ENS’05 Paris, France, 14-16 December 2005

ULTRASONIC PRODUCTION OF NANO-SIZE DISPERSIONS AND EMULSIONS

Thomas Hielscher

Dr. Hielscher GmbH, Warthestrasse 21, 14513 Teltow, Germany, (http://www.hielscher.com)

High-intensity ultrasound is used for the processing of

ABSTRACT liquids such as mixing, emulsifying, dispersing and
deagglomeration, or milling. When sonicating liquids at
Ultrasound is a well-established method for particle size high intensities, the sound waves that propagate into the
reduction in dispersions and emulsions. Ultrasonic liquid media result in alternating high-pressure
processors are used in the generation of nano-size (compression) and low-pressure (rarefaction) cycles, with
material slurries, dispersions and emulsions because of rates depending on the frequency. During the low-
the potential in the deagglomeration and the reduction of pressure cycle, high-intensity ultrasonic waves create
primaries. These are the mechanical effects of ultrasonic small vacuum bubbles or voids in the liquid. When the
cavitation. Ultrasound can also be used to influence bubbles attain a volume at which they can no longer
chemical reactions by the cavitation energy. This is absorb energy, they collapse violently during a high-
sonochemistry. As the market for nano-size materials pressure cycle. This phenomenon is termed cavitation.
grows, the demand for ultrasonic processes at production Cavitation, that is "the formation, growth, and implosive
level increases. At this stage, energy efficiency becomes collapse of bubbles in a liquid. Cavitational collapse
important. Since the energy required per weight or produces intense local heating (~5000 K), high pressures
volume of processed material links directly to the (~1000 atm), and enormous heating and cooling rates
equipment size required, optimization of the process (>109 K/sec)" and liquid jet streams (~400 km/h)” [4].
efficiency is essential to reduce investment and Cavitation can be produced in different ways: e.g. by
operational costs. Furthermore it is required to scale the high-pressure nozzles, rotor-stator mixers, or ultrasonic
lab and bench top configurations to this final level processors. In all those systems the input energy is
without any variations in the process achievements. Scale transformed into friction, turbulences, waves and
up by power alone will not do this. cavitation. The fraction of the input energy that is
transformed into cavitation depends on several factors
1. INTRODUCTION describing the movement of the cavitation generating
equipment in the liquid. The intensity of acceleration is
one of the most important factors influencing the efficient
Ultrasound is a very effective processing method in the transformation of energy into cavitation. Higher
generation and application of nano-size materials. In acceleration creates higher-pressure differences. This in
general, ultrasonic cavitation in liquids may cause fast turn increases the probability of the creation of vacuum
and complete degassing: initiate various chemical bubbles instead of the creation of waves propagating
reactions by generating free chemical ions (radicals); through the liquid. Thus, the higher the acceleration the
accelerate chemical reactions by facilitating the mixing of higher is the fraction of the energy that is transformed
reactants; enhance polymerization and depolymerization into cavitation. In case of an ultrasonic transducer, the
reactions by temporarily dispersing aggregates or by amplitude of oscillation describes the intensity of
permanently breaking chemical bonds in polymeric acceleration. Higher amplitudes result in a more effective
chains; increase emulsification rates; improve diffusion creation of cavitation. In addition to the intensity, the
rates; produce highly concentrated emulsions or uniform liquid should be accelerated in a way to create minimal
dispersions of micron-size or nano-size materials; assist losses in terms of turbulences, friction and wave
the extraction of substances such as enzymes from generation. For this, the optimal way is a unilateral
animal, plant, yeast, or bacterial cells; remove viruses direction of movement.
from infected tissue; and finally, erode and break down
susceptible particles, including micro-organisms [2]. 3. MATERIALS
Ultrasound can be tested in lab and bench-top scale before
the results are scaled up to the commercial level.
Nanomaterials have become integral components of
2. ULTRASONIC CAVITATION products as diverse as sunscreens, electrically conductive
coatings, and strong, lightweight plastic composites or
paints and inks. The production and processing of these
Low-intensity or high-frequency ultrasound is mainly materials is a quickly progressing technology. Indeed, it is
used for analysis, non-destructive testing and imaging. advancing rapidly and creating new possibilities for many
 Thomas Hielscher
Ultrasonic Production of Nano-Size Dispersions and Emulsions

industrial processes. Solid nanomaterials fall into three cavitation. Investigations at different materials, such as
broad categories: metal oxides, nanoclays, and carbon aqueous solutions of nanoparticulate siliciumdioxid
nanotubes. Metal-oxide nanoparticles include nanoscale powder and spray frozen agglomerates with a variable
zinc oxide, titanium oxide, iron oxide, cerium oxide and solid content have demonstrated the considerable
zirconium oxide, as well as mixed-metal compounds such advantage of ultrasound when compared with other
as indium-tin. In general, nanomaterials are defined as technologies, such as rotor-stator mixers (e.g. turrax) or
materials of less than 100nm in size. When matter is colloid mills. In particular for small matter from several
reduced in size it changes its characteristics, such as color nanometers to couple of microns, ultrasonic cavitation is
and interaction with other matter such as chemical very effective in breaking agglomerates, aggregates and
reactivity. The change in the characteristics is caused by even primaries. When ultrasound is being used for the
the change of the electronic properties. By the particle milling of high concentration batches, the liquid jets
size reduction, the surface area of the material is streams resulting from ultrasonic cavitation, make the
increased. Due to this, a higher percentage of the atoms particles collide with each other at velocities of up to
can interact with other matter, e.g. with the matrix of 1000km/h. This breaks van der Waals forces in
resins. Surface activity is a key aspect of nanomaterials. agglomerates and even primary particles. Large particles
Agglomeration and aggregation blocks surface area from are subject to surface erosion (via cavitation collapse in
contact with other matter. Only well-dispersed or single- the surrounding liquid) or particle size reduction (due to
dispersed particles allow to utilize the full beneficial fission through interparticle collision or the collapse of
potential of the matter. In result good dispersing reduces cavitation bubbles formed on the surface).
the quantity of nanomaterials needed to achieve the same
effects. As most nanomaterials are still fairly expensive, 4.2 Emulsifying
this aspect is of high importance for the
commercialization of product formulations containing If a cavitation bubble implodes near the phase boundary
nanomaterials. Today, many nanomaterials are produced of two immiscible liquids the resultant shock wave can
in a dry process. As a result, the particles need to be provide a very efficient mixing. Stable emulsions
mixed into liquid formulations. This is where most produced by sonication can be used in the textile,
nanoparticles form agglomerates during the wetting. cosmetic, pharmaceutical, food, and petrochemical
Especially carbon nanotubes are very cohesive making it industry. Ultrasonically generated emulsions are often
difficult to disperse them into liquids, such as water, more stable and require less, if any surfactant than those
ethanol, oil, polymer or epoxy resin. Therefore effective produced conventionally. Since ultrasound is fully
means of deagglomerating and dispersing are required to controllable and adaptable by the choice of amplitude,
overcome the bonding forces after wettening the micron- pressure and temperature, sonication is an effective
powder or nano-powder. instrument to obtain emulsions with smaller droplet sizes
within a narrow size distribution.
4. EFFECTS
4.3 Sonochemistry
Ultrasound is used in a wide range of physical, chemical
and biological processes. Homogenizing, emulsifying, Recent studies on the effect of sonication on suspended
and dispersing are examples for physical processes. Most powders have shown that the particles can be forced into
of the applications of high-intensity ultrasound are based violent collision that, in the case of metals, fusion can
on cavitational effects. The physical effects of cavitation occur. In some cases the colliding particles undergo
are being used in a top-down generation of nano-particles. chemical reactions. Thus, when copper and sulphur are
Here, particles are reduced in size by the forces of sonicated together in hexane for 1 hour, 65% Cu2S is
cavitation. This includes the breaking of agglomerates generated [1]. The chemical effects include the formation
and aggregates. The physical effects are used in of OH- and H+ species and hydrogen peroxide. The
combination with the chemical effects (sonochemistry) in ultrasonic effects to chemical reactions – sonochemistry –
the bottom-up production of nano-particles and crystals, include hydrolysis, oxidation, and depolymerization
i.e. during precipitation or crystallization. Here, processes, too.
ultrasound serves a number of roles in the initiation of
seeding and subsequent crystal formation and growth. 5. PROCESSING

4.1 Dispersing and Deagglomeration Ultrasound describes a wide range technology. From
cleaning tanks to sensors, from submersible transducers to
Dispersion by ultrasound is a consequence of nebulizers, from dental tools to baby images. These
microturbulences caused by fluctuation of pressure and applications differ from each other because the
 Thomas Hielscher
Ultrasonic Production of Nano-Size Dispersions and Emulsions

parameters of the ultrasound differ a lot. For each specific 5.1.3 Pressure
application and process there is a specific optimal Elevated pressure allows cavitation at temperatures close
parameter configuration. For new processes and to or above the boiling point. It also increases the
formulations this configuration has to be identified. In the intensity of the implosion, which is related to the
following the parameters important to the liquid difference between the static pressure and the vapor
processing are examined. pressure inside the bubble [5]. Since the ultrasonic power
and intensity changes quickly with changes in pressure, a
5.1 Parameters constant-pressure pump is preferable. When supplying
liquid to a flow-cell the pump should be capable of
Ultrasonic liquid processing is described by a number of handling the specific liquid flow at suitable pressures.
parameters. Most important are amplitude, pressure, Diaphragm or membrane pumps; flexible-tube, hose or
temperature, viscosity, and concentration. The process squeeze pumps; peristaltic pumps; or piston or plunger
result, such as particle size, for a given parameter pump will create alternating pressure fluctuations.
configuration is a function of the energy per processed Centrifugal pumps, gear pumps, spiral pumps, and
volume. The function changes with alterations in progressive cavity pumps that supply the liquid to be
individual parameters. Furthermore, the actual power sonicated at a continuously stable pressure are preferred.
output per surface area of the sonotrode of an ultrasonic
unit depends on the parameters. 5.1.4 Power and Intensity vs. Energy
Surface intensity and total power do only describe the
5.1.1 Surface intensity intensity of processing. The sonicated sample volume and
The power output per surface area of the sonotrode is the the time of exposure at a certain intensity have to be
surface intensity (I). The surface intensity depends on the considered to describe a sonication process in order to
amplitude (A), pressure (p), the reactor volume (VR), the make it scalable and reproducible. For a given parameter
temperature (T), viscosity (η) and others. configuration the process result, e.g. particle size or
chemical conversion, will depend on the energy per
I [W / mm²] = f ( A[ µm], p[bar],VR. [ ml ], T [°C ],η[ cP],...) volume (E/V).
+ + − − +
The impact of the generated cavitation depends on the Result = f ( E / V )
surface intensity. So does the process result. The total
power output of an ultrasonic unit is the product of Where the energy (E) is the product of the power output
surface intensity (I) and surface area (S): (P) and the time of exposure (t).

PL [W ] = I [W / mm²] * S [ mm²] E[Ws] = P[W ] * t[ s ]

5.1.2 Amplitude Changes in the parameter configuration will change the

The amplitude of oscillation describes the way the result function. This in turn will vary the amount of
sonotrode surface travels in a given time (e.g. 1/20,000s energy (E) required for a given sample value (V) to obtain
at 20kHz). The larger the amplitude, the higher is the rate a specific result value. For this reason it is not enough to
at which the pressure lowers and increases at each stroke. deploy a certain power of ultrasound to a process to get a
In addition to that, the volume displacement of each result. A more sophisticated approach is required to
stroke increases resulting in a larger cavitation volume identify the power required and the parameter
(bubble size and/or number). When applied to configuration at which the power should be put into the
dispersions, higher amplitudes show a higher process material.
destructiveness to solid particles. Table 1 shows general
values for some ultrasonic processes. 6. THREE STEP APPROACH
Process Amplitude
Cleaning 0.5 to 2 micron By dividing the process development into three stages, the
Intensive Cleaning 10 to 20 micron costs and risks in the development can be reduced.
Dispersing/Deagglomeration 10 to 30 micron Therefore the three steps are introduced: Feasibility
Emulsifying 20 to 60 micron Study, Optimization and Scale-Up. Because the sample
Primary Particle Reduction 40 to 120 micron volume is kept low, the development process can be
speeded up while generating reproducible and scalable
Table 1 - General Recommendations for Amplitudes
results based on the energy/volume.
 Thomas Hielscher
Ultrasonic Production of Nano-Size Dispersions and Emulsions

6.1 Feasibility Study

The objective of the feasibility study is the identification

of the potential for a specific product formulation or
process. Unless there is data available from similar
formulations and processes, this incorporates a trial-and-
error testing of various parameter configurations.
When starting with a random parameter configuration, the
likelihood to be at the optimal configuration is fairly low.
Also the energy per volume required to obtain a result at
this random or the optimal configuration is still to be
discovered. Based on the premises that the process result
for a given parameter configuration is a function of the
energy per processed volume, if any result can be
obtained, it will be better for a higher energy input. For
this reason, the first tests should use a very high energy
per volume level at high intensity levels. In this stage,
trials using small sample volumes are preferred to shorten
the time using a given equipment size. Lower volumes
reduce the sample amount, too. This can be important for
more precious materials. Most important is the even
distribution of the sonication energy in the sample.
Because the sonic intensity decreases with distance from
the emitting surface, short distances are preferred. When a
small liquid volume is exposed, the distance from the Picture 1 – 100W Setup for Feasibility Testing
sonotrode can be kept short. By recording the actual power input, via a PC-interface or
Table 2 shows typical energy/volume levels for sonication powermeter, the time of sonication and the actual
processes when being optimized. Since the first trials are amplitude and temperature in combination with the results
not at optimum configuration, sonication at 10 to 50 times of each trial a bottom line for the energy/volume can be
the typical value will show if there is any effect to the established. If by chance an optimal configuration has
sonicated material or not. been chosen, this configuration performance could be
verified during optimization and could be scaled up to
ProcessEnergy/ Sample Power Time
commercial level.
Volume Volume
Simple < 100Ws/ml 10ml 50W <20s During feasibility study, the limits of sonication, e.g.
Medium 100Ws/ml to 10ml 50W 20 to temperature, amplitude or energy/volume for specific
500Ws/ml 100s formulations should be examined, too. As ultrasound
Hard > 500Ws/ml 10ml 50W >100s could generate negative effects to chemicals or particles,
the critical levels for each parameter need to be examined
Table 2 - Typical Sonication Values in order to limit the following optimization to the
As energy is transmitted into the liquid, the liquid will parameter range where the negative effects are not
heat up. In order to allow for the input of high observed.
energy/volume levels cooling is required. Picture 1 shows For the feasibility study small lab or bench-top units are
a simple setup for the conduct of the feasibility trials. A recommended to limit the expenses for equipment and
cold water (or other coolant) bath is used to dissipate the samples in such trials. Generally 100 to 1,000 Watts units
heat generated in the small sample tube (green). serve the purposes of the feasibility study very well.

6.2 Optimization

The results achieved during the feasibility study may

show high energy/volume levels which when scaled up
may be not cost effective. As these trials were to show the
general impact of ultrasound only, optimization is needed
to evaluate the cost effectiveness of ultrasound for the
process. To identify the most energy and cost efficient
way to deploy the ultrasonic energy in order to obtain the
 Thomas Hielscher
Ultrasonic Production of Nano-Size Dispersions and Emulsions

potential benefits observed in the feasibility study, a

systematic optimization is required. In this step, the
correlations between the relevant parameters – in
particular amplitude, pressure and liquid formulation –
are investigated. The objective is to find the optimal
parameter configuration in which a minimum of energy is
utilized to obtain the required benefit. This is the most
efficient configuration. As this energy per volume value is
the basis for the scale up to commercial level, efficiency
gains from thorough optimization result in savings in
operation and maintenance cost.
In this stage, systematic batch samples may help to
identify the most important parameters for the specific
process. Batch trials may also serve as indicators for the
correlation between the specific parameter and the
process result. Picture 2 shows the results of trials using
different intensity and mass concentration values. The
results indicate, that a higher Aerosil concentration
improves the process efficiency.
Picture 3 - Flow Chart for Optimization Setup
For the optimization, versatile ultrasonic units of 500 to
2,000 watts are suitable for this stage. In particular, if
there is no information available on the sonication of
similar materials the systems should be capable of
covering a wide range for each parameter. For
nanomaterials amplitudes from 10 to 100 micron should
be tested. For most applications pressures from ambient to
2 or 3 bars above ambient are sufficient. For strong
materials higher pressures of up to 50 bars above ambient
may show better performance.
Again, the actual power input, the time of sonication, and
the amplitude, pressure and temperature used are recorded
together with the results of each trial. In the end the trial
using the lowest energy per volume achieving a satisfying
result will be chosen for scale up. It may be recommended
Picture 2 - Influence of solid concentration on
to validate this particular trial by a second run at the same
dispersion (UIP1000) [3]
configuration.
In a batch testing as shown in Picture 1 the pressure is
limited to ambient pressure. For this reason, flow cells are 6.3 Scale Up
required to determine the correlation between pressure
and process efficiency. Ultrasound is reproducible. When ultrasound is applied to
an identical liquid formulation at an identical processing
parameter configuration, the same energy per volume is
required to obtain an identical result independent of the
scale of processing. This allows for a linear scale up of
the optimized parameter configuration to the full
commercial scale.
 Thomas Hielscher
Ultrasonic Production of Nano-Size Dispersions and Emulsions

low compared to the savings when scaling up to the

production level. This approach does also help to find the
important parameters behind the process result. This in
turn can be used to obtain better results and a high
reproducibility.

8. REFERENCES

[1] Goh, N.K., Teah, A., Chia, L.S. (1994): Investigations

of the effect of ultrasound on some metal and nonmetal
systems, in: Ultrason. Sonochem., 1, 41 (1994).
[2] Kuldiloke, J. (2002): Effect of Ultrasound,
Temperature and Pressure Treatments on Enzyme
Activity an Quality Indicators of Fruit and Vegetable
Juices; Ph.D. Thesis at Technische Universität Berlin
(2002).
[3] Pohl, M., Schubert, H.: Dispersion and
deagglomeration of nanoparticles in aqueous solutions, in:
Partec 2004.
[4] K.S. Suslick (1998) in Kirk-Othmer Encyclopedia of
Chemical Technology; 4th Ed. J. Wiley & Sons: New
York, 1998, vol. 26, 517-541.
[5] Vercet, A., Lopez, P., and Burgos, J. (1999):
Inactivation of heat-resistant pectinmethylesterase from
Picture 4 - Commercial 4,000 Watts (left) and orange by manothermosonication, in: J. Agric. Food.
16,000 Watts (right) System for Inline Operation Chem., 47, 432 (1999)
Based upon the optimal parameter configuration found
during optimization and the related energy/volume additional information can be found at:
required the power capacity required for scale up can be http://www.hielscher.com/ultrasonics/nano_00.htm
calculated. The parameter configuration of the final
system is to be identical to the optimal configuration.
Commercial systems of up to 16,000 watts per single
device are available. Such systems can be widely adapted
to amplitude and pressure requirements in order to
perform at the optimal efficiency. Picture 4 shows a
complete 16,000 watts with generator, transducer,
sonotrode and flow cell. For larger industrial setups,
several such units can be used in parallel or in series.
Such clusters are almost unlimited in total power. As the
adaptation of such ultrasonic units is mostly limited to
boosters, sonotrodes and flow cells, it mostly possible to
re-adapt the units to new parameter configurations if
necessary. This my be required, if the product formulation
or the required result changes.

7. CONCLUSIONS

By a systematic approach to the development of

ultrasonic processes, the costs and risks involved in the
development and commercialization can be reduced.
Because feasibility and optimization tests can be done in
small lab or bench-top scale requiring small to medium
size equipment, the time and expenses for this systematic
identification of the optimal parameter configuration are