Ultrasonics Sonochemistry 18 (2011) 226–230

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

New evidence for the inverse dependence of mechanical and chemical effects on
the frequency of ultrasound
T.J. Mason a,*, A.J. Cobley a, J.E. Graves a, D. Morgan b
a
The Sonochemistry Centre at Coventry University, Faculty of Health and Life Sciences, Priory Street, Coventry CV1 5FB, UK
b
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, UK

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

Article history: Acoustic cavitation has been the subject of research and discussion for many years and it is the underly-
Received 29 March 2010 ing driving force for sonochemistry. The collapse of acoustic cavitation bubbles in water near to a surface
Received in revised form 19 May 2010 can bring about significant surface modification in terms of the mechanical damage caused by the asym-
Accepted 20 May 2010
metric collapse of the bubbles which cause erosion and abrasion. A second effect of acoustic cavitation is
Available online 17 June 2010
the formation of short lived radicals caused by the breakdown of water inside the bubble. For the first
time the dependence of these effects has been observed on the surface of a plastic material as a function
Keywords:
of ultrasonic frequency.
Sonochemistry
Mechanical effects
Ó 2010 Elsevier B.V. All rights reserved.
Chemical effects
Frequency
Surface modification
Plastic

1. Introduction The mechanical effects of ultrasound are however important in

In the early years of sonochemistry, when it was first becoming
recognised as a discipline, most researchers worked within the fre-
quency range of 20 and 40 kHz because these were the common
frequencies available in laboratories when using ultrasonic cell dis-
ruptors or cleaning baths respectively. One exception to this was
the work of Arnim Henglein who used 1 MHz [1]. At that time
however no research group seemed to work over the whole range
of frequencies which led to a misconception that as long as the
ultrasound power was above the cavitation threshold the resulting
sonochemical effects would be independent of the frequency
employed.
The mechanism of sonochemical effects was always of interest
and centred around the idea that the collapse of acoustic cavitation
bubbles would give rise to so-called ‘‘hotspots” of energy. This had
been the domaine of physicists for many years and the origins of
the theory can be traced back to 1950 and the work of Noltingk
and Neppiras [2]. Chemists who began working on sonochemistry
soon became aware that the remarkable effects of cavitation col-
lapse could be crudely subdivided into chemical effects and
mechanical effects. Indeed there were some quite lengthy discus-
sions at conferences about these two possibilities that Jean-Louis
Luche referred to as ‘‘True” and ‘‘False” effects respectively [3].
* Corresponding author.
E-mail address: t.mason@coventry.ac.uk (T.J. Mason).
processes such as mixing and particle size reduction and indeed
a whole research field exists outside of sonochemistry which con-
cerns the mechanical effects induced by friction between particles
and is known as Mechanochemistry [4]. Some years ago Mason ob-
served that the so-called mechanical effects were of little interest
to synthetic chemists but nevertheless they are certainly important
in areas such as processing and that the ever expanding interests in
applications of power ultrasound would see ‘‘false” sonochemistry
born again as a significant research area [5].
Subsequently Luche refined his ideas and classified sonochemi-
cal reactions into three different types (Table 1) [6]. A rather broad-
er classification was introduced by Suslick [7] which covered the
whole range of sonochemical reaction rather than the purely syn-
thetic reactions considered by Luche (Table 2).
2. The effect of changes in ultrasonic frequency on the chemical
effects of cavitation
When researchers began to work across a series of different fre-
quencies in the 20 kHz to 1 MHz range it soon became clear that
the choice of ultrasonic frequency was very important in terms
of both physical and chemical effects. Consider for example the
well known generation of free radicals in the sonolysis of water.
In an important paper on this topic Petrier compared the effective-
ness of 20 and 514 kHz irradiation in the oxidation of aqueous KI to
iodine and the generation of hydrogen peroxide in water at the

1350-4177/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2010.05.008
 T.J. Mason et al. / Ultrasonics Sonochemistry 18 (2011) 226–230 227

Table 1
Classification of sonochemical reactions (J.-L. Luche).

Sonochemistry
Type 1 Type II Type III
Homogeneous solution where radical Heterogeneous systems where ionic reactions can be Heterogeneous systems that follow either ionic or
intermediates are generated stimulated by mechanical effects radical mechanism

Table 2
Classification of sonochemical reactions (K.S. Suslick).

Sonochemistry
Homogeneous Heterogeneous
Bond breakage/radical formation leading to chemical Increased chemical reactivity due to enhanced mass transport (primary radicals may also play a significant
reactions role)
Aqueous Organic sonochemistry Reactions involving Reactions involving solids and liquids
sonochemistry immiscible liquids
Water is used as the Organic liquids are used as For example, emulsion For example, catalytic reactions on solid surfaces where the reactants are
solvent the solvent polymerisation kept in the liquid phase

same input power [8]. The rate of production of iodine in oxygen
saturated KI (10 2M) was some six times faster and peroxide for-
mation 12 times faster at the higher frequency. This result is as-
cribed to the fate of the OH radical formed by the breakdown of
water on cavitation bubble collapse. The OH can be destroyed by
reactions in the bubble or can migrate into the bulk solution and
produce peroxide. At the higher frequency a shorter bubble life-
time allows more of the OH to migrate from the bubble resulting
in a greater proportion of radical reactions. There is also some evi-
dence for this frequency effect in work involving hydroxyl radical
reaction with terephthalate [9]. When aqueous sodium terephthal-
ate reacts with OH it forms fluorescent hydroxyterephthalate and
its concentration can be estimated spectroscopically. The results in
Table 3 show the fluorescence yield after 30 min irradiation for
10 3 M terephthalate at three different frequencies together with
the energy input to the reaction estimated calorimetrically. The
sonochemical efficiency for this reaction can be obtained by divid-
ing OH yield (directly proportional to fluorescence) by power in-
put. The results clearly indicate that the efficiency of OH
production increases as the irradiation frequency is increased.
Thus it can be demonstrated that at higher frequencies there is
a greater propensity for radical reactions.
3. The effect of changes in ultrasonic frequency on the
mechanical effects of cavitation
Perhaps the most obvious practical example of the mechanical
effects of cavitation can be found in the field of ultrasonic cleaning.
Traditional cleaning baths operate at the lower end of the ultra-
sound range, generally around 40 kHz. This frequency used not
only for cleaning jewellery and small metal components but also
for the majority of heavy duty cleaning [10]. However for the
cleaning of electronic wafers the cavitation induced at this fre-
quency is sufficiently powerful to damage them. At much higher
frequencies (around 1 MHz) the wafers can be cleaned efficiently
and without significant surface damage. This process is often
termed Megasonic cleaning and the acoustic power used is critical
in order to avoid damage [11,12].
There are very few reports of the relationship between applied
acoustic frequency and the resulting radical and mechanical ef-
fects. However Portenlanger observed that for the ultrasonic deg-
radation of dextran mechanical effects were most important at
low frequencies (35 kHz) whereas only radical reactions are
responsible for the degradation at higher frequencies (>500 kHz)
[13]. A general summary of the two effects in aqueous systems is
that as the frequency of ultrasound is increased the mechanical ef-
fects decrease but the chemical effects increase and that the latter
are associated with radical production.
4. Mechanical versus chemical effects in sonochemical surface
modification
For several years we have been investigating the effects of
acoustic cavitation in water as a means of surface modifying the
plastic substrates used in printed circuit board manufacture. In
the past there had been a few reports of the use of ultrasound
for surface treatment but these were often in combination with
chemicals for example, in the surface modification of polyethylene
[14], ABS [15] and PVC [16]. In our recent work we have described
sonochemical surface modification of some materials important to
the electronics industry in water in the absence of added chemicals
[17,18]. These studies have used low ultrasonic frequencies be-
tween 20 and 40 kHz which favours the mechanical effects of cav-
itation. However this current study we have chosen to investigate
the effect of a range of ultrasonic frequencies from 20 to 1176 kHz
on the surface modification of a Noryl material (a blend of poly-
phenylene oxide and polystyrene) together with the resultant
chemical and physical changes to the substrate.

5. Experimental
Table 3
The effect of frequency on OH radical production.
The material used in this study was Noryl HM4025, a glass filled
Frequency (kHz) Fluorescence F Power (W) P Yield = F/P polyphenylene ester, polystyrene blend that has been employed in
20 30 50 0.6 electronic manufacturing for the production of moulded intercon-
40 40.2 26 1.6 nect devices (MIDs). Eight 2 mm thick coupons (of dimensions
60 29.3 11 2.7
25  30 mm) of this test material (from the same batch) were pro-
Terephthalate 0.001 M, sonication time 60 min, volume 50 cm3, 30 °C. cessed at each frequency.
228 T.J. Mason et al. / Ultrasonics Sonochemistry 18 (2011) 226–230
Five ultrasonic frequencies were used to treat this material
using three ultrasonic devices. 20 kHz was provided by an ultra-
sonic probe with tip diameter 300 mm (Sonic Systems Ltd., model
P100/3–20). The probe was immersed in a jacketed beaker to
which 200 ml of de-ionized (DI) water was added. The probe was
held 5 mm above the sample surface and the temperature was con-
trolled by pumping cold water via a chiller around the jacketed
beaker. 40 kHz was provided by an ultrasonic bath (Langford Ultra-
sonic, Model 375TT). This was filled with 2 l of DI water and main-
tained at 40 °C by immersion of a cooling coil attached to a chiller.
The higher frequencies of 582, 863 and 1142 kHz were generated
by a multi-frequency bath system (Meinhardt generator and ultra-
sonic transducer E805TM) using a solution volume of 430 ml
which was again held within a jacketed cell to enable cooling via
a chiller. The distance between the sample face and the emitting
surface in these cases was 15 mm.
In all cases DI water was employed as the liquid medium at a
temperature of 40 °C with a sonication time of 30 min. An estima-
tion of the actual power entering the system was determined by
calorimetry [19], 3 measurements being made at each frequency.
As a control, 8 samples were suspended in mechanically stirred
DI water at 40 °C for 30 min.
Two of the 8 samples at each frequency were subjected to either
Scanning Electron Microscopy (SEM), or X-ray photoelectron spec-
troscopy (XPS) analysis whilst the others were evaluated by weight
loss using the method reported [18].
6. Results and discussion
Comparing the effects of varying ultrasonic frequencies in terms
of acoustic energy can be problematic because the effects must be
Table 4
Measurements of specific acoustic power using calorimetry.
Frequency (kHz) Power by calorimetry (W) Power intensity (W/dm3)
20 38.5 192.5
40 74.4 37.2
582 10.9 25.3
863 8.1 18.8
1142 7.5 17.4
Fig. 1. Effect of frequency on weight loss.
measured using different equipment which, almost inevitably,
have different reaction volumes, ultrasonic sources and power con-
trols. The generally accepted laboratory method of taking these dif-
ferences into account is to measure the actual acoustic power
entering the system by calorimetry [19] in watts and this is then
converted into specific acoustic power by dividing by the volume
sonicated (Table 4).
All of the ultrasonic equipment used was of the bath type ex-
cept for the 20 kHz probe which delivered the highest intensity.
In the case of the bath systems the intensities decreased with
increasing frequency.
A very clear relationship between decreasing weight loss and
increasing ultrasonic frequency can be seen in Fig. 1. The effect
of cavitation collapse on the surface is revealed in the SEM pictures
in Fig. 2.
The differences in surface erosion can be seen in the SEM pic-
tures of the coupons. The Noryl surface without ultrasonic treat-
ment is shown in Fig. 2a which shows the glass fibres partially
protruding from the plastic surface. In the area below the probe ef-
fected by 20 kHz sonication the surface is clearly eroded to reveal
more underlying glass fibres (Fig. 2b).
The samples produced at 40 kHz confirm a smaller weight loss
than at 20 kHz with a smaller change in surface morphology
(Fig. 2c). When the multi-frequency equipment was used the sam-
ples produced at 582 and 863 kHz had increasingly smaller weight
losses at these higher frequencies indicating that little material has
actually been removed and the SEM pictures do not reveal signifi-
cant erosion (Fig. 2e and f). At 1142 kHz the plaques had very low
weight loss and the similarity between its morphology (Fig. 2g)
and that of the control sample (Fig. 2a) seems to indicate that son-
icating the sample at this high frequency does not affect the phys-
ical properties of the material.
There are both mechanical and chemical effects produced by a
collapsing cavitation bubble in water. The mechanical effects are
produced by shear forces and jetting close to the surface but chem-
ical effects can also occur due to the formation of oxidising species
from the decomposition of water [20].
The changes in surface chemistry induced by species generated
from the sonochemical decomposition of water will be oxidation
resulting in the formation of hydroxyl or carbonyl groups from
the polymeric surface. It is now generally accepted that the pro-
 T.J. Mason et al. / Ultrasonics Sonochemistry 18 (2011) 226–230 229

Fig. 2. Effect of different ultrasonic frequencies on the surface morphology by SEM (magnification 500).

duction of free radicals is more efficient in the higher range ultra-
sonic frequencies rather than in the 20–40 kHz range [21]. This
phenomenon has been applied in other waste-water treatments,
for example the degradation of azo-dyes at 850 kHz has been
shown to be due primarily to radical formation [22].
The trend in increased radical activity with increase in ultra-
sonic frequency is demonstrated by XPS data shown in Fig. 3. There
is a clear relationship between increase in frequency and increase
in surface oxidation (although the changes in atomic percentage
oxygen are relatively small). A maximum in the percentage of
230 T.J. Mason et al. / Ultrasonics Sonochemistry 18 (2011) 226–230
Fig. 3. Effect of frequency on atomic percentage oxygen by XPS.
atomic oxygen on the surface is seen at 863 kHz. However as the
frequency was further increased to 1142 kHz there is essentially
no surface oxidation which we believe is due to a drop in the en-
ergy of cavitation that reduces the sonochemical effects, both
mechanical and chemical, in keeping with the results obtained in
megasonic surface cleaning [12].
7. Conclusions
This study has indicated that the frequency of ultrasound used
in the sonochemical surface modification of materials can bring
about very different surface effects. At lower frequencies physical
surface modification occurs due to the abrasive action of energetic
micro-jetting. When the 20 kHz ultrasonic probe is used this pro-
duces significant changes to the surface morphology resulting in
high weight loss. However, this ultrasonic set-up also produced
an ultrasonic intensity which was at least five times higher than
those observed at other frequencies and this must also be consid-
ered. The 40 kHz ultrasonic bath produced relatively high weight
loss with a more uniform surface modification. At both these low
frequencies chemical changes to the surface as evidenced by XPS
investigation were less prevalent. However at higher frequencies
the weight loss is low and physical modification of the surface
structure is less obvious. The XPS data suggest that some oxidation
of the substrate is occurring at the higher frequencies which can be
ascribed to attack by sonochemically generated radical species.
Acknowledgments
The authors thank the IeMRC for funding this study and EPSRC
for supporting this work through the Access to Materials Research
Equipment Initiative (EP/F019823/1).
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