1.

Introduction
1.1 Nanofluids:
Nano fluids are fluid containing nanometer sized particles called nano particles. They are
obtained by the dispersion of nano materials into the base fluid. Nano particles or nano materials
are the material whose sizes are in nano-meter. The nanoparticles used in nanofluids are usually
made of metals, oxides, carbides, or carbon nanotubes. Commonly water, ethylene glycol and oil
are used as base fluid. Nanofluids have many properties, making them useful in many
applications in heat transfer, micro-electronics, fuel cells, pharmaceutical processes, hybrid-
powered engines, engine cooling/vehicle thermal management, refrigerator, chiller, heat
exchanger, grinding, machining and on boiler flue gas temperature reduction. They also provide
enhanced thermal conductivity and heat transfer co-efficient in comparison with base fluid.
Nanofluids are primarily used for their enhanced thermal properties as coolants in heat transfer
equipment such as heat exchangers, electronic cooling system and radiators. Nanofluids in solar
collectors is another application.

1.2 Ultrasonication:
Sonication is the act of applying sound energy to agitate particles in a sample, for various
purposes. Ultrasonic frequencies (>20 kHz) are usually used, leading to the process also being
known as ultrasonication and the device used for this purpose is called as sonicator or
ultrasonication. Sonicators operate on a system of high-intensity ultrasonic waves. These
ultrasonic waves create small vacuum bubbles in the liquid. When the bubblesattain a volume at
which they can no longer absorb energy, they collapse violently during a high-pressure cycle.
This phenomenon is termed cavitation, thus breaking higher size particle into lower size.
Sonication can be used for the production of nanoparticles, such as nanoemulsions, nanocrystals,
liposomes and wax emulsions, as well as for wastewater purification, degassing, extraction of
plant oil, extraction of anthocyanins and antioxidants, production of biofuels, crude oil
desulphurization, cell disruption, polymer and epoxy processing, adhesive thinning and many
other process.
Sonicators are of different types and play a vital role in preparation of nanofluid.

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Sonication processes can be carried out by the use of a probe-type ultrasonic homogenizer or an
ultrasonic bath. Although, both techniques apply ultrasound to the sample, there are significant
differences in effectiveness, efficiency and process capabilities.

Fig1(a) Bath type sonicator Fig1(b) Probe type sonicator

In an ultrasonic-bath as shown in fig1.(a), cavitation occurs non-conformable and uncontrollably
distributed throughout the tank. The sonication effect is of low intensity and unevenly spread.
The repeatability and scalability of the process is very poor.

In probe-type ultrasonicator as shown in fig1.(b), a high localized intensity compared to tank-

type is produced. This means a higher intensity and efficiency of the sonication process. In these
type of sonicator ultrasonication can be carried out for different amplitude and for varying horn
tip diameter.

In a sonicator because of the cavitation in the surface, cracks are formed in the surface and they
enhance to break down the nanomaterial into smaller sizes. Cavitation is very much intense in
probe sonicator in comparison with bath type. Probe sonicator has a good performance in
comparison with bath sonicator for similar parameters as shown in fig2.

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 Fig2. Performance of probe sonicator and bath sonicator
for similar parameters

Fig3. SEM image showing surface crack in CuO nanoparticle

In fig3. the surface crack in CuO (copper oxide) nanoparticle is visible, implying that in
sonication surface crack is formed foremost which the gets enhanced.

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The oxygen molecules present in water or any air molecule would impinge into these cracks and
thus cause rigorous vibration and lead to breakage of the particle.

Ultrasonication is needed for better dispersion of nanoparticle into base fluid. As the sonication
time increases the better the dispersion takes place. This is due to the fact that the sonication
breaks the particle into finer size.

Fig4(a) Nanoparticles Fig4(b) Nanoparticles

without sonication after sonication
Fig.4 (a) shows that without sonication the nanoparticles are clustered and settle down, thus
forming sediments or settlements, due to which the nanoparticles gets separated from base fluid.
With this there will be no enhancement in the characteristics of basefluid. Fig.4 (b) shows that
after ultrasonication the nanoparticles are dispersed uniformly. The property of the base fluid is
enhanced. A uniform solution is formed.

2. Thermal Conductivity:
Thermal conductivity of nanofluid increases immensely up to optimal sonication time for certain
temperature depending on nanofluid and later it declines on further sonication. This was usually
due to the fact that the nanoparticles broke into finer particles and thus increasing surface area
for thermal interaction and on further sonication the nanoparticles would coagulate and thus
depriving thermal conductivity.

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 Fig5. Enhancement in thermal conductivity for varying temperature
of MWCNT nanofluid sonicated for different time duration
From fig5. Apparently 40mins is the optimum time of sonication since thermal conductivity is
high. This is because at 40 mins the nanoparticles dispersed well in base fluid, before optimum
time of sonication the particles were agglomerated and after optimum time the particles re-
agglomerated thus effecting thermal conductivity.

Fig6. Thermal conductivity of ZnO-EG nanofluid at 30ºC

for different sonication time.

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From fig.6. it is seen that thermal conductivity increased till optimum time and then started to
decrease due to re-agglomeration.

Thermal conductivity is even effected by volume concentration of nanofluid as shown in fig7.

Thermal conductivity shows linear relation with concentration.

This is because the nanomaterial is having higher thermal conductivity than base fluids. Hence,
when the volume concentration of nanomaterial is increased the amount of nanomaterial is more,
thus interaction between nanomaterials increases. On contrary viscosity showed non-linear
relation with concentration.

Fig7.Effect of volume concentration on thermal conductivity

Initially the thermal conductivity is low because the particles are aggregated, as sonication time
increases the particles get dispersed well in the base fluid causing the thermal conductivity to
increase up to an optimum sonication time and then reduces due to sedimentation as shown in
fig8.

Thermal conductivity is usually checked through transient hot wire method, where the sensor is
being dipped into the nanofluid and thermal conductivity is measured. For particles with good
dispersion of nanoparticle, thermal conductivity is very good as shown in fig9(a). This is caused
because of complete dispersion, the particles are suspended in the base fluid and thus there is a

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good interaction between particles and also the particles are closer to the sensor because of
which thermal conductivity increases.

If the particle is insoluble of if there is any moderate sedimentation, the nanoparticles gets
combine and form aggregates which then tend to settle because of its density. In this case the
particles are farther to sensor because of which thermal conductivity reduces as shown in fig(b).

Fig8.Aggregation effect on thermal conductivity

Thermal conductivities are also dependent on base fluids. Since different fluids have certain
thermal conductivity and oils have better thermal conductivity than water. But are need to be
wisely selected as oils usually have higher viscosity and interaction of nanoparticles and oils are
also of greater concern.

Though oils have higher thermal conductivity than water as shown in fig10, they have higher
viscosity which would lead to higher pressure drops and also lead to pumping loss. Also, the
affinity of nanomaterials to oil is to be checked. Since, some nanomaterials are insoluble.

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Oils are usually avoided as base fluids. Since they usually damp ultrasonic vibration and absorb
the vibration instead of transmitting it, this would demand for a higher power sonication. The
lesser viscous the fluid the easier to disperse, since they enhance cavitation in the nanoparticles.

(a) Clusters are nearer to the sensor (b) clusters farther to sensor

Fig9. Different colloidal state during thermal conductivity measurement

Fig10. Thermal conductivity of different base fluids

When the base fluid is chosen it should be made sure that the fluid is having a good thermal
conductivity, because the overall conductivity of a nanofluid is the sum of thermal conductivity
of base fluid and nanomaterial. But also to be taken care that base fluid is having other desirable
properties

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3. Viscosity:
Viscosity of a fluid is defined as resistance to flow. Hence different nanofluids have different
flow property dependent on base fluid and volume concentration of nanoparticles. The higher the
volume concentration the viscosity of fluid increased thus causing pumping losses and also being
a cause for agglomeration. Water as a base fluid is having low viscosity than most of the fluids
hence, usually preferred over other fluids.

Viscosity of the nanofluids increases with sonication time until a maximum value is reached and
decreases thereafter. The initial increase is associated with declustering of nanomaterials,
resulting in formation of a better dispersion. The later decrease in viscosity can be explained by
increased breakage rate of nanomaterials, resulting in shorter nanotubes, and hence, inferior
networking of nanomaterials in dispersion.

Fig11. Effect of ultrasonic duration on viscosity

From fig11. It can be seen that the viscosity increases and then decreasing after passing through
optimum time, due to re-agglomeration as discussed earlier. This trend is usually followed in
nanofluids. It can be also seen that MWCNT is having lower optimum ultrasonication time in
comparison with alumina nanofluid, because the effect of ultrasonication depends upon physical
properties of materials too. The viscosity increased till the optimum time, further sonication
lowered viscosity. It was always a challenge to obtain a low viscous fluid with better dispersion.
As the dispersion is better the more the viscous the fluid becomes. The viscosity of nanofluid is

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also dependent on temperature, like most of the fluids the viscosity of nanofluid reduces greatly
as temperature increases.

Fig12. Viscosity of Al2O3 nanofluid for 0.01-0.3vol% concentrations

The viscosity of a nanofluid is influenced by concentration of nanomaterials. The more the
concentration of nanomaterial the more is the viscosity and higher the tendency to sediment.
Hence for this reason usually volume concentrations of nanomaterials and surfactant are
calculated using certain formula. In fig12 it can be seen that as concentration of nanoparticle
increased viscosity also increased and the viscosity decreased irrespective of concentration for
higher temperature.

4. Stability:
Stability of a nanofluid is a main concern before preparing it. The stability of the nanofluid is the
ability of nanoparticle to stay dispersed in the base fluid without forming any clusters. Stability
of a nanofluid depends on various parameter such as particle size, surfactant used, sonication
time, volume concentration, type of sonication (pulse or nonplused) etc. Ultrasonication time had
a great influence on stability, the farther the solution sonicated the more stable it was. This was
due to the fact that as the sonication proceeded further the fineness of the particle reduced for a

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certain time. Thus causing the particles to stay suspended for a longer time. The more finer the
particle size the more the stable it was.

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Fig13. Sedimentation rate for six prepared samples within 7days after preparation.

Despite the fact that higher ultrasonication time increased stability, but the sedimentation is
inevitable. It is clearly visible that the stability of the nanofluid is dependent on ultrasonication
time. This is because, the particle size decreased upon sonication and making the particle very
finer, thus leading to a better suspension.

From fig13. It is observed that after some time the particles sediment and sedimentation rate
increased with concentration. Sedimentation usually happens when the nanomaterials are
insoluble in base fluid or if the repulsive force between the particles are very less.

14(a) 14(b)
Fig14. Mg (OH)2-water nanofluid at the solid concentration of 0.8% without using surfactant in
different ultrasonication times after 14(a) 1 day, 14(b) 7 days, and 14(c) 30 days.

14 (c)

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As time pass by the repulsive forces between nanoparticles decrease and settle down and the rate
of settling is dependent on material type and sonication time as shown in fig14(a) sample was
milky white with no sign of sedimentation, but after a week as shown in fig 14(b) sedimentation
was more and nanomaterial totally separated from base fluid after a month as shown in fig14(c).
In fig14(a) and fig 14(b) as sonication time increased sedimentation decreased.

To reduce the rate of agglomeration surfactants are used. Surfactants suppressed agglomeration
for relatively long time, thus enhanced stability. The volume concentration of surfactant is of
concern if it gets higher it may increase viscosity. Surfactants, also known as surface-active
agents, are chemical compounds that reduce the surface tension of a liquid and increase the
immersion of particles. Surfactants adhere to the surface of nanomaterials, due to the similar
charge the nanomaterials are repelled by surfactants. Thus, inhibiting sedimentation. Use of a
surfactant is necessary for insoluble particles such as carbon nanotubes (CNTs) that do not
disperse in most solvents.

The stability of the nanofluid depended on type of surfactant used. Surfactant used are usually
nanomaterial specific. The concentration of surfactant used is also of concern. Using lesser
concentration may lead to lower stability and over use may increase viscosity and thus increasing
pressure drop. The stability of the nanofluid with surfactant is very much enhanced in
comparison with the nanofluid without surfactants. With surfactant the nanofluids achieved
stability for over months.

CTAB provides more stability that SDS and Oleic acid as shown in fig15. The same result cannot
be expected for different nanoparticles with same surfactants. Different surfactants interact
differently with different nanoparticles.

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Fig15. Stability of Mg(OH)2 –W nanofluid containing different surfactants after 30 days

16(a)

16(b)

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 16 (C)

Fig16.Mg (OH)2-water nanofluid at the solid concentration of 0.8% using CTAB surfactant in
different sonication times after 16(a) 1 day, 16(b) 7 days, and 16(c) 30 days.
From fig15(a,b,c) and fig 16(a,b,c) the prominence of surfactant in stability of a nanofluid is very
much visible. Without surfactant the nanofluids sedimented within days fig15(a,b,c) and with
surfactant the nanofluid was stable for over a month fig16(a,b,c).

5. ZETA POTENTIAL:
Zeta potential is a measure of effective electric charge on the nano particle surface. The
magnitude of the zeta potential provides information about particle stability, with particles with
higher magnitude zeta potentials exhibits increased stability due to a larger electrostatic repulsion
between particles fig17. Surfactant thus increases zeta potential by providing charges. The more
the magnitude the more will be the repulsion and thus higher the stability. Hence zeta potential
changed for different surfactant.

Fig17. Zeta potential range

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 Fig18.Zeta potential analysis of prepared sample containing
different surfactants
CTAB provided more stability than SDS and Oleic acid since CTAB is having higher value of
zeta potential in comparison with other samples from fig18.

Fig19. Effect of ultrasonication on zeta potential

From fig19 the effect of sonication on zeta potential value of CuO particles is shown. Particles
are dispersed in ethylene glycol. Zeta potential has the minimum value when duration of
sonication is 9 hours, hence the dispersion is regarded as the best under this condition.

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zeta potential is dependent on ultrasonication time too. At first it increased since the particles got
well dispersed and then the magnitude of zeta potential decreased because of reagglomeration.

6. Particle size:
The particle size of a nanoparticle reduced with increase in sonication time. This is mainly
because of breaking of the particles due to ultrasonication. Sonicator power is dominant on this
matter. The surface crack is instigated by cavitation and this then enhances and finally breaks. As
sonication was carried out, larger particle split into equal smaller parts which later then
broke.This way particle size reduces with advancement in time. For some nanomaterials such as
CNT the length of the tube increased before breaking, thus the particle size is also dependent on
property of material as its dependent on time.

Fig20.Effect of sonication on particle size

The particle size of nanoparticle decreases upto optimum time and then increases due to
reagglomeration fig20.

After 18 hours of sonication CNT particle size changed from 60micro meter to 1-5 micro meter, due to
rigorous sonication the particle size goes on decreasing and becomes very fine. In fig21 the surface
cracks are visible, these cracks then cause breakage of particle.

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 Fig21.TEM image of CNT particle size

7. Agglomeration size:
Cluster size or agglomeration size is the size clusters formed by cohesive action between
nanoparticles as shown in fig22. It is high before sonication and disperses after sonication and
tends to re-agglomerate after optimum sonication time. The higher the agglomeration size the
lower is the stability, due to change in density they tend to settle down thus reducing stability.
This also effects thermal conductivity, higher the agglomeration size lower is the thermal
conductivity. Therefore the agglomeration is to be subdued as much as possible.

Fig22. Cluster or aggregate size of particles

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 Fig23. Average cluster sizes ofAl 2O3 nanoparticles after varying
ultrasonication durations, at 25% and 50% amplitudes
Cluster size reduced for higher amplitudes and are depedent on sonicator type and its power from
fig23.

8. Conclusion:
 Ultrasonication time is having a prominent role in achieving higher thermal conductivity,
stability, cluster size etc but all these were on peak for an optimum sonication time.

 Ultrasonication time has twofold effect on the nanofluids. Below the optimum processing
time, the ultrasonication aids in forming better dispersions, however, once the optimum
time has been reached further ultrasonication results in an re-agglomeration, and hence
reduces thermal conductivity and viscosity.

 The optimum ultrasonication time is dependent on sonicator power, frequency used,

volume concentration, nanomaterial type, base fluid, ultrasonicator type etc.

 The more the sonication the finer the particle obtained the more the stable solution was.

 Nanofluids with the same nanoparticles and base fluids can behave differently due to
different nanofluid preparation methods and sonication time.

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9. References:
I.M. Mahbubul, I.M. Shahrul, S.S. Khaleduzzaman, R. Saidur, M.A. Amalina, A.Turgut,
Experimental investigation on effect of ultrasonication duration on colloidal dispersion
and thermo physical properties of alumina–water nanofluid, Int. J. Heat Mass Transfer 88
(2015) 73–81.

Garg, P.; Alvarado, J. L.; Marsh, C.; Carlson, T. A.; Kessler, D. A.; Annamalai, K. An
experimental study on the effect of ultrasonication on viscosity and heat transfer
performance of multi-wall carbon nanotube-based aqueous nanofluids. Int. J. Heat Mass
Transfer 2009,52, 5090.

M. Kole, T.K. Dey, Effect of prolonged ultrasonication on the thermal conductivity of

ZnO–ethylene glycol nanofluids, Thermochim. Acta 535 (2012) 58–65.

The effect of surfactant and sonication time on the stability and thermal conductivity of
water-based nanofluid containing Mg(OH)2 nanoparticles: An experimental
investigation, Int. Commun. Heat Mass Transfer 108 (2017) 191–198

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