and selective heating of solid
particles. Thus one might expect some advantages in the combina-
tion.
My own first acquaintance with microwaves in synthesis was in
1989 when I was Visiting Professor of Chemistry at the University
Paris Sud with George Bram and Andre Loupy. At that time they
were involved in the development of phase transfer catalysis reac-
tions in the solid state where the support matrix was heated rapidly
by microwaves [77]. My interest at that time was in sonochemistry
it did not seem that there was much hope of combining the two
techniques of ultrasound and microwaves. However it was only a
short while after my period at Paris Sud that I became involved in
annual courses for French industrialists held at ENSIGC, Toulouse
between 1991 and 1995. There I discovered some of the pioneering
work that was being performed by Jacques Berlan on the combina-
tion of the two techniques and the existence of a prototype hybrid
reactor [78]. In fact there is one previous record in1995 of a com-
bined reactor but that particular work does not seem to have been
followed up [79].
Now it would seem that interest has rekindled in this hybrid
technology. In a review on sonochemistry in synthesis Cravotto and
Cintas made an observation about the conjoint application of ultra-
sound and microwaves that “This combination of energy sources
can promote or improve a number of chemical processes such as
synthesis, extraction of natural products and sample preparation
in chemical analysis” [80].
The main question about the combined technology is how
the two separate technologies can be combined given that any
approach involving placing a metal ultrasonic horn inside a
microwave zone is hazardous. There are two approaches:
898 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900

Fig. 22. High power ultrasound down-hole tool for improving heavy oil extraction
(courtesy of Novita, Russia).

• Use separate reactors one using ultrasound and another using Fig. 23. Sake improved using ultrasonic atomization.

MW with a recirculating pump to allow the liquid to be trans-

ferred from one reactor to another. hole. This is achieved by placing a substantial metallic o-ring in the
• Use a single reactor with both US and MW inside. hole.
Another combined reactor design has been developed using a
The latter is the system of choice since it is a synchronous appli- glass reactor and arranging that both the MW antenna and the US
cation but if the source of ultrasound is a horn immersed in the transducer is in the reacting mixture [85]. Such a design is novel
reaction liquid within the MW cavity it cannot be metallic but alter- and could well be developed further provided that care is taken to
nate glass or ceramic horns are available. If a metal horn is to be avoid any risk of MW leaching from the reaction vessel and also
used then this must be located outside of the MW zone (Fig. 24) [81]. that no damage is done to the antenna when the ultrasonic power
This type of system has been used in analytical systems including is high.
enhanced digestion.
If a ceramic or glass horn is used there is a limitation in that
because of the characteristics of ceramic materials they cannot
operate at high vibrational amplitudes and so the ultrasonic power
of the hybrid reactor will be limited but they do exist [82]. A
reported application of such a system is in improved determina-
tion of nitrogen using a Pyrex® horn (Fig. 25). The advantage of
simultaneous and direct MW and US irradiation in this system is
shown by the significant reduction in digestion time for the deter-
mination of total Kjeldahl nitrogen from 30 min to 25 min and 7 min
using classical Kjeldahl, US-assisted and MW/US-assisted digestion
methods [83].
The two styles of reactor above use recognisable scientific
microwave ovens in conjunction with ultrasound. Another design
of combined ultrasound/MW device that can be used is shown in
Fig. 26 [84]. Here the microwave energy is generated externally and
guided through an outer circular waveguide. From this it exits into
the reactor itself that is located in the centre of the instrument,
here again the horn is non-metallic. The system has the advan-
tage of being more convenient to use but in such a system it is Fig. 24. Hybrid reactor with a metallic horn outside the microwave zone (courtesy
very important to avoid MW leakage through the sonotrode access of F Chemat).
 C. Leonelli, T.J. Mason / Chemical Engineering and Processing 49 (2010) 885–900
Fig. 25. Hybrid reactor with a Pyrex® horn inside the microwave zone (courtesy of
G Cravotto).
Fig. 26. Hybrid reactor with a Pyrex® horn inside of a microwave zone formed via
a circular wave guide (courtesy of A Canals).
4. Concluding remarks
At the time of writing there can be no doubt that the devel-
opment of both microwave and ultrasound reactors have reached
an industrial scale. This is undoubtedly the result of the fact that
industry is rightly convinced of the need to move towards process
optimisation and green technology. For those of us involved in the
development of reactors incorporating these energy sources it is an
exciting time and process analysis is now becoming more impor-
tant as is modelling as a method of reducing development time and
costs.
In the case of microwave heating systems it is preferable
to install hybrid systems with hot air or IR lamps. The use of
899
radiofrequency energy would be preferred, rather than microwave,
especially when high penetration, large power or peculiar tem-
perature profiles are needed. Once the microwave applicator is
developed it is of course vital that the materials to be placed inside
as insulation or reactant should be carefully chosen to match cur-
rent safety regulation and avoid inflammables. When a microwave
applicator is operating heating homogeneity is not guaranteed and
temperature measurement still remains a problem. The advent of
large throughput flow systems incorporating microwaves has been
the development of most interest for industrial users.
For ultrasound applications there is a longer history of industrial
applications mainly in the cleaning and welding fields. Nowadays
the expansion of interest in sonochemistry and sonoprocessing in
a range of fields including environmental protection and materi-
als technology has seen the development of a range of batch and
flow reactors on an industrial scale. Similar considerations to that
of microwave technology apply in terms of ensuring homogeneous
energy distribution through the reactor but ultrasound does not
have the same problem in terms of the leakage of energy because
sound insulation is relatively easy to achieve.
The combination of microwaves with ultrasound has great
potential since the two activations are different and provide real
advantages in terms of improved heat and mass transfer. The prob-
lems of building a combined system are great and as yet we are
only at the laboratory stage. Rapid advances are being made and
it would not be surprising to find that a combined reactor on an
industrial scale could be developed within the next 5 years.
Both microwave irradiation and ultrasound definitely meet the
Process Intensification rules through the improvement of energy
transfer, the reduction of energy consumption, the reduced vol-
umes of reactors/plants, the improved product quality, the ease of
process automation as well as remote reaction control. Thus we can
conclude that both methods of activation are here to stay and will
contribute to the future of a cleaner world for all of us.
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