Accepted Manuscript

Title: Intensification of heat transfer using PANI nanoparticles

and PANI-CuO nanocomposite based nanofluids

Author: B.A. Bhanvase S.D. Kamath U.P. Patil H.A. Patil

A.B. Pandit S.H. Sonawane

PII: S0255-2701(16)30061-7
DOI: http://dx.doi.org/doi:10.1016/j.cep.2016.03.004
Reference: CEP 6770

To appear in: Chemical Engineering and Processing

Received date: 16-1-2016

Accepted date: 9-3-2016

Please cite this article as: B.A.Bhanvase, S.D.Kamath, U.P.Patil, H.A.Patil, A.B.Pandit,
S.H.Sonawane, Intensification of heat transfer using PANI nanoparticles and
PANI-CuO nanocomposite based nanofluids, Chemical Engineering and Processing
http://dx.doi.org/10.1016/j.cep.2016.03.004

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Intensification of Heat Transfer Using PANI Nanoparticles and PANI-CuO

Nanocomposite Based Nanofluids

B. A. Bhanvase1,*, S. D. Kamath2, U. P. Patil2, H. A. Patil2, A. B. Pandit3, S. H. Sonawane4

1
Department of Chemical Engineering, Laxminarayan Institute of Technology, Rashtrasant

Tukadoji Maharaj Nagpur University, Nagpur-440033, MS, India

2
Department of Chemical Engineering, Vishwakarma Institute of Technology, Pune-411037, MS,

India

3
Department of Chemical Engineering, Institute of Chemical Technology, Mumbai-400019, MS,

India

4
Department of Chemical Engineering National Institute of Technology Warangal-506004,

Telangana State, India

Corresponding author
*
B. A. Bhanvase:

E-mail address: bharatbhanvase@gmail.com, Tel: +91- 712-2531659

  1
Abstract

The present work deals with the preparation of CuO, polyaniline (PANI) and PANI-CuO

nanocomposite by in-situ emulsion polymerization which is subsequently dispersed in water to get

PANI and PANI-CuO nanocomposite based nanofluid to study its convective heat transfer

performance. The enhancement in the convective heat transfer of PANI and PANI-CuO

nanocomposite based nanofluids was investigated by adding 0.1 to 0.5 volume % PANI and PANI-

CuO nanocomposite particles individually (having particle size less than 100 nm) in deionized

water (basefluid), respectively. Further, the effect of percentage of PANI and PANI-CuO

nanocomposite particles and inlet temperature, on convective heat transfer performance was

investigated. The experimental results show an enhancement by more than 12 % and around 38%

in heat transfer coefficient, when 0.5 volume % of PANI and PANI-CuO nanocomposite particles

were added to the base fluid, respectively. This is attributed to use of PANI encapsulated CuO

nanocomposite particles in nanofluids, which enhances the heat transfer coefficient significantly

compared to PANI nanoparticles alone in nanofluid.

-----------------------------------------------------------------------------------------------------------------------

Keywords: PANI Nanoparticles; PANI-CuO Nanocomposite; Nanofluids; Convective Heat

Transfer Coefficient

1. Introduction

The nanofluids have found applications in numerous industries [1-5]. Several industrial

technological systems also necessitate ultrahigh cooling performance so as to maintain the

instruments cool for an efficient operation [6,7]. Inefficient heat transfer performance of

  2
conventional heat transfer fluids is the major limitation for the development of energy efficient

heat transfer fluids which are meant for cooling purposes. Further, because of the inherent poor

thermal conductivities of the conventional fluids, various efforts to create turbulence, increase in

the area, etc. have been attempted in order to increase the heat transfer performance. With the

addition of nanoparticles in base fluids resulting into a nanofluid is expected to have a significant

effect on heat transfer performance. This is generally attributed to several hundred times higher

thermal conductivity of the metallic solids or some polymers than that of conventional heat

transfer fluids such as water, oil, ethylene glycol etc. [8-13]. A stable suspension of these particles

in the base fluid to enhance the heat transfer performance is an innovative approach. This

enhancement in heat transfer performance by the suspension of these particles is attributed to a

significant increase in the overall thermal conductivity of the resulting fluid [14-23]. However,

millimeter or micrometer sized particles have many limitation and cannot be used in many

industrial applications such as microsystems because of several problems like increase in the

pressure drop, clogging of microchannels, rapid settling, damage or wear out of pipes, pumps or

bearings, etc.

Recently, nanotechnology has given a smart solution to these problems. Nano-sized particles have

greater surface to volume ratio for conduction and these particles show better suspension

properties due to low dimensional structure in base fluids and give an increase in heat transfer

performance. Nanoparticles, uniformly suspended in a base fluid will not have higher pressure

drop, do not clog the microchannels and prevent sedimentation. The term nanofluid refers a

mixture of a continuous liquid phase and a dispersed phase made of extremely fine metallic/metal

oxide particles (of size below 100 nm). The addition of these nanoparticles to base fluids does

increase the heat transfer performance by the virtue of increase in thermal property values of the

  3
resulting nanofluid [24-32]. Sommers and Yerkes [33] studied the convective heat transfer

performance dilute suspensions of 10 nm aluminum oxide nanoparticles in propanol (0.5, 1, and 3

wt%). A small but significant enhancement in the heat transfer coefficient was recorded over a

Reynold’s number range of 1800<Re<2800, which is attributed to an earlier transition to turbulent

flow. Pak and Cho [34] have shown that the Nusselt number of Al2O3/water and TiO2/water

nanofluids increases with an increase in the volume fraction of the suspended nanoparticles and the

Reynolds number for forced convective heat transfer. He et al. [14] have investigated the heat

transfer and flow behaviour of TiO2/water nanofluids flowing in an upward direction through a

vertical pipe in both, laminar and turbulent flow regimes under a constant heat flux boundary

condition. Ghasemi and Aminossadati [35] have studied natural convection heat transfer in an

inclined enclosure filled with a water-CuO nanofluid. The effect of parameters like Rayleigh

number, inclination angle, and solid volume fraction on the heat transfer characteristics of natural

convection has been also studied. The reported results indicate that addition of nanoparticles into

pure water improves its heat transfer performance. Wan et al. [7] have prepared polyaniline

nanofibers and nanofluids in deionized water and have reported thermal conductivities of the

prepared nanofluids, over a temperature range of 10-80 oC with transient plane source method. The

effect of polyaniline nanofibers loading (0.08%, 0.16%, and 0.24% in volume) on the thermal

conductivities of the prepared nanofluids has been also studied. It has been reported that the

thermal conduction performance with nanofluids is increased appreciably due to higher

crystallinity and morphological uniformity of reinforced nanofibers.

Several research groups have carried out experimental work to study the enhancement in the

effective thermal conductivity and heat transfer performance. The effect of different important

parameters have been studied by several researchers, these are particle volume concentration,

  4
particle material, particle size, particle shape, base fluid, temperature, other additive, and pH.

However, not a single report was found yet in the literature on the use of conducting polymer

nanoparticles and its composite with metal or metal oxide nanoparticles based nanofluids for an

enhancement in the heat transfer performance. Therefore, the present study is focussed on the

investigation of the heat transfer enhancement for nanofluids of different concentration of PANI

nanoparticles and PANI-CuO composite nano-particles in water (basefluid). The nanofluids were

prepared by dispersing PANI nanoparticles and PANI-CuO composite particles in water. The other

parameters considered in experimental analysis are, nanoparticle concentration and the inlet

temperature.

2. Experimental methods

2.1 Materials

Analytical grade monomer aniline was procured from M/s Thomas Baker and is used as received.

Ammonium persulphate (APS, (NH4)2S2O8), sodium lauryl sulphate (SLS) were of analytical

grade and were purchased from M/s CDH. Copper acetate (Cu(CH3COO)2:H2O) and sodium

hydroxide (NaOH) were of analytical grade and were procured from M/s Merck. Glacial acetic

acid (CH3COOH) was also of analytical grade. All the chemicals were used as received. Prepared

CuO nanoparticles were used in nanofluid in varying quantities. Millipore water was used in all the

experimentation and for the preparation of nanofluids.

2.2 Preparation of CuO, PANI and PANI-CuO composite nanoparticles

CuO nanoparticles were prepared using 600 mL copper acetate solution (0.2 M), 2 mL glacial

acetic acid and 30 mL sodium hydroxide solution (8 M) in deionized water. Initially 600 mL of

copper acetate solution (0.2 M) and 2 mL glacial acetic acid were mixed into a beaker. The

  5
solution present in the beaker was heated till boiling under constant stirring with magnetic stirrer.

The colour of the resulting solution was bluish. Addition of 30 mL sodium hydroxide solution (8

M) was done into the beaker at once and the colour of the solution turned from blue to black

immediately with simultaneous formation of black precipitate. The reaction was carried out for 2 h

under constant boiling under refluxing and stirring condition [36]. The obtained mixture was then

cooled to room temperature, centrifuged and the obtained CuO nanoparticles were washed with

Millipore water several times in order to remove the impurities. The wet CuO nanoparticles were

dried in an oven at 600C. These CuO nanoparticles were further used for the synthesis of PANI-

CuO nanocomposites.

The preparation of PANI nanoparticles were carried out by ultrasound assisted semi-batch

emulsion polymerization as per the procedure reported by Bhanvase and Sonawane [37]. During

the synthesis of PANI nanoparticles, initially, surfactant and initiator solution was prepared by

adding 1 g of SLS in 50 mL deionized water and 7:33 g of APS in 30 mL of deionized water in a

separate beaker and then were transferred to a semi-batch sonochemical reactor (Stainless Steel

Probe, UP200S, Make Hielscher Ultrasonics GmbH Germany, working frequency: 24 kHz,

nominal output power: 200 W). During emulsion polymerization of aniline for the preparation of

PANI, 1 g of aniline was added to the reactor initially and then remaining 8 g was added

continuously within a span of 70 min [37]. Reaction temperature was maintained at 10 0C

throughout the experimental investigation. All the experiments were carried out using an ultrasonic

probe so as to enhance the reaction rate and micro-mixing of reaction mass. After a time lapse of

20 min a dark green suspension was observed, which goes to confirm the formation of PANI. The

reaction was continued for a further period of 90 min and then the resulting polymerized colloidal

dispersion was kept undisturbed for 2 h [37]. The resultant solution was centrifuged and then

  6
washed several times with Millipore water to separate out the PANI nanoparticles. These

nanoparticles were dried in an oven at 60 0C. These PANI nanoparticles were further used for the

preparation of PANI based nanofluids in water as a basefluid.

Synthesis of PANI-CuO composite nanoparticles were also carried by ultrasound assisted in-situ

semi-batch emulsion polymerization according to the procedure reported by Bhanvase and

Sonawane [37]. In a separate beaker, surfactant solution was prepared with the addition of 1 g SLS

in 50 mL water and the initiator solution was prepared by adding 7:33 g of APS in 30 mL

deionized water and then both the solutions were transferred to a semi-batch sonochemical reactor

(Stainless Steel Probe, UP200S, Make Hielscher Ultrasonics GmbH Germany, working frequency:

24 kHz, nominal output power: 200 W). 0.37 g of CuO nanoparticles (4 weight % of total aniline

quantity) was added to the semi-batch reactor. To start with the polymerization reaction, 1 g of

aniline was added to the reactor initially and remaining 8 g was added dropwise manner over a

period of 70 min. Reaction temperature was maintained at 10 0C throughout the reaction. The use

of ultrasonic irradiation during the synthesis of PANI-CuO composite nanoparticles to enhance the

reaction rate and micro-mixing of the reaction medium so as to get finely dispersed nanocomposite

materials. After a time lapse of 20 min, a dark green suspension was observed, which goes to

confirm the formation of PANI. The reaction was continued for a further period of 90 min and then

the resulting polymerized colloidal dispersion was kept undisturbed for 2 h. The obtained colloidal

suspension was centrifuged and then washed several times with Millipore water to separate out the

PANI-CuO composite nanoparticles. These composite nanoparticles were dried in an oven at 60 0C

and were further used for the preparation of PANI-CuO composite nanoparticles based nanofluids.

  7
2.3 Nanofluids preparation

The PANI and PANI-CuO composite nanoparticles and deionized water were used for the

preparation of nanofluids. In the present study, PANI and PANI-CuO composite nanoparticles of

particles size of around 100 nm have been used. These PANI and PANI-CuO composite

nanoparticles were prepared as per the procedure reported in the earlier section. Nanofluid samples

were prepared by dispersing dry PANI or PANI-CuO composite nanoparticles into deionized water

(basefluid) with varying loading percentage. The nanofluid preparation was carried out by the

addition of PANI or PANI-CuO composite nanoparticles in water with magnetic stirring and then

sonicated. This was continued for about 30 min in order to obtain uniform dispersion of PANI or

PANI-CuO composite nanoparticles in a base fluid [38]. SLS was used as a dispersant and it was

added in 1:4 ratios with PANI or PANI-CuO composite nanoparticles concentration. Nanofluids

containing 0.1 to 0.5 % PANI or PANI-CuO composite nanoparticles by weight were prepared as

mentioned above.

2.4 Experimental set up and procedure for heat transfer coefficient measurements

The convective heat transfer mechanism was studied using an indigenously fabricated setup. The

schematics of used setup in this work is already reported in our earlier publication Bhanvase et al.

[13]. The experimental set up consists of a test section which is provided with 750 mm long copper

pipe (ID 8 mm and OD 10 mm), heating coil, 8 mm thick asbestos insulation in order to avoid the

heat losses and thermocouples. Further the temperature indicators, a power supply unit, a pump

(Power: 0.5 HP, Monoblock 2800 RPM) and a condenser to maintain the required experimental

conditions were used. The desired inlet temperature of nanofluid at inlet of test section was

maintained by using Julaboo cooling unit (REMI). The complete test section was heated with the

help of a heating coil placed around the copper tube and connected to an adjustable AC power

  8
supply (0–230 V, 0–5 Amp). The experiments were carried out under constant heat flux

conditions. Six surface-mount thermocouples were mounted on the test section at axial positions

located at and denoted as of 2.5 cm (TS,1 ), 16.5 cm (TS,2), 30.5 cm (TS,3), 44.5 cm (TS,4), 58.5 cm

(TS,5) and 72.5 cm (TS,6) from the inlet of the test section, and were used to measure inner surface

temperatures. In addition to this, two thermocouples were mounted before and after the heat

transfer test section in order to measure the fluid bulk temperature at the inlet and outlet of the heat

transfer section. All the thermocouples were calibrated before the commencement of the

experiments. The nanofluid was then passed through a condenser to get required inlet temperature

and recycled back to the storage tank. The centrifugal pump was used with a bypass arrangement

that was used to control the flow rate of the nanofluid in the test section. Steady state readings of

temperatures and flow rates were noted for each experiment and used for heat transfer analysis.

The experiments were carried out to study the effect of concentration of nanoparticles, nanofluid

flow rates and the inlet temperature on heat transfer performance.

2.5 Physical properties and convective heat transfer measurement

The physical properties such as density, specific heat and viscosity of the prepared PANI or PANI-

CuO composite nanoparticles nanofluids with varying concentration of PANI or PANI-CuO

composite nanoparticles were measured using Specific Gravity Bottle, Calorimeter and Brookfield

Viscometer respectively. The thermo-physical properties of PANI and PANI-CuO composite

nanoparticles based nanofluids are reported in Table 1.

Further the convective heat transfer coefficient h(x) at an axial distance ‘x’ from inlet is estimated

used following equation:

qs
h( x ) 
Ts ( x)  Tb ( x ) (1)

  9
where qs , Ts(x) and Tb(x) are heat fluxes applied to the fluid, the wall temperature measured at a

distance ‘x’ from the inlet, and the fluid bulk temperature being measured at a distance ‘x’ from the

inlet, respectively.

From the energy balance equation, the bulk temperature of the fluid, Tb(x) at an axial distance x

can be found using an equation (2),

qs P
Tb ( x)  Tb,i 
m  C p (2)

where Tb,i, P, x, m and Cp are fluid bulk temperature at the inlet, perimeter of the copper tube,

axial distance from the inlet of the test section, mass flow rate of the fluid, and specific heat

capacity of the fluid, respectively.

The heat flux applied to the fluid can be estimated using equation (3).

m C p ( T b , o  T b , i )
qs 
A (3)

Where, Tb.o, Tb.i and A are the bulk fluid outlet temperature, bulk fluid inlet temperature and inner

surface area of the copper pipe.

3. Results and discussion

3.1 TEM, XRD and EDS analysis

The morphology of CuO, PANI and PANI-CuO composite nanoparticles were characterised by

transmission electron microscopy (TEM) analysis. Fig. 1 depicts the TEM image of CuO, PANI

and PANI-CuO composite nanoparticles. The CuO nanoparticles having nearly spherical

morphology with average particles size less than 10 nm without any agglomeration and uniform

  10
particle dispersion is observed from TEM image of CuO nanoparticles (Fig. 1 A). Fig. 1(B)

represents the TEM image of PANI nanoparticles. From the Fig. 1(B) it is observed that the PANI

nanoparticles are well below 100 nm with slightly agglomerated morphology. This reduced

particle size of PANI nanoparticles is attributed to the use of ultrasonic irradiation during its

preparation by semi-batch emulsion polymerization. Further Fig. 1 (C and D) depicts the TEM

images of PANI-CuO composite nanoparticles prepared by ultrasound assisted semibatch in-situ

emulsion polymerization. It is found from the TEM images of PANI-CuO composite nanoparticles

that the CuO nanoparticles are finely dispersed into PANI matrix. This is attributed to intense

turbulence and micro-mixing caused by cavitational effects due to ultrasonic irradiation leading to

the formation of finely dispersed PANI-CuO composite nanoparticles [37,39-41]. Also the particle

size of PANI-CuO composite nanoparticles is observed to be less than 100 nm.

X-ray diffraction pattern of CuO, PANI and PANI-CuO composite nanoparticles is shown in Fig.

2. The XRD pattern of the as-prepared CuO nanoparticles is depicted in Fig. 2. The peaks at 35.5,

38.7, 48.9, 52.6, 58.2, 61.5, 66.4 and 68.2o are the peaks of the monoclinic CuO phase (JCPDS

Card. No. 89-5899) which are corresponding to the planes at (1 1 1), (1 1 1), (2 0 2), (0 2 0), (2 0

2), (1 1 3), (3 1 1) and (2 2 0) [42]. This is an indication of the formation of crystalline CuO

nanoparticles. X-ray diffraction pattern of neat PANI synthesized by ultrasound assisted semi-

batch emulsion polymerization is shown in the Fig. 2. Diffraction peaks at different 2θ values i.e.

2θ =20.1, 23.4, 25.2°, highlights the characteristic peak of PANI [43,44]. Further the XRD pattern

of PANI-CuO composite nanoparticles prepared by ultrasound assisted semi-batch in-situ

emulsion polymerization with 4 wt % of CuO nanoparticles loading in PANI is shown in Fig. 2.

The diffraction pattern of PANI-CuO composite nanoparticles shows peaks at 2θ = 20.3, 24.1,

25.3, 35.4, 36.4, 46.9, 48°. This is an indication of complete encapsulation of CuO nanoparticles

  11
by PANI matrix. Further it is also found that, there is a slight shift of peak when encapsulation of

CuO nanoparticles is carried out in PANI matrix.

Further, EDS of CuO and PANI-CuO composite nanoparticles have been depicted in Fig. 3. The

presence of Cu and O element peaks in the EDS analysis of CuO nanoparticles (Fig. 3A) is an

indication of the formation of CuO nanoparticles. Also, Fig. 3B shows the presence of Cu, O, C,

and N element peaks which is an indication of the successful formation of PANI-CuO composite

nanoparticles by an ultrasound assisted semibatch in-situ emulsion polymerization.

3.2 Effect of volume fraction of PANI and PANI-CuO composite nanoparticles on heat transfer

performance of nanofluids

The diverse studies in the literature have reported an enhancement in the heat transfer coefficients

with an increase in the concentration of nanoparticles efficiently. Fig. 4 depicts the local

convective heat transfer coefficients for nanofluids with various weight fractions of PANI and

PANI-CuO composite nanoparticles (0.1, 0.2, 0.3, 0.4, and 0.5 volume %) and basefluid at

Reynolds number of 2100 ± 50. The convective heat transfer coefficient at the entrance of the test

section up to x/Di = 20.6 is considerably higher than that of the other regions. It is attributed to

entrance effect of the nanofluid in the test section. From Fig. 4 (A), it is observed that the increase

in the concentration of PANI nanoparticles in nanofluid increase the local heat transfer coefficient

significantly. At 0.1 volume % loading of PANI nanoparticles in basefluid i.e. water, the heat

transfer coefficient is 308.17 W/m2 oC and it is found to be 338.48 W/m2 oC at 0.5 volume %

loading of PANI nanoparticles i.e. an increase of nearly 10%. The possible reasons for this

enhancement in the heat transfer coefficient in nanofluids would be due to i) translational

Brownian motion, ii) the existence of an inter-particles potential and convection in the liquid due

to the Brownian motion. At lower temperatures mean free path due to the collision of PANI

  12
nanoparticles increases and it leads to enhancement of thermal conductivity (enhancement in

thermal conductivity due to Brownian particle) which enhances the heat transfer rate due to an

increase in the heat transfer coefficient. Also this significant enhancement in heat transfer

coefficient can be described by two mechanisms. (1) The addition of the PANI nanoparticles may

have been instrumental for an earlier transition from laminar to turbulent flow which would result

in higher heat transfer coefficient value. This enhancement would only be anticipated to take place

within a very narrow region of Reynolds numbers. (2) A second mechanism that explains this

observed enhancement in heat transfer coefficient lies with the rheology of the fluid. Because the

nanofluid is shear-thinning and the shear rate is highest near the wall, better fluid flow

performance should be realized near the wall. The addition of PANI nanoparticles in nanofluid can

drastically increase the convective heat transfer coefficient and it increases with an increase in the

PANI nanoparticle concentrations. Further the superior effective thermal conductivity of nanofluid

and crystalline behaviour of PANI nanoparticles [7] are important parameters for an improvement

in the heat transfer and is also attributed to particle migration, which caused a non-uniform

distribution of thermal conductivity and viscosity field along the tube cross-section (and/or the

possibility of a reduced boundary layer) [3]. Also an increase in the volume fraction of the PANI

nanoparticles boosts the interaction and collision of the nanoparticles and the diffusion and relative

movement of these particles near the walls lead to the fast heat transfer from the walls to the

nanofluid.

Further heat transfer coefficient also found to be enhanced significantly with an increase in the

PANI-CuO composite nanoparticles (Fig. 4 B). The heat transfer coefficient value is 314.85 W/m2
o
C at 0.1 volume % loading of PANI-CuO composite nanoparticles and it is 413.15 W/m2 oC at 0.5

volume % loading of PANI-CuO composite nanoparticles (an increase of nearly 30%). The

  13
possible reasons are reported above which supports the enhancement in the heat transfer

coefficient with an addition of PANI-CuO composite nanoparticles in base fluid water. Apart from

these reasons, the enhancement in the heat transfer coefficient is attributed to the presence of PANI

and CuO nanoparticle in the PANI-CuO composite which enhances the thermal conductivity and

then heat transfer coefficient of PANI-CuO composite nanoparticle based nanofluid significantly.

Also, finely dispersed CuO nanoparticles in PANI matrix due to ultrasound assisted semi-batch in-

situ emulsion polymerization, significantly enhances the heat transfer performance of the resultant

nanofluid.

Fig. 5 reports the percentage enhancement in the heat transfer coefficient of PANI and PANI-CuO

composite nanoparticles based nanofluid at constant Reynolds number. On comparison, the

percentage enhancement in the heat transfer coefficient of PANI based nanofluid is found to be

around 12.19 % higher than the water for 0.5 volume % loading of PANI nanoparticles and it is

observed to be 36.94% higher than the water for 0.5 volume % loading of PANI-CuO composite

nanoparticles in basefluid. This significant percentage enhancement in the heat transfer coefficient

in case of PANI-CuO composite nanoparticles based nanofluid is attributed to the presence CuO

nanoparticles in the composite and its fine dispersion in PANI matrix.

3.3 Effect of inlet temperature on heat transfer of nanofluids

Fig. 6 depicted the effect of inlet temperature on the heat transfer coefficient of PANI and PANI-

CuO composite nanoparticles based nanofluids. The heat transfer coefficient at 27.5 oC inlet

temperature is found to be 308.17 W/m2 oC in case of PANI nanoparticle based nanofluid and it

increases with an increase in the inlet temperature of PANI nanofluid to 462.33 W/m2 oC at 36 oC.

However the heat transfer coefficient value is found to be 314.86 W/m2 oC at 27.5 oC inlet

temperature in case of PANI-CuO composite nanoparticles based nanofluid and it increases to

  14
576.63 W/m2 oC at 36 oC inlet temperature. The higher values in case of PANI-CuO composite

based nanofluid are attributed to the presence of CuO nanoparticles in PANI matrix. Also in case

of nanofluids, the change of inlet temperature affects the Brownian motion of nanoparticles and

clustering of nanoparticles [45], which results in remarkable changes in thermal conductivity of

nanofluids with temperature. This in turn enhances the heat transfer coefficient of PANI and

PANI-CuO composite nanoparticle based nanofluids. This significant enhancement in the heat

transfer coefficient in both the type of nanofluids may be attributed to the effect of temperature on

Brownian motion of nanoparticles and clustering/ dispersion of nanoparticles which is attributed to

the increased thermal conductivity of the nanofluid.

4. Conclusions

In the present work, preparation of CuO, PANI and PANI-CuO composite nanoparticles were

successfully prepared by hydrothermal method, ultrasound assisted semi-batch emulsion

polymerization and ultrasound assisted semi-batch in-situ emulsion polymerization, respectively.

Further PANI and PANI-CuO composite nanoparticles were dispersed in water separately in order

to prepared PANI nanoparticle based nanofluid and PANI-CuO composite nanoparticle based

nanofluid. The convective heat transfer performance of these nanofluids in copper tube has been

investigated. The particles size of PANI as well as PANI-CuO composite nanoparticles used in

nanofluids were less than 100 nm which was confirmed from TEM analysis. Significant increases

in the heat transfer coefficient (12.19 % for 0.5 volume % of PANI nanoparticles and 36.94 % for

0.5 volume % of PANI-CuO composite nanoparticles) have been observed with the PANI and

PANI-CuO composite nanoparticle addition. This significant percentage enhancement in the heat

transfer coefficient in case of PANI-CuO composite nanoparticles based nanofluid is due to the

presence CuO nanoparticles in the composite and its fine dispersion in PANI matrix with the use

  15
of ultrasound assisted in-situ emulsion polymerization technique. It is also observed that with an

increase in the nanofluid inlet temperature there is noteworthy increase in the heat transfer

coefficient which can be attributed to the effect of temperature on the thermo-physical properties

of nanofluid. Thus, improvement in the heat transfer characteristics with the use of PANI and

PANI-CuO composite nanoparticles based nanofluids, which decreases the heat transfer area, can

be a great option in heat transfer equipments.

ACKNOWLEDGMENT

Dr. B. A. Bhanvase acknowledges Science & Engineering Research Board (SERB), Department of

Science and Technology (Government of India) for providing the funding through Start Up

Research Grant (Young Scientists), Sanction order no. YSS/2014/000889.

References

[1] S. M. Peyghambarzadeh, S. H. Hashemabadi, M. Seifi Jamnani, S.M. Hoseini, Improving

the cooling performance of automobile radiator with Al2O3/water nanofluid, Applied

Thermal Engineering 31 (2011) 1833–1838.

[2] P. Naphon, P. Assadamongkol, T. Borirak, Experimental investigation of titanium

nanofluids on the heat pipe thermal efficiency, International Communications in Heat and

Mass Transfer 35 (2008) 1316–1319.

[3] D. Wen, Y. Ding, Experimental investigation into convective heat transfer of nanofluids at

the entrance region under laminar flow conditions, International Journal of Heat and Mass

Transfer 47 (2004) 5181–5188.

  16
 [4] D. Wen, Y. Ding, Formulation of nanofluids for natural convective heat transfer

applications, International Journal of Heat and Fluid Flow 26 (2005) 855–864.

[5] J. A. Eastman, S. R. Phillpot, S. U. S. Choi, P. Keblinski, Thermal transport in nanofluids,

Annual Review of Materials Research 34 (2004) 219–246.

[6] C. T. Nguyen, G. Roy, C. Gauthier, N. Galanis, Heat transfer enhancement using Al2O3–

water nanofluid for electronic liquid cooling system, Applied Thermal Engineering 27

(2007) 1501-1506.

[7] M. Wan, R.R. Yadav, K.L. Yadav, S.B. Yadaw, Synthesis and experimental investigation

on thermal conductivity of nanofluids containing functionalized Polyaniline nanofibers,

Experimental Thermal and Fluid Science 41 (2012) 158–164.

[8] S. U. S. Choi, Enhancing thermal conductivity of fluids with nanoparticles, in: D.A.

Siginer, H.P. Wang (Eds.), Developments Applications of Non-Newtonian Flows, FED-

vol. 231/MD-vol. 66, ASME, New York, 1995, pp. 99–105.

[9] H. Masuda, A. Ebata, K. Teramae, N. Hishiunma, Alteration of thermal conductivity and

viscosity of liquid by dispersed by ultra-fine particles (dispersion of γ-Al2O3 SiO2 and TiO2

ultra-fine particles), Netsu Bussei (Japan) 4 (1993) 227–233.

[10] S. D. Park, S. W. Lee, S. Kang, S. M. Kim, H. Seo, I. C. Bang, Effects of Al2O3/R-123

nanofluids containing C19H40 core–shell phase change materials on critical heat flux,

International Journal of Heat and Mass Transfer 55 (2012) 7144–7150.

[11] X. Q. Wang, A. S. Mujumdar, Heat transfer characteristics of nanofluids: a review,

International Journal of Thermal Sciences 46 (2007) 1–19.

  17
 [12] W. Duangthongsuk, S. Wongwises, A critical review of convective heat transfer of

nanofluids, Renewable and Sustainable Energy Reviews 11 (2007) 797–817.

[13] B. A. Bhanvase, M. R. Sarode, L. A. Putterwar, Abdullah K. A., M. P. Deosarkar, S. H.

Sonawane, Intensification of convective heat transfer in water/ethylene glycol based

nanofluids containing TiO2 nanoparticles, Chem. Eng. Process. 82 (2014) 123–131.

[14] Y. He, Y. Jin, H. Chen, Y. Ding, D. Cang, H. Lu, Heat transfer and flow behaviour of

aqueous suspensions of TiO2 nanoparticles (nanofluids) flowing upward through a vertical

pipe, International Journal of Heat and Mass Transfer 50 (2007) 2272–2281.

[15] W. Duangthongsuk, S. Wongwises, An experimental study on the heat transfer

performance and pressure drop of TiO2–water nanofluids flowing under a turbulent flow

regime, International Journal of Heat and Mass Transfer 53 (2010) 334–344.

[16] S. P. Jang, S. U. S. Choi, Role of Brownian motion in the enhanced thermal conductivity of

nanofluids, Applied Physics Letters 84 (2004) 4316–4318.

[17] W. Yu, D. M. France, J. L. Routbort, S. U. S. Choi, Review and comparison of nanofluid

thermal conductivity and heat transfer enhancements, Heat Transfer Engineering 29 (2008)

432–460.

[18] P. Bhattacharya, S. K. Saha, A. Yadav, P. E. Phelan, R. S. Prasher, Brownian dynamics

simulation to determine the effective thermal conductivity of nanofluids, Journal of

Applied Physics 95 (2004) 6492–6494.

[19] H. Xie, J. Wang, T. Xi, Y. Liu, F. Ai, Dependence of the thermal conductivity of

nanoparticles-fluid mixture on the base fluid, Journal of Materials Science Letters 21

(2002) 1469–1471.

  18
 [20] H. Xie, J. Wang, T. Xi, Y. Liu, Thermal conductivity of suspensions containing nanosized

SiC particles, International Journal of Thermophysics 23 (2002) 571–580.

[21] C. Pang, J. Y. Jung, Y. T. Kang, Thermal conductivity enhancement of Al2O3 nanofluids

based on the mixtures of aqueous NaCl solution and CH3OH, International Journal of Heat

and Mass Transfer 56 (2013) 94–100.

[22] K. G. K. Sarojini, S. V. Manoj, P. K. Singh, T. Pradeep, S. K. Das, Electrical conductivity

of ceramic and metallic nanofluids, Colloids and Surfaces A: Physicochemical and

Engineering Aspects 417 (2013) 39–46.

[23] C. Pang, J. Y. Jung, J. W. Lee, Y. T. Kang, Thermal conductivity measurement of

methanol-based nanofluids with Al2O3 and SiO2 nanoparticles, International Journal of

Heat and Mass Transfer 55 (2012) 5597–5602.

[24] S. U. S. Choi, Z. G. Zhang, W. Yu, F. E. Lockwood, E. A. Grulke, Anomalous thermal

conductivity enhancement in nanotube suspensions, Applied Physics Letters 79 (2001)

2252-2254.

[25] P. Keblinski, S. R. Phillpot, S. U. S. Choi, J. A. Eastman, Mechanisms of heat flow in

suspensions of nano-sized particles (nanofluids), International Journal of Heat and Mass

Transfer 45 (2002) 855-863.

[26] S. K. Das, N. Putra, P. Thiesen, W. Roetzel, Temperature dependence of thermal

conductivity enhancement of nanofluids, Journal of Heat Transfer 125 (2003) 567–574.

[27] X. Wang, X. Xu, S. U. S. Choi, Thermal conductivity of nanoparticle fluid mixture, Journal

of Thermophysics and Heat Transfer 13 (1999) 474-480.

  19
 [28] S. M. Peyghambarzadeh, S. H. Hashemabadi, S. M. Hoseini, M. Seifi Jamnani,

Experimental study of heat transfer enhancement using water/ethylene glycol based

nanofluids as a new coolant for car radiators, International Communications in Heat and

Mass Transfer 38 (2011) 1283-1290.

[29] H. Xie, J. Wang, T. Xi, F. Ai, Q. Wu, Thermal conductivity enhancement of suspensions

containing nanosized alumina particles, Journal of Applied Physics 91 (2002) 4568–4572.

[30] S. Lee, S. U. S. Choi, S. Li, J. A. Eastman, Measuring thermal conductivity of fluids

containing oxide nanoparticles, Journal of Heat Transfer 121 (1999) 280-289.

[31] Y. Xuan, Q. Li, Heat transfer enhancement of nanofluids, International Journal of Heat and

Fluid Flow 21 (2000) 58–64.

[32] S. M. S. Murshed, K. C. Leong, C. Yang, Enhanced thermal conductivity of TiO2-water

based nanofluids, International Journal of Thermal Sciences 44 (2005) 367–373.

[33] Andrew D. Sommers, Kirk L. Yerkes, Experimental investigation into the convective heat

transfer and system-level effects of Al2O3-propanol nanofluid, J Nanopart Res (2010)

12:1003–1014.

[34] B. C. Pak, Y. L. Cho, Hydrodynamic and heat transfer study of dispersed fluids with

submicron metallic oxide particles, Experimental Heat Transfer: A Journal of Thermal

Energy Generation, Transport, Storage, and Conversion 11 (1998) 151–170.

[35] B. Ghasemi, S. M. Aminossadati, Natural Convection Heat Transfer in an Inclined

Enclosure Filled with a Water-Cuo Nanofluid, Numerical Heat Transfer, Part A:

Applications: An International Journal of Computation and Methodology, 55 (2009) 807-

823.

  20
 [36] H. Zhu, D. Han, Z. Meng, D. Wu, C. Zhang, Preparation and thermal conductivity of CuO

nanouid via a wet chemical method, Nanoscale Research Letters 6 (2011) 181-190.

[37] B.A. Bhanvase, S. H. Sonawane, New approach for simultaneous enhancement of

anticorrosive and mechanical properties of coatings: Application of water repellent nano

CaCO3-PANI emulsion nanocomposite in alkyd resins, Chemical Engineering Journal 156

(2010) 177 -183.

[38] P. Garg, J. L. Alvarado, C. Marsh, T. A. Carlson, D. A. Kessler, K. Annamalai, An

experimental study on the effect of ultrasonication on viscosity and heat transfer

performance of multi-wall carbon nanotube-based aqueous nanofluids, International

Journal of Heat and Mass Transfer 52 (2009) 5090–5101.

[39] B.A. Bhanvase, D.V. Pinjari, P.R. Gogate, S.H. Sonawane, A.B. Pandit, Process

intensification of Encapsulation of Functionalized CaCO3 nanoparticles using Ultrasound

Assisted Emulsion Polymerization, Chemical Engineering and Processing: Process

Intensification, 50 (2011) 1160 – 1168.

[40] B.A. Bhanvase, D.V. Pinjari, S.H. Sonawane, P.R. Gogate, A.B. Pandit, Analysis of

semibatch emulsion polymerization: Role of ultrasound and initiator, Ultrasonics

Sonochemistry, 19 (2012) 97 – 103.

[41] B. A. Bhanvase, D. V. Pinjari, P.R. Gogate, S. H. Sonawane, A. B. Pandit, Synthesis of

Exfoliated Poly(Styrene-co-Methyl Methacrylate)/Montmorillonite Nanocomposite using

Ultrasound Assisted In-Situ Emulsion Copolymerization, Chemical Engineering Journal,

181–182 (2012) 770 – 778.

  21
 [42] Di Chen, Guozhen Shen, Kaibin Tang, Yitai Qian, Large-scale synthesis of CuO shuttle-

like crystals via a convenient hydrothermal decomposition route, Journal of Crystal Growth

254 (2003) 225–228.

[43] M. Çelik, M. Onal, Intercalated polyaniline/Na-montmorillonite nanocomposites via

oxidative polymerization, J. Polym. Res. 14 (2007) 313-317.

[44] J. Jiang, L. H. Ai, Microemulsion-mediated in-situ synthesis and magnetic characterization

of polyaniline/Zn0.5Cu0.5Fe2O4 nanocomposite, Appl. Phys. A: Mat. Sc. Eng. 2 (2008) 341-

344.

[45] R. Prasher, W. Evans, P. Meakin, J. Fish, P. Phelan, P. Keblinsk, Effect of aggregation on

thermal conduction in colloidal nanofluids, Applied Physics Letters 89 (2006) 143119 -

143119-3.

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Fig. 1. Transmission Electron Microscopy (TEM) images of (A) CuO nanoparticles, (B) PANI
nanoparticles and (C and D) PANI-CuO nanocomposite used in heat transfer enhancement studies
using nanofluids.

  23
 7000

(1 1 1)

(1 1 1)
6000

5000

(3 1 1)
(1 1 3)
(2 0 2)

(2 2 0)
(2 0 2)
(0 2 0)
4000
Intensity (CPS)

CuO Nanoparticles
3000 PANI Nanoparticles
PANI-CuO Nanocomposite
2000

1000

0
20 30 40 50 60 70
2 (Degree)

Fig. 2. X-ray diffraction pattern of CuO, PANI and PANI-CuO composite nanoparticles used in
the heat transfer enhancement studies using PANI and PANI-CuO composite nanoparticles based
nanofluids.

  24
 (A)

(B)
Fig. 3. EDS of (A) CuO nanoparticles and (B) PANI-CuO nanocomposite used in heat transfer
enhancement studies using nanofluids.

  25
 380 0.1 Vol % 0.2 Vol % 0.3 Vol %
370 0.4 Vol % 0.5 Vol % DI Water

360
350
h(x)

340
330
320
310
300

(A) 0 20 x/D i 40 60 80

450 0.1 Vol % 0.2 Vol % 0.3 Vol %

430 0.4 Vol % 0.5 Vol % DI Water

410
390
h(x)

370
350
330
310
290

(B) 0 20 40 60 80
x/D i

Fig. 4. Axial variation of Convective heat transfer co-efficient as a function of (A) PANI and (B)
PANI-CuO nanocomposite concentration in basefluid at Re = 2100

  26
 20 0.1% Vol % 0.2% Vol %
0.3% Vol % 0.4% Vol %
% Enhancement (Δh /hbf )×100

18 0.5% Vol %
16
14
12
10
8
6
4
2
0
(A) 0 20 x/D i 40 60 80

45 0.1% Vol % 0.2% Vol %

0.3% Vol % 0.4% Vol %
% Enhancement (Δh /hbf )×100

40 0.5% Vol %
35
30
25
20
15
10
5
0
(B) 0 20 x/D i 40 60 80

Fig. 5. Axial variation of percentage enhancement in heat transfer coefficient of nanofluid at Re =

2100 as a function of (A) PANI and (B) PANI-CuO nanocomposite concentration in basefluid

  27
 27.5 Deg. C 30.0 Deg. C
530
33.0 Deg. C 36.0 Deg. C
480

430
h(x)

380

330

280
(A) 0 20 x/D i 40 60 80

645 27.5 Deg. C 30.0 Deg. C

33.0 Deg. C 36.0 Deg. C
595
545
495
h(x)

445
395
345
295
(B) 0 20 x/D i 40 60 80

Fig. 6. Effect of inlet temperature on heat transfer coefficient of nanofluid for 0.1 vol. % of (A)
PANI and (B) PANI-CuO nanocomposite concentration in basefluid at Re = 2100

  28
 Table 1. The thermo-physical properties of PANI and PANI-CuO composite nanoparticles based

nanofluids

PANI-CuO composite concentration (Vol. %) in PANI nanoparticles concentration (Vol. %) in

Physical Nanofluid Nanofluid
Properties
0.1 0.2 0.3 0.4 0.5 0.1 0.2 0.3 0.4 0.5

ρ (kg/m3) 1041.7 1042.8 1043.4 1044.3 1046.2 999.9 1001.8 1003.7 1005.6 1007.5

μ (cP) 1.250 1.255 1.285 1.300 1.320 1.275 1.300 1.305 1.310 1.335

Cp
(J/kg.°C) 4063.87 3995.65 3929.46 3894.16 3823.36 3992.57 3811.14 3629.71 3448.28 3266.86

  29