Accepted Manuscript

Experimental Investigation on Thermal Performance of Kerosene-Graphene

Nanofluid

Deepak Kumar Agarwal, Aravind Vaidyanathan, S. Sunil Kumar

PII: S0894-1777(15)00304-0
DOI: http://dx.doi.org/10.1016/j.expthermflusci.2015.10.028
Reference: ETF 8618

To appear in: Experimental Thermal and Fluid Science

Received Date: 26 June 2015

Revised Date: 20 October 2015
Accepted Date: 24 October 2015

Please cite this article as: D.K. Agarwal, A. Vaidyanathan, S. Sunil Kumar, Experimental Investigation on Thermal
Performance of Kerosene-Graphene Nanofluid, Experimental Thermal and Fluid Science (2015), doi: http://
dx.doi.org/10.1016/j.expthermflusci.2015.10.028

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Experimental Investigation on Thermal Performance of Kerosene-

Graphene Nanofluid

Deepak Kumar Agarwala, Aravind Vaidyanathanb, S Sunil Kumara*

a
Liquid Propulsion Systems Centre, ISRO, Thiruvananthapuram, Kerala, India - 695 547,

b
Indian Institute of Space Science and Technology, Thiruvananthapuram, Kerala, India - 695

547,

*
Corresponding author. email: sunil_plamood@yahoo.com, ph: +91 471 256 7535, fax: +91

471 256 7039

Abstract

Current study experimentally investigates the thermal performance of kerosene based

nanofluid containing graphene nanoplatelets (GNP) for its potential use in regenerative

cooling of semi-cryogenic rocket thrust chamber. Stable kerosene-GNP nanofluids at 0.005,

0.02, 0.05, 0.1, 0.2 weight percentage (wt%) and 300, 500, 750 m2/g, specific surface area

(SSA) are prepared using ultrasonication and steric stabilization technique. Oleylamine is

found to be the suitable surfactant with an optimum oleylamine to GNP mass ratio of 0.6, for

maximum stability of nanofluid. Dynamic Light Scattering (DLS) technique along with

thermal conductivity measurements are used to identify the stability of nanofluid with time.

23% enhancement in thermal conductivity and 8% increase in viscosity at room temperature

are observed for 750 SSA, 0.2 wt% kerosene-GNP nanofluid. Lower enhancement in thermal

conductivity and viscosity are noticed for nanofluid that is prepared with lower SSA GNPs.

The study shows less significant effect of temperature on the thermal conductivity of

kerosene-GNP nanofluid compared to kerosene-alumina nanofluid. The behaviour observed

1
is collaborated due to the combined effect of Brownian motion in smaller size sheets and

thermal conduction in longer chain structure. Maximum effect of temperature on thermal

conductivity is observed for 750 SSA nanofluid as compared to other sizes of GNPs.

Experimental study on convective heat transfer performance of the nanofluids at turbulent

flow regime show significant improvement in heat transfer performance of kerosene-GNP

nanofluid as compared to pure kerosene. 49% enhancement in convective heat transfer

coefficient is noticed for 750 SSA, 0.2wt% kerosene-GNP nanofluids. A correlation for

friction factor based on the experimental data is also determined. Merit number, used to

determine the total heat transfer performance shows the utility of these nanofluids as heat

transfer fluids.

Keywords: Kerosene, Nanofluid, Reynolds number, convective heat transfer, thermal

conductivity, dynamic viscosity

Nomenclature

Cp Specific heat (J/kgK)

Di Diameter of test section, (m)

D Hydrodynamic diameter (nm)

f Friction factor

h Heat transfer coefficient (W/m2K)

I Current (A)

k Thermal conductivity (W/mK)

L Length of test section (m)

Le Equivalent length of graphene sheet (nm)

2
N Particle count

Nu Nusselt number

Pr Prandtl number

Q Heat energy (W)

Re Reynolds number

T Temperature (ºC)

V Voltage (V)

Ṽ Volume flow rate (m3/s)

X Axial distance along the test section (m)

Greek Symbol

Φ Nanoparticle mass concentration (%)

φ Nanoparticle volume concentration (%)

μ Dynamic viscosity ( kg/ms)

ρ Density (kg/m3)

δ Thermal boundary layer thickness

ΔP Pressure drop (Pa)

Subscripts

bf base fluid

c current value

f fluid

3
i initial value

nf nanofluid

np nanoparticle

s surface

4
1. Introduction

In rocket engines, the increased thrust requirement lead to increased heat flux on the thrust

chamber walls and therefore needs to be regeneratively cooled by circulating one of the

propellants along the outer surface of the nozzle wall through cooling channels. The cooling

efficiency of any fluids depends upon its thermo-physical properties and flow velocity. The

increase in flow velocity increases the pressure drop in the system which in turn increases

requirement of pumping power. Kerosene is used as a fuel in semi cryogenic engine.

Regenerative cooling is used to protect the thrust chamber wall from the hot combustion

products. Kerosene is used as coolant in the regenerative passage before admitting it into the

combustion chamber. Kerosene with low thermal conductivity is also susceptible to coking if

the fluid temperature through the regenerative passage increases beyond a certain limit.

Therefore, to enhance the applicability limit of semi cryogenic engine at higher thrust levels

and reusability of the thrust chamber, it is pertinent to increase the thermal conductivity of its

fuel. Thermo-physical properties of kerosene can be enhanced by addition of small amount of

nanoparticles in it. Choi [1] in 1995 at the Agronne National Laboratory, Chicago has carried

out the pioneering work of dispersing nano-sized particle in a base fluid and named this

colloidal solution as “Nanofluid”. Nanoparticles used in nanofluids are a class of materials

that exhibit unique physical and chemical properties compared to those of larger particles of

the same materials. The presence of nanoparticles with large surface area is expected to

enhance the heat transfer and also stability of the nanofluid. This property of nanoparticle is

utilized to develop nanofluids with an unprecedented combination of two features that are

highly desirable for heat transfer systems; extreme stability and very high thermal

conductivity.

5
Over the past one and half decade, many researchers have investigated the nanofluids for

their enhanced heat transfer properties. Researchers have carried out wide range of

experimental studies [2] using spherical particles made of oxides, carbide and metal

nanoparticles in water or ethylene glycol. Most of these studies clearly indicate higher heat

transfer performance for nanofluids as compared to the respective base fluid. The enhanced

thermal conductivity of nanofluid made of non-spherical particles, viz; multiwalled carbon

nanotube (MWCNT) was first reported by Choi et al. [3]. An increase of 160% in thermal

conductivity for 1 vol% MWCNTs dispersed in poly-(αolefin) oil was noticed. The main

reason for the selection of carbon nanotubes (CNT) was its very high thermal conductivity.

Subsequently, many studies were carried out using MWCNT [4,5] and single walled carbon

nanotube SWCNT [6,7] and most of the studies reported significantly higher heat transfer

properties for these nanofluids in comparison to spherical particle nanofluids.

Graphene, a single atomic layer of graphite has two-dimensional form of carbon and found to

exhibit high crystal quality as it has ballistic electronic transport at room temperature.

Graphene attracted much attention since it was discovered by Novoselov et al. [8] in year

2004. Graphene has superior thermal conductivity and therefore would expect to result

higher heat transfer performance as a nanofluid. According to Hamilton and Crosser [9],

when the particle to liquid thermal conductivity ratio of a suspension is above 100, the

particle shape can play a substantial effect on its effective thermal conductivity. More

recently Balandin et al. [10] reported very high value of thermal conductivity of 5000 W/mk

for single-layer graphene. This has generated increased interest among the scientific

community to use this novel material as suspension in base fluid to be used as a heat transfer

fluid.

6
The first study on graphene based nanofluid was simultaneously reported by two researcher

groups, Yu et al. [11] and Baby and Ramaprabhu [12]. Yu et al. [11] experimentally

determined the thermal conductivity of Graphene Oxide based nanofluid and reported 30.2%,

62.3% and 76.8% enhancement in thermal conductivity for 5 vol% Graphene oxide

nanosheets in water, propyl glycol and liquid paraffin respectively. Baby and Ramaprabhu

[12] used functionalized thermal exfoliated graphene oxide (f-TEG) in Deionized (DI) water

and Ethylene glycol (EG) as nanofluid. They found significant increase in thermal

conductivity of water based nanofluid as compared to those with EG. The reported value for

0.056% vol% f-TEG water nanofluid was 14% at 25⁰C and 64% at 50⁰C. Further, in their

study, the authors [13] found 76% enhancement in heat transfer coefficient at 0.01 vol% f-

TEG water nanofluid for a Reynolds number of 4500. In their subsequent work [14] the

thermal performance of Ag/HEG nanofluid are determined and nanofluids was found to be

stable for a period of more than 3 month.

Mehrali et al. [15] prepared water-GNP nanofluids without using surfactant and observed

maximum enhancement of 27.64% in thermal conductivity for 0.1wt% GNP. They

determined the rate of sedimentation of GNPs with time and reported the effect of specific

surface area (SSA) and concentration of sedimentation rate. They also observed increased

viscosity for higher SSA nanofluids.

Effect of temperature on thermal conductivity was first reported by Das et al. [16] for metal

oxide based nanofluids. The authors observed 2 to 4 fold increase in thermal conductivity of

nanofluid as the temperature was increased from 21⁰C to 51⁰C. Subsequently, large number

of researchers carried out study in this area and some of them reported significant

enhancement of thermal conductivities with temperature [12, 17-21] whereas, some have

reported none [11, 22-24].

7
Baby and Ramprabhu [12] observed significant effect of temperature on thermal conductivity

for water- graphene nanofluid. Ijam et al. [17] prepared GNP - glycerol + water nanofluids

and monitored the stability of nanofluids with time. It was found that their nanofluids were

stable for more than 5 months. The study also showed significant effect of temperature on the

thermal conductivity of nanofluids. Wang et al. [18] prepared stable graphene based

nanofluid in ionic liquid without surfactant and reported 15.5% and 18.6% increase in

thermal conductivity at 25⁰C and 65 ⁰C respectively for 0.06 wt% of graphene. They found

decrease in viscosity for graphene based nanofluid as compared to the base fluid. Thermal

conductivity of nanofluid at very high temperature is measured by Liu et al. [19] for

[HMIMM]BF4-graphene nanofluid. Increase in thermal conductivity from 15.2% at 20 ⁰C to

22.9% at 200⁰C for 0.06 wt% GNP nanofluid is observed.

Contrary to above mentioned findings, Yu et al [11] did not observe any increase in thermal

conductivity for graphene oxide nanofluids with temperature. Kole and Dey [22] determined

the thermal conductivity and viscosity at various volume fractions of graphene nanosheets in

water + EG fluid and also reported the insignificant effect of temperature on thermal

conductivity of the nanofluids. The increase in viscosity reported for their nanofluid was up

to 100% for 0.395 vol% loading.

Gupta et al [25] noticed different behaviour of temperature dependency on thermal

conductivity of graphene based nanofluids in comparison with spherical particles nanofluid.

Based on the experimental observations they proposed a possible mechanism of Brownian

motion-percolation hybrid to exist in graphene based nanofluid. The phenomenon of

Brownian motion of nanosheets depends upon the fluid temperature whereas the percolation

of nanosheet is temperature independent phenomenon. This hybrid mechanism explains GNP

8
behaviour in between the metal oxides and carbon nanotubes. A role of percolation and sheet

dynamics in graphene nanofluid is reported by Dhar et al. [26].

Recent studies of, Li et al. [27] and Sonawane et al. [20] respectively with kerosene and

Aviation Turbine fuel (ATF) based nanofluids determines thermo-physical properties of

nanofluid. Li et al [27] experimentally determined thermal conductivity and viscosity of

kerosene- lipophilic Cu nanofluid and reported the effect of surface modification on the

thermal properties. In the study of Sonawane et al. [20] with ATF-alumina nanofluid, the

thermo-physical properties and heat transfer coefficient at various volume fractions were

determined. They found higher increase in viscosity as compared to thermal conductivity at

same particle volume fraction.

A study carried out by Justin et al. [28] on combustion characteristics of graphene based

fuels, indicates higher combustion performance of graphene based nanofuels. They studied

the linear burning rates of nitro-methane in presence of aluminium, silicon oxide and

graphene sheets and reported highest increase in burning rate with graphene sheets. The

authors attributed it to the enhanced burning rate of graphene-nitromethane, due to its

increased thermal conductivity. Pure aluminium particles are used as additive in solid rocket

motor to enhance combustion characteristics. The handling of pure aluminium is very

difficult as it spontaneously gets oxidized in presence of atmosphere and catches fire. As the

heat of combustion of carbon and aluminium is 31.1 kJ/g and 32.8 kJ/g respectively,

graphene could be considered as an alternate option to be used as fuel additive in rocket

engine. Kerosene is an aviation fuel and is also used as a fuel in semi cryogenic engine.

Moreover the use of graphene in fuel will not contribute to any particulate matter of plume

“signature”. It will undergo complete combustion and will result in CO 2.

9
Through many experimental studies on thermal conductivity of graphene based nanofluids

are available in the literature; the studies on convective heat transfer are limited. Very few

researchers have worked on kerosene as base fluid. Literature review also indicates large

disparity among the researchers on the percentage enhancement in thermal conductivity with

respect to its temperature dependency even for the same nanofluid. The disagreement

between these reported values may be attributed to the different techniques used for realizing

nanoparticles and the method of preparing the nanofluid itself as discussed by the authors

[21]. Thus a systematic study with the standardization of experimental method from

nanofluid preparation till measurement is essential to evaluate the true potential of nanofluid

in heat transfer applications. In the best knowledge of the authors, no study has been carried

out so far using kerosene-graphene nanofluid. Thus a systematic study is presented in this

paper for kerosene- GNP nanofluid for its potential application in thrust chamber cooling of

rocket engine.

The current experimental investigation involves preparation of stable kerosene-GNP

nanofluid using various surfactants for stabilization and determination of its thermo-physical

and turbulent flow convective heat transfer properties at different particle mass fraction. Total

heat transfer performance of these nanofluids is evaluated by measuring the pressure drop in

the test section during each test. The study also aims to determine the potential use of

kerosene-GNP nanofluids as a thrust chamber coolant in rocket engine.

2. Experimental Techniques

2.1. Particle size measurement

The particle size of the nanofluids is measured using Malvern Zetasizer, which is used by

many researchers in their study [2, 21]. Zetasizer works based on the principle of Dynamic

Light Scattering (DLS) and the particles are illuminated with a laser source. The fluctuations

10
in the intensity of laser light were detected, recorded and used for particle size determination.

In the present study, Zetasizer is used to compare and assess the stability of nanofluids by

measuring the hydrodynamic diameter (d) distribution of GNPs with time. The hydrodynamic

diameter (d) is the diameter of an equivalent sphere that has the same translational diffusion

coefficient as the particle. Zetasizer estimate the hydrodynamic diameter (d=KT/3πµD) using

Stokes-Einstein Equation. Where K is Boltzmann’s constant, T is absolute temperature, D is

diffusion coefficient.

2.2. Measurements of thermo-physical properties

In the present work, both thermal conductivity and dynamic viscosity of nanofluids are

measured under static condition. Transient hot wire (THW) method for thermal conductivity

measurement of nanofluids was successfully used by many researchers [12-15, 17, 21]. In

current study thermal conductivity is measured using thermal property analyser named KD2-

Pro, with a specified accuracy of ±5%. It works on the principle of transient hot wire method.

The nanofluid sample is kept in a constant temperature bath for the thermal conductivity

measurement at various temperatures.

The dynamic viscosity is measured using Brookfield digital viscometer (model: LVDV-II

pro) equipped with constant temperature bath [21, 22]. In this technique, a controller drives a

spindle that is immersed in nanofluid. The resultant viscous drag generated due to the spindle

rotation is measured during the experiment and the fluid viscosity is determined. The rotation

of spindle for viscosity measurements was maintained at 100 rpm, as it provides the

maximum range of 3.04 cP for viscosity measurements. The accuracy specified for the

equipment is 1% of the maximum measurement range ie; 0.03 cP for the current

measurement setup. The measurement procedure detailed by the authors [21] is followed in

the current study to determine the viscosity of different nanofluids under investigation.

11
2.3. Convective heat transfer setup

The schematic of the closed loop convective heat transfer experimental setup is shown in Fig.

1. The experimental setup consists of a test section, resistively heated by a DC power source,

nanofluid ultrasonication unit, variable flow gear pump, turbine flow meter, heat exchanger, a

differential pressure indicator and data acquisition system. Turbine type flow meter used in

the experiments measures the flow rate with an accuracy of ±0.25%. A variable high current

DC power source of 20 kW (1000A, 20V) is used for resistive heating of test section. Water

cooled plate heat exchanger with cooling capacity of 25 kW is used to cool the fluid after the

test section. The differential pressure indicator with a range of 300 mbar is connected to the

test section for pressure drop measurement. A 30 channel data acquisition system is used to

record surface temperatures as well as inlet and outlet fluid temperature during the test. Test

section is made up of 1.2 m long stainless steel tube having 9.5 mm outer diameter with 0.9

mm thickness. Ten T-type thermocouples are welded on to the test section for measuring the

surface temperatures and two T-type thermocouples each of which are positioned at the inlet

and outlet of the test section respectively for measuring the corresponding fluid temperatures.

The accuracy of T-type thermocouple used in the setup is ±0.5⁰C. Experiments are carried out

in turbulent flow regime. The entrance length (X) for fully developed flow [29] in turbulent

regime can be defined as:

X ≥ 10Di (1)

Di is the inner diameter of the test section. The minimum entrance length estimated for the

current setup is 0.077 m. The tube diameter in the setup is constant everywhere and before

the test section, a length of 0.2 m is provided for the flow to become hydrodynamically fully

developed. An entrance length of 0.5 m, (X /Di = 65) in the test section is taken before

making the measurements for computing heat transfer coefficient, to ensure fully developed

thermal and flow profiles. The test section is insulated with glass wool to ensure negligible
12
heat loss to the ambient. Kerosene used in the present study is Rocket grade kerosene,

without aromatic contents. Property of Rocket grade kerosene is determined and reported by

Deepak et al [30]. Thermal properties of kerosene and GNP at 30⁰C used in the current study

are given in Table 1.

2.4. Experimental procedure

Nanofluid of desired particle mass concentration and quantity is prepared using oleylamine as

surfactant. Thermal conductivity and viscosity of nanofluid is measured using KD2 pro and

Brookfield viscometer respectively. Thermo-physical properties are determined at various

temperatures from 20 ⁰C to 70 ⁰C for each weight percentage and particle size. Samples are

kept at a constant temperature during the measurement using a constant temperature bath.

Nanofluid is filled in the reservoir and is continuously ultrasonicated with the help of

ultrasonic probe, flow cell and peristaltic pump. A variable speed gear pump delivers the

desired volume flow of nanofluid to the test section. The test section is resistively heated with

DC power source. The heated nanofluid after the test section gets cooled near room

temperature using water cooled plate heat exchanger and is emptied into the reservoir. The

process is continued till the attainment of steady state condition. The inlet fluid temperature

to the test section is maintained constant during the test. The experiments are carried out for

different Reynolds number by varying the flow rate and each test is repeated for four times to

ensure repeatability.

After each test, nanofluid is flushed out from the test setup using nitrogen gas. Subsequently,

purging is done with isopropyl alcohol to remove kerosene.

2.5. Uncertainty and data reduction

A series of convective heat transfer experiments are carried out to investigate heat transfer

characteristics of nanofluid at turbulent flow regime. Steady state fluid temperature, surface
13
temperature, current (I) and voltage (V) from DC power source and flow rate are measured

during the experiment for calculating heat transfer coefficient and Nusselt number at various

particle mass concentrations and Reynolds numbers. Measured thermal conductivity and

viscosity at various temperatures are curve-fitted to estimate the values at any intermediate

temperature point. The effective density and specific heat of nanofluid are estimated based on

the physical principle of the mixture rules as follows;

ρnf = Φ ρnp + (1- Φ) ρbf (2)

Cpnf = (Φ ρnpCpnp + (1- Φ) ρbfCpbf)/ρnf (3)

Heat absorbed by the nanofluid in test section is calculated by

Qf = ρnfṼnfCpnf (Tout-Tin) (4)

Where, Tin , Tout are fluid temperature at inlet and outlet of the test section respectively.

Electrical heat supplied to the test section Qe is given as,

Qe = V I (5)

As the value of specific heat of nanofluid is calculated by mixing rule, the correctness of

specific heat is ensured by comparing heat absorbed by the nanofluid, Qf in test section to the

electrical heat supplied, Qe to test section. In all the experiments (Qe - Qf) is found to be

positive and the value is less than 5.9% and this indicated the effectiveness of the insulation

provided on the test section. Reynolds number and Prandtl number of nanofluid is determined

using the expressions

Renf =4ρnfṼnf / πDi µnf (6)

Prnf = µnf Cpnf / knf (7)

Local Heat transfer coefficient, hnf = Qf/ (πDi L (Ts -Tf)) (8)

14
where, Ts and Tf is the local surface and fluid temperature respectively.

Tf = Tin + x/L(Tout -Tin) (9)

Nusselt Number Nunf = hnfDi/knf (10)

Friction factor, f = 2ΔpDi/(ρnf Lu2nf) (11)

Where, Δp is the measured pressure dro and .unf = Ṽnf/( πDi2) is nanofluid velocity at test

section.

The merit number is calculated using heat transfer coefficient and measured pressure drop

and is defined as

Merit Number = (hnf/hbf)/(ΔPnf/ΔPbf) (12)

An uncertainty analysis of the experimental data is carried out and the maximum uncertainty

in all important parameters is presented in Table 2.

3. Results and Discussion

The detailed experimental investigation involved the preparation of kerosene-GNP nanofluids

at various GNP mass concentrations and sizes. Nanofluids are prepared and stabilized using

various surfactants. Elaborate characterization of the nanofluids is carried out to determine

the stability of these nanofluids with time. Measurement of thermo-physical properties along

with convective heat transfer experiments are carried out to investigate the utility of these

nanofluids as a heat transfer fluid. Table 3 presents matrix of experiments carried out in the

present study. Detailed discussions related to the results obtained from the set of experiments

are summarized as follows.

3.1. Synthesis of nanofluid

15
Uniform dispersion of nanoparticle in the base fluid is an important requirement for any

colloidal system to be effectively used for heat transfer application. This has been analysed in

detail in the present work wherein nanofluids are prepared using a two-step technique. Three

catalogue sizes of Graphene Nano Platelets (GNP) 750, 500 and 300m2/g, procured from M/s

XG Sciences, USA are used in the present investigation. Kerosene used in the present study

is rocket grade kerosene used as a fuel in semi cryogenic engine. Initially, water and kerosene

based nanofluids were prepared with different ultrasonication time. The stability of

nanofluids is visually inspected with time and it is observed that, irrespective of

ultrasonication time, GNPs were found to settle immediately (within few minutes) in

kerosene. However, water based nanofluids were visually stable for few hours. As kerosene is

a nonpolar solvent, the dispersion of graphene becomes difficult in kerosene as it forms a

large bulk in organic solvents.

The stability of any colloidal system depends on the balance of repulsive and attractive forces

existing between the particles. The repulsive force must be larger as compared to the

attractive forces between the particles for stable nanofluids. The force between the particles

depends on the ionic concentration near the particles and it can be changed by either

electrostatic or steric stabilization techniques as reported by many researchers [2, 31- 33] to

stabilize nanofluids.

In the present work various surfactants are chosen based on its affinity towards the fluid and

were used to stabilize the GNP-kerosene nanofluid. Initially, based on our previous research

experience [21] Oleic acid was tried for stabilizing 0.05 wt% kerosene - GNP nanofluid but it

could not stabilize the nanofluids and GNPs started settling after few hours. At higher mass

concentrations above 0.1wt%, settling started after few minutes itself. Subsequently many

other surfactants were tried and behavior and stability of nanofluids are visually observed.

Table 4 reports the outcome of the stability study using various surfactants. The kerosene-
16
GNP nanofluids prepared using Oleylamine, Oleic acid and Tween-20 surfactants are shown

in Figure 2. It can be clearly seen that the nanofluid prepared using Oleic acid and Tween-20

are not stable. Oleylamine provides good colloidal stability of GNP in kerosene and is found

to be suitable for longer stability of kerosene-GNP nanofluids. Oleylamine is added in to the

nanofluid using a syringe and the nanofluid is continuously ultrasonicated during the addition

process. The surfactant to particle mass ratio was varied from 0.3 to 1.2 in steps. The stability

of nanofluid was very poor for the mass ratio of less than 0.6. An optimum quantity of

Oleylamine of 0.2 ml in 1 kg of kerosene for 0.05% mass concentration with surfactant to

particle mass ratio of 0.6 was found to yield the maximum visual stability.

Subsequently, nanofluids of different concentration at constant oleylamine to particle mass

ratio of 0.6 are made. Different ultrasonication time of 40 min for 0.005 wt% to 3 hrs for

0.2wt% is employed. The stability of nanofluids is found to be directly related to the

concentration of the GNPs. Nanofluids at lower mass fraction up to 0.05wt% were very

stable (> 4-12 months) as compared to those with higher particle mass concentration of

0.1wt% and 0.2wt% nanofluids for which the stability was found to be around 20-30 days.

3.1.1. Particle size measurement

Nanofluids at 0.05 wt % are prepared for 750 and 500 SSA GNPs. Particle sizing of the

nanofluid are measured with time (days) to determine the stability of nanofluid. The particle

size distribution for the samples is measured using Malvern Zetasizer. All the size

measurement is performed at 25⁰C with a scattering angle of 173 ⁰. Each sample is tested

three times and the mean value is reported here.

Nanofluid from the top portion in the bottle is used as the sample for testing in first day, 30th

day, and at 60th day after preparation and particle size measurement is conducted. Figures 3

and 4 represents the particle size distribution based on intensity measurement from DLS

17
technique for 750 and 500 SSA kerosene-GNP nanofluid respectively. The size (d, nm) given

in figure is hydrodynamic diameter of the GNPs measured by the Zetasizer in nanometer. It

can be seen from the Figs 3 and 4 that intensity curve of 750 SSA nanofluid remains nearly

unchanged even after 60 days of preparation. The mean Z-average value measured for 750

SSA GNP nanofluid is found to vary only from 184.6 to 192.4 in 60 days. Z-average value is

a harmonic intensity averaged particle diameter reported by the measurement system and it is

very sensitive to small changes in the sample, viz particle agglomeration or settling. A

constant value of Z-average seen in the present study indicates highly stable nanofluid. The

particle intensity plot for 500 SSA GNPs nanofluid is slightly changed with time. The mean

Z-average value for 500 SSA nanofluids varies from 442 to 463 in 60 days. The maximum

dispersion in Z average particle size among the three DLS measurements was within 1.2% for

750SSA and 0.9% for 500SSA nanofluid. It can be noticed from these figures that though

both the nanofluids are stable up to 60 days, stability of 750 SSA nanofluid is higher

compared to 500 SSA nanofluid.

3.2. Thermo-physical properties

Heat transfer performance of any heat transfer system depends upon the thermal conductivity

of coolant medium. The increased viscosity due to addition of nanoparticles in the base fluid

increases the pressure requirement of the heat transfer system. Detailed measurements of

thermal conductivity and viscosity are made at 0.005wt%, 0.02wt%, 0.05wt%, 0.1wt%, and

0.2wt% GNPs in kerosene for 750, 500,300 SSA graphene sheets and the results are

presented here.

3.2.1. Thermal conductivity

Thermal conductivity of nanofluid is measured using THW technique. Prior to

measurements, the instrument is calibrated with DI water and glycerine. The sample is kept

18
at a constant temperature of 30⁰C ± 0.25⁰C using a constant temperature bath. To reduce the

effect of convection current outside the sample tube, a special holder is made and the

constant temperature bath is kept switched off during the measurement process. For each

mass fraction, six measurements are taken and all of them fall within ±0.02 W/mK. Mean

value of these reading are presented in the paper.

Ratio of thermal conductivity of kerosene-GNP nanofluid to pure kerosene at various particle

mass concentrations for three different sizes of 750, 500 and 300 SSA is shown in Fig.5. The

ratio of thermal conductivity of nanofluid to base fluid increases with particle loading for all

sizes of GNPs. The enhancement ratio of thermal conductivity of nanofluid to base fluid is

found to be higher for the higher SSA particles as compared to the lower SSA for a range of

particle concentrations. The enhancement ratio at 0.2 wt% concentration for 750, 500, 300

SSA GNPs nanofluid is found to be 1.23, 1.17 and 1.13 respectively. The effect of particle

size on thermal conductivity can be attributed mainly to two reasons, viz, specific surface

area (SSA) and Brownian motion as discussed by Deepak et al [21]. The higher surface area

per unit volume of GNPs will result in increased interaction between the solid particles to the

base fluid and will also enhance the possibility of Brownian motion due to lower mass of

individual particles. The frequent interactions results in higher thermal conductivity and also

explain the reason for the higher enhancement in thermal conductivity for 750 SSA GNPs

nanofluid as compared to the other sizes.

Deepak et al [21] reported 7.4% increases in thermal conductivity for 0.05vol% (equivalent

to 0.25 wt%) kerosene – alumina nanofluid. In the current investigation thermal conductivity

enhancement is 23.2% for 0.2 wt% GNP-kerosene nanofluid. The higher enhancement in

thermal conductivity of kerosene-GNP nanofluid as compared to kerosene- alumina

nanofluid can be explained based on percolation model [26, 34]. According to the model,

19
long chain present in CNT works as interconnecting thermal network which acts as a heat

conducting path. Gupta et al [25] reported similar networks for GNPs. Moreover the thermal

conductivity of graphene is higher as compared to CNT and is expected to have the enhanced

thermal conductivity for GNP based nanofluids. Graphene, a two-dimensional structure with

very high aspect ratio has largest surface area as compared to CNT or other spherical

nanoparticles. Due to the large interface area between the particle and fluid, it has lowest

contact resistance that result in increased thermal conductivity. In addition, due to the shape

of the GNPs as discussed by Hamilton and Crosser [9], higher effective thermal conductivity

of nanofluids is expected.

A bench mark study carried out by the researchers [35], of various organizations have used

Nan’s model [35] to compare their finding and showed a good agreement in the measured

thermal conductivity to the model. According to Nan’s model,

knf / kbf = (3 + φ [2β11 (1-L11 ) + β33 (1-L33 )])/(3 – φ (2β11 L11 + 2β33 L33)) (13)

Where, Lii and φ are the geometrical factor and the volume fraction of particles respectively.

βii is given as

βii=(kp - kbf)/(kbf + Lii (kp-kbf)) (14)

Where, kp is in-plane thermal conductivity [22] of nanoparticle. As the aspect ratio of GNPs

is very high, the values taken is L11=0 and L33 =1.

Zheng and Hong [36] reported a model by modifying the original Yamada-Ota model [37]

with the inclusion of effect of thermal boundary layer (TBR). The model is represented as;

knf /kbf = ( (kx/kbf ) + α - αφ[ 1-(kx/kbf ) ] ) / ( (kx/kbf ) + α + φ[ 1-(kx/kbf ) ] ) (15)

Where, kx=knp/(1+((2knpTBR)/Le)) and α=2φ0.2 Le/d.

In Fig. 6 the comparison of thermal conductivity measurements from the current study with

those calculated based on models by Naan et al. [36] and the Zheng and Hong model [37] for

20
three sizes of GNPs nanofluid are presented in detail. It is to be noted that the TBR value play

a significant role in the modified Yamda and Ota model [38] which is unknown for the

current nanofluid under investigation. Therefore TBR value for the present nanofluids are

estimated using the measured thermal conductivity and is found to be 10 -7 m2 KW-1, for 750

and 500 SSA nanofluid and 0.7x10 -7 m2 KW-1 for 300SSA nanofluid. The value of TBR

estimated is comparable to the value used by other researchers [6, 39]. In the current work,

Le is taken as 1000nm for 750 GNP nanofluids. In the case of 500 and 300 GNP, Le is

calculated in proportionate to its specific surface are per unit volume. Le/d is taken as 400 for

all size GNPs nanofluid.

Figure 7 shows the ratio of thermal conductivity of nanofluid to the base fluid with change in

temperature for various GNP sizes and weight percentage. The ratio of thermal conductivity

for 750 GNPs particle size increases from 1.23 to 1.30 over 20⁰C to 70⁰C temperature range.

It can be noted that for kerosene-alumina nanofluid as reported by Deepak et al. [21], thermal

conductivity ratio was increases from 1.12 to 1.25 (> 2 times) for 13nm particle size in the

25⁰C to 65⁰C temperature range. Such a large enhancement in thermal conductivity with

temperature is not noticed for the current nanofluid. The present observation of lesser

temperature dependence is very similar to the observation made by other researchers [11, 18,

and 19]. It is to be noted that the significant effect of temperature on thermal conductivity

reported by previous researchers is mainly for metallic and ceramic nanofluids and is mainly

attributed to the micro convection caused by Brownian motion of particles in nanofluids at

higher temperature. It is expected that at high temperature, the random motion of nanoparticle

along with the decrease in base fluid viscosity causes increased micro convection and results

in enhanced thermal conductivity. The CNT based nanofluid does not show temperature

dependency [33] due to the network structure as discussed earlier. GNPs used in the current

study has minimum 2.5 nm thickness sheet with varying length from 100nm to 2000nm. The
21
smaller GNPs would participate in Brownian motion and result in enhanced thermal

conductivity with temperature. However the longer GNPs will not produce Brownian motion

and the thermal conductivity increase in such case is due to percolation theory [25, 34].

Percolation does not depend upon temperature, hence thermal conductivity of these GNPs

does not result increase in thermal conductivity with temperature.

In the present study the ratio of thermal conductivity increases from 1.23 to 1.30 for 750

GNPs, 1.14 to 1.18 for 500 GNPs and 1.11 to 1.14 for 300 GNPs particle size over the 20⁰C

to 70⁰C temperature range. The effect of temperature on thermal conductivity of nanofluids

is higher for 750 GNPs nanofluid as compared to the others. This can be attributed to the

different sized GNP particles present in the nanofluids. The smaller sized particle undergoes

random movement and thereby contributes to the Brownian motion, whereas with bigger

sized particle, network like chain structure, as postulated in percolation model could be

dominant. Gupta et al [25] also observed the similar hybrid behaviour of GNPs nanofluid

and reported that the thermal conductivity of Graphene nanofluids lies in between CNT and

metallic nanofluids.

3.2.2. Stability of nanofluids

The consistency in the measured thermal conductivity of the nanofluid with time indicates the

stability of nanofluids. Thermal conductivity of nanofluids at 30⁰C temperature are measured

periodically and presented in Fig. 8. It can be seen that the thermal conductivity of 0.1wt%

and 0.2wt% nanofluids indicates marginal drop over time for initial 20 days and remain

nearly constant afterwards. It is to be noted that the thermal conductivity of nanofluids at

lower concentration of 0.005 wt%, 0.02 wt% and 0.05wt% does not show any drop with time

and remain almost constant. This trend from thermal conductivity indicates very high

stability for the current kerosene- GNP nanofluids and is considered to be a prime

requirement of such fluid to be used for heat transfer application in rocket engine. This
22
observation is in line with the observation made using particle size distribution presented in

section 3.1.1 for 0.05 wt% kerosene- GNP nanofluid.

3.2.3. Dynamic viscosity

Before measuring the viscosity of nanofluids, viscosity of pure kerosene is measured at

different temperatures. Nanofluids of particle mass fraction 0.005%, 0.02%, 0.05%, 0.1% and

0.2% are tested for the dynamic viscosity for three particle sizes along with pure kerosene.

Ratio of dynamic viscosity of nanofluids to the base fluid at various fluid temperatures and

particle concentrations for 300, 500 and 750 SSA particle size nanofluids is presented in Fig.

10. It is observed that the dynamic viscosity of nanofluid is higher as compared to the base

fluid and the enhancement in viscosity increases with particle loading and specific surface

area (SSA). The increase in viscosity with particle concentration is due to the formation of

agglomeration and clustered structure, at higher concentration, and could result in increased

internal shear stress for the nanofluid. The increase in dynamic viscosity for higher SSA

GNPs is large as compared to the lower SSA GNPs nanofluids. Higher surface area led to

higher interfacial resistance with the fluid layer and result in increased viscosity for 750 SSA

GNPs nanofluid as compared to others. The ratio of dynamic viscosity of nanofluid to the

base fluid is 1.076, 1.068 and 1.06 for 750, 500 and 300 GNP nanofluid respectively at 0.2wt

% and 30 ⁰C.

The effect of temperature on the viscosity of nanofluids is investigated by measuring

dynamic viscosity of 0.2 wt% nanofluid at various temperatures ranging from 20⁰C to 70⁰C.

Dynamic viscosity of nanofluid for three sizes of GNP nanofluids along with pure kerosene is

plotted in Fig. 11. The viscosity decreases rapidly with rise in temperature and display an

asymptotic behaviour. For the base fluid, as the temperature increases, due to thermal

expansion viscous shear stress goes down resulting in lower viscosity at high temperature.

23
The decrease in nanofluid viscosity with increase in temperature is expected due to the

weakening of the interparticle and intermolecular adhesion forces and similar trends have

also been observed in almost all type of nanofluids by many researchers [21, 32].

3.3. Convective heat transfer

While an increase in effective thermal conductivity is an indication of improved heat-transfer

behaviour of nanofluids, the net benefit of nanofluid as heat transfer fluids is evaluated

through the heat transfer coefficients. The convective heat transfer performance of any fluid

depends upon various physical and thermo-physical properties. Though the enhanced thermal

conductivity of nanofluid will result in reduced resistance to thermal diffusion in the laminar

sub layer, increased viscosity of nanofluid could increase the thickness of sub layer and in

turn increase the thermal resistance to heat transfer.

The test setup and experimental procedure used in current study is validated with pure

kerosene and is also used for the determination of convective heat transfer performance of

kerosene-alumina nanofluid by the authors [30].

Detailed investigation on convective heat transfer characteristics of nanofluid using the

closed loop experimental test rig is carried out for 0.005wt%, 0.05wt% and 0.2wt% particle

concentration kerosene-GNP nanofluid. Effect of particle specific surface area on heat

transfer is experimentally studied for 750, 500 and 300 SSA GNPs nanofluids. Thermo-

physical properties at average film temperature ((Ts+Tf)/2) is used for the estimation of heat

transfer coefficient from the experimental data. Each experiment is repeated four times and

the mean values are used for the subsequent analysis. The maximum dispersion in the

calculated heat transfer coefficients among the experiments for any particular case is within

±2.7%.

24
Figure 11 shows the heat transfer coefficient for 750, 500 and 300 SSA GNPs nanofluids

derived from the experimental data at various particle concentrations and Reynolds numbers.

It can be clearly seen that kerosene- GNP nanofluids show enhanced heat transfer properties

as compared to the pure kerosene at all Reynolds numbers. As expected, the heat transfer

coefficient of kerosene-GNP nanofluid is found to increase with Reynolds number and

particle concentrations. Higher increase in heat transfer coefficient is noticed for higher SSA

nanofluids at higher concentration. This observation is similar to many other researchers [30-

32, 40] for their nanofluids. Highest increase in heat transfer coefficient is noticed for 0.2wt%

750 SSA kerosene-GNP nanofluid.

Ding et al. [4] proposed the reason for higher heat transfer coefficient observed using

nanofluid due to the increase in effective thermal conductivity (k) of nanofluid and the

decreases in thickness of the thermal boundary layer (δ); together it results in augmentation in

heat transfer coefficient (h=k/δ). The hypothesis of thinning of boundary layer was developed

based on the assumption of chaotic motion of nanoparticles in the nanofluid, which tends to

disturb the boundary layer, resulting in thinning of the same. This trend represented by Ding

et al [4] is also discussed by Aravind et al [41] and in authors opinion; it is true in the present

investigation too. The large enhancement observed in convective heat transfer is due to

increased thermal conductivity, particle re-arrangement; shear induced thermal conduction

enhancement and reduction in boundary layer thickness due to presence of GNPs as

discussed by Aravind et al [41]. The possible reasons for boundary layer thickness reduction

include particle migration in nanofluids due to shear action, viscosity gradient, and Brownian

motion as discussed by Phillips et al [42] and Ding et al [43]. Further as suggested by Xuan

and Li [44], the increase in effective thermal conductivity due to dynamic condition could be

another major factor for significant enhancement in convective heat transfer coefficient. It

has to be recalled that the thermal conductivity measurements carried out in the present study
25
is at static conditions and significant effect of shear could exist under the flowing condition

which would improve the thermal conductivity of nanofluid during convective experiments.

Figure 12 shows the ratio of convective heat transfer coefficient of nanofluid to base fluid at

various wt% and Reynolds number range. Higher enhancement is noticed for higher SSA

nanofluid for all the particle mass fractions. The higher performance of lower sized particle

(higher specific surface area) was observed by many researchers in the past [30-32, 40]. The

maximum enhancement noticed is 49% for 750 SSA nanofluid and 38% for 500 SSA

nanofluid at 0.2 wt% of GNPs in kerosene.

3.4. Pressure drop and friction factor

Though the current investigation show enhanced heat transfer coefficient of the kerosene-

GNP nanofluid, it is expected that the increased viscosity of nanofluids could also result in

higher pressure drop. Higher pressure drop may limit nanofluid applicability in thrust

chamber cooling as it may necessitate a bigger sized pump to push the fluid though the

regenerative passage in thrust chamber.

The friction factor for kerosene- GNP nanofluid at various particle mass concentration and

sizes is computed from the measured pressure drop. It is to be noted that the increase in

viscosity of the current nanofluids are not very significant. Figure 13 shows the variation of

friction factor calculated in the present study along with the correlation developed using the

measurements at various Reynolds number. The correlation for friction factor is obtained in

present study by curve fitting all the data points and is expressed as;

f = 0.26Re-0.22 (16)

and is valid over a range of Re = 6700 to 28000.

It can be noted that the maximum dispersion in the friction factor from the above correlation

is within 11%. The above correlation is very similar to Blasius correlation (f = 0.314 Re -0.25),

and shows that a homogeneous fluid correlation can be used to accurately predict pressure
26
drop characteristics of the nanofluids as used in the current study. Though the nanofluid

friction factor obtained from the present study does not significantly differ from the pure

fluid, a clear trend of higher friction factor is observed for higher SSA and for higher

concentration kerosene-GNP nanofluids. Maximum increase in friction factor is observed for

0.2wt% 750 SSA kerosene-GNP nanofluid. It is to recall that the trend observed in friction

factor is very similar to the trend observed in heat transfer coefficient as discussed in section

3.3.

The pressure drop and friction factor depends upon the Reynolds number and GNP

concentration. As expected, similar to the pure fluid, the friction factor decreases with

increase in Reynolds number. Table 5 shows the increase in friction factor at various GNP

sizes and concentrations for Reynolds number range of 6700-28000. It can be noted that the

higher enhancement in friction factor is noticed for 750 GNP nanofluids and it increases with

particle concentration. At higher particle concentration, the density of fluid changes and

results in higher viscous drag thereby increasing the friction factor. The dynamic viscosity of

750 SSA nanofluid is also noticed higher compared to other particle size as discussed in

section 3.2.3. The maximum enhancement in friction factor noticed in the present study is

21% for 0.2wt%, 750 SSA kerosene-GNP nanofluid.

3.5. Total heat transfer performance

The total heat transfer performance of kerosene- GNP nanofluid is determined by Merit

number, comparing the heat transfer augmentation of nanofluid to the pressure penalty due to

increased density and the viscosity of nanofluid. Merit number is used by Deepak et al [30]

and Yu et al. [45] for evaluating the total heat transfer performance of kerosene- Al2O3 and

water- SiC nanofluid respectively. It is defined as the ratio of heat transfer enhancement to

the increase in pressure drop and the expression is given in Eq. (12).

27
Figures 14 show the heat transfer performance of 750 and 500 SSA nanofluid based on merit

number with respect to Reynolds number for 0.05% and 0.2% GNP mass concentrations. For

nanofluid with particle mass fraction of 0.05%, Merit number is found to be lower than one

and indicates lower performance of these nanofluids as a coolant medium. Merit Number is

found to be above unity for 0.2% mass concentration nanofluid for both sizes of GNPs.

Figure 15 presents the heat transfer coefficient of nanofluid with respect to the measured

pressure drop. A solid line shown in figure represents the heat transfer coefficient of pure

kerosene with respect to pressure drop. It is to be noted that the data point lies left to the solid

line indicate higher heat transfer performance of nanofluid compared to pure kerosene for an

identical value of pressure drop. Higher heat transfer coefficient with minimum pressure drop

is observed for 0.2wt% nanofluid for all sizes of GNPs. The study clearly suggests the total

heat transfer performance of 0.2wt% GNP-kerosene nanofluids to be higher than that of pure

kerosene and can be used as a better coolant in regenerative passage of semi-cryo thrust

chamber.

4. Conclusion

The present study aims at syntheses, characterization and assessing the potential use of

kerosene-GNP nanofluid for thrust chamber cooling in a semi-cryogenic rocket engine.

Stable kerosene-GNP nanofluids are prepared using Oleylamine surfactant. Detailed

measurements are made to determine the effect of particle mass concentration, size and

temperature on the thermo-physical properties of kerosene-GNP nanofluid. Following are the

major outcome of the studies.

1. An optimum oleylamine to particle mass ratio of 0.6 is determined after a series of trials

for enhanced stability.

28
2. Stability of nanofluids is accessed by measuring thermal conductivity along with particle

size and time. Both thermal conductivity and particle size measurements show good

stability of current nanofluids in presence of surfactant.

3. Enhancement in thermal conductivity and viscosity of nanofluids is observed with

particle loading and sizes. The highest thermal conductivity enhancement ratio of 1.3,

1.18 and 1.14 is noticed for 750, 500 and 300 SSA for 0.2wt% kerosene-GNP nanofluid

respectively. Similarly, the increase in viscosity ratio is limited to 1.076 for 750 SSA at

0.2wt% kerosene-GNP nanofluid.

4. Thermal conductivity enhancement from 23% at 20⁰C to 29% at 70⁰C is noticed for

0.2wt% 750SSA nanofluid. Not so significant effect of fluid temperature noticed for

GNP-kerosene nanofluid compared to spherical particle based nanofluid. The lower

temperature dependency noticed is collaborated due to the presence of various sizes

sheet in the GNPs. Brownian motion in smaller size sheets and thermal conduction in

longer chain structure plays important role for enhanced thermal conductivity of

kerosene-GNP nanofluids.

5. Convective heat transfer performance of kerosene- GNPs nanofluids at turbulent flow

regime is also carried out at various particle loading and sizes. Experimental data

indicate enhanced heat transfer performance of GNP-kerosene nanofluid as compared to

pure kerosene and the maximum enhancement ratio observed is 1.49, 1.38 for 750 and

500 SSA GNPs respectively at 0.2% mass concentration nanofluid. Higher enhancement

is noticed for higher SSA nanofluid.

6. Based on the measured pressure drop during the convective heat transfer experiments a

correlation for friction factor is developed, which lies within ±10% for all the sizes and

mass concentration of kerosene-GNP nanofluids.

29
7. Detailed analysis of convective heat transfer coefficient and measured pressure data

shows Merit number to be above unity for nanofluids with particle mass concentration

above 0.2wt% for 750 and 500 SSA kerosene-GNP nanofluids. Merit number above

unity indicates potential use of these nanofluids as a suitable heat transfer fluid in

regenerative cooling of semi-cryogenic rocket engine.

Acknowledgement

The authors acknowledge the help of Shri. Jophy Peter, Thermal Engineering Division,

LPSC, ISRO, Trivandrum in setting up measurement facilities for the experiments.

30
References:

[1] S. U. S Choi, J. A. Eastman. “Enhancing thermal conductivity of fluids with

nanoparticles.” Report submitted to Argnone National Laboratory, Illinous, (1995),

ANL/MSD/CP-84938.

[2] S. K. Das, S. U. S.Choi, W. Yu, T. Pradeep, “Nanofluids-Science and Technology.”

John Wiley & Sons, 2008.

[3] Choi, S. U. S., Z. G. Zhang, Wu Yu, F. E. Lockwood, and E. A. Grulke. "Anomalous

thermal conductivity enhancement in nanotube suspensions." Applied physics letters

79, no. 14 (2001): 2252-2254.

[4] Ding, Yulong, Hajar Alias, Dongsheng Wen, and Richard A. Williams. "Heat transfer

of aqueous suspensions of carbon nanotubes (CNT nanofluids)." International Journal

of Heat and Mass Transfer 49, no. 1 (2006): 240-250.L

[5] Aravind, SS Jyothirmayee, Prathab Baskar, Tessy Theres Baby, R. Krishna Sabareesh,

Sumitesh Das, and S. Ramaprabhu. "Investigation of structural stability, dispersion,

viscosity, and conductive heat transfer properties of functionalized carbon nanotube

based nanofluids." The Journal of Physical Chemistry C 115, no. 34 (2011): 16737-

16744.

[6] Harish, Sivasankaran, Kei Ishikawa, Erik Einarsson, Shinya Aikawa, Shohei Chiashi,

Junichiro Shiomi, and Shigeo Maruyama. "Enhanced thermal conductivity of ethylene

glycol with single-walled carbon nanotube inclusions." International Journal of heat and

mass transfer 55, no. 13 (2012): 3885-3890.

[7] Horton, Mark, Haiping Hong, Chen Li, Bo Shi, G. P. Peterson, and Sungho Jin.

"Magnetic alignment of Ni-coated single wall carbon nanotubes in heat transfer

nanofluids." Journal of Applied Physics 107, no. 10 (2010): 104320.

31
[8] Novoselov, Kostya S., Andre K. Geim, S. V. Morozov, D. Jiang, Y_ Zhang, S. V.

Dubonos, I. V. Grigorieva, and A. A. Firsov. "Electric field effect in atomically thin

carbon films." science 306, no. 5696 (2004): 666-669

[9] R. L. Hamilton and O. K. Crosser, Thermal conductivity of heterogeneous two

component systems, I & EC Fundamentals Vol.1, No. 3 (1962): 187-191.

[10] Balandin, Alexander A., Suchismita Ghosh, Wenzhong Bao, Irene Calizo, Desalegne

Teweldebrhan, Feng Miao, and Chun Ning Lau. "Superior thermal conductivity of

single-layer graphene." Nano letters 8, no. 3 (2008): 902-907.

[11] Yu, Wei, Huaqing Xie, and Wei Chen. "Experimental investigation on thermal

conductivity of nanofluids containing graphene oxide nanosheets." Journal of Applied

Physics 107, no. 9 (2010): 094317.

[12] Baby, Tessy Theres, and S. Ramaprabhu. "Investigation of thermal and electrical

conductivity of graphene based nanofluids." Journal of Applied Physics 108, no. 12

(2010): 124308.

[13] Baby, Tessy Theres, and Sundara Ramaprabhu. "Enhanced convective heat transfer

using graphene dispersed nanofluids." Nanoscale research letters 6, no. 1 (2011): 1-9.

[14] Baby, Tessy Theres, and Sundara Ramaprabhu. "Synthesis and nanofluid application of

silver nanoparticles decorated graphene." Journal of Materials Chemistry 21, no. 26

(2011): 9702-9709.

[15] Mehrali, Mohammad, Emad Sadeghinezhad, Sara Tahan Latibari, Salim Newaz Kazi,

Mehdi Mehrali, Mohd Nashrul Bin Mohd Zubir, and Hendrik Simon Cornelis

Metselaar. "Investigation of thermal conductivity and rheological properties of

nanofluids containing graphene nanoplatelets." Nanoscale research letters 9, no. 1

(2014): 1-12.

32
[16] S. K. Das, N. Putra, P. Thiesen, W. Roetzel, Temperature dependence of thermal

conductivity enhancement for nanofluids, Journal of Heat Transfer, 125 (2003): 567-

574.

[17] Ijam, Ali, A. Moradi Golsheikh, R. Saidur, and P. Ganesan. "A glycerol–water-based

nanofluid containing graphene oxide nanosheets." Journal of Materials Science 49, no.

17 (2014): 5934-5944.

[18] Wang, Fuxian, Lijuan Han, Zhengguo Zhang, Xiaoming Fang, Jingjing Shi, and Wenshi

Ma. "Surfactant-free ionic liquid-based nanofluids with remarkable thermal

conductivity enhancement at very low loading of graphene." Nanoscale research letters

7, no. 1 (2012): 1-7.

[19] Liu, Jian, Fuxian Wang, Long Zhang, Xiaoming Fang, and Zhengguo Zhang.

"Thermodynamic properties and thermal stability of ionic liquid-based nanofluids

containing graphene as advanced heat transfer fluids for medium-to-high-temperature

applications." Renewable Energy 63 (2014): 519-523.

[20] S. Sonawane, K. Patankar, A. Fogla, B. Puranik, U. Bhandarakar, S. Sunil Kumar, “An

experimental investigation of thermo-physical properties and heat transfer performance

of AL2O3-Aviation Turbine Fuel nanofluids.” Applied Thermal Engineering 31 (2011):

2841-2849.

[21] Deepak Kumar Agarwal, Aravind Vaidyanathan, and S. Sunil Kumar. "Synthesis and

characterization of kerosene–alumina nanofluids." Applied Thermal Engineering 60,

no. 1 (2013): 275-284.

[22] Kole, Madhusree, and T. K. Dey. "Investigation of thermal conductivity, viscosity, and

electrical conductivity of graphene based nanofluids." Journal of Applied Physics 113,

no. 8 (2013): 084307.

33
[23] E. V.Timofeeva, A. N. Gavrilov, J.M. McCloskey, Y.v. Tolmachev, “Thermal

conductivity and particle agglomeration in Alumina nanofluids: Experiments and

theory.” Physics Review letter E76 061203-1- 16 (2007).

[24] Y. S. Ju, J. Kim, Ming-Tsung Hung, “Experimental study of heat conduction in aqueous

suspensions of Aluminum Oxide nanoparticles.” Journal of Heat Transfer 130 (2008):

092403-1-6.

[25] S.S Gupta, et al “Thermal conductivity enhancement of nanofluids containing graphene

nanosheets”. Journal of Applied Physics 110 (2011): 084302

[26] P Dhar, S. S. Gupta, S. Chakaraborty, A. Pattamatta, S. K. Das, “ The role of

percolation and sheet dynamics heat conduction in poly dispersed graphene nanofluids.”

Physics Review letter 163114 (2013).

[27] D. Li, W. Xie, W. Fang, “Preparation and properties of copper-oil-based nanofluids.”

Nanoscale Research Letters , 6:373 (2011).

[28] Justin L. Sabourin , Daniel M. Dabbs , Richard A. Yetter , Frederick L. Dryer, Ilhan A.

Aksay “Functionalized graphene sheet colloids for enhanced fuel/ propellant

combustion.” ACS Nano, (2009): 3 (12), pp 3945–3954, DOI: 10.1021/nn901006w

[29] Incropera Frank P., DeWitt David P., “Fundamental of heat and mass transfer.” USA,

John Wiley & Sons. Ed 7, (2011).

[30] Deepak Kumar Agarwal, Aravind Vaidyanathan, and S. Sunil Kumar. “Investigation on

convective heat transfer behaviour of kerosene-Al2O3 nanofluid" Applied Thermal

Engineering 84, no. 1 (2015): 64-73.

[31] Wang, Xiang-Qi, and Arun S. Mujumdar. "Heat transfer characteristics of nanofluids: a

review." International journal of thermal sciences 46, no. 1 (2007): 1-19.

[32] K. Khanafer, K. Vafai, A critical synthesis of thermo physical characteristics of

nanofluids, International Journal of Heat and Mass Transfer, 54 (2011): 4410-4428.

34
[33] S. K. Das, S.U.S Choi, H. E. Patel, “Heat transfer in nanofluids - a review (2006).” Heat

Transfer Engineering 27 (10) (2006): 3-19.

[34] Sastry, N N Venkata, Avijit Bhunia, T. Sundararajan, and Sarit K. Das. "Predicting the

effective thermal conductivity of carbon nanotube based nanofluids." Nanotechnology

19, no. 5 (2008): 055704.

[35] J. Buongiomo, D. C Venerus, N. Prabhat, T. Mckrell and J. Townsend, “A benchmark

study on the thermal conductivity of nanofluids.” Journal of Applied Physics 106 09312

(2009): 1-14.

[36] C. W. Nan, Z. Shi, Y. Lin, “A simple model for thermal conductivity of carbon

nanotube-based composites.” Chemical Physics Letters 375, (2003): 666-669.

[37] Zheng, Yingsong, and Haiping Hong. "Modified model for effective thermal

conductivity of nanofluids containing carbon nanotubes." Journal of Thermophysics and

Heat Transfer 21, no. 3 (2007): 658-660.

[38] Yamada, Etsuro, and Terukazu Ota. "Effective thermal conductivity of dispersed

materials." Wärme-und Stoffübertragung 13, no. 1-2 (1980): 27-37.

[39] Harish, Sivasankaran, Kei Ishikawa, Shohei Chiashi, Junichiro Shiomi, and Shigeo

Maruyama. "Anomalous thermal conduction characteristics of phase change composites

with single-walled carbon nanotube inclusions." The Journal of Physical Chemistry C

117, no. 29 (2013): 15409-15413.

[40] S. S. J. Aravind, S. Ramaprabhu, “Graphene weapper multiwalled carbon nanotubes

dispersed nanofluids for heat transfer applications.” Journal of Applied Physics 112,

(2012): 124304.

[41] S. S. J. Aravind, S. Ramaprabhu, “Graphene- multiwalled carbon nanotube-based

nanofluids for improved heat dissipation.” Royal Society of Chemistry Advances, 3,

(2013): 4199-4106.
35
[42] Ronald J. Phillips, , Robert C. Armstrong, Robert A. Brown, Alan L. Graham, and

James R. Abbott. "A constitutive equation for concentrated suspensions that accounts

for shear‐ induced particle migration." Physics of Fluids A: Fluid Dynamics (1989-

1993) 4, no. 1 (1992): 30-40.

[43] Ding, Yulong, Hajar Alias, Dongsheng Wen, and Richard A. Williams. "Heat transfer

of aqueous suspensions of carbon nanotubes (CNT nanofluids)." International Journal

of Heat and Mass Transfer 49, no. 1 (2006): 240-250.

[44] Y. Xuan, Q. Li, Investigation on convective heat transfer and flow features of

nanofluids, Journal of Heat Transfer 125, (2003): 151.

[45] Yu, W., France, David M., Smith, David S., Singh, D., Timofeeva, Elena V., Routbort,

Jules L., Heat transfer to a silicon carbide/water nanofluid, International Journal of Heat

and Mass Transfer 52, (2009): 3606-3612.

36
List of figures

Figure 1 Schematic of convective heat transfer setup

Figure 2 Kerosene- GNP nanofluid with (a) Oleylamine (b) Oleic acid (c) Tween-20

Figure 3 Particle size distribution of 750 SSA 0.05 wt% kerosene-GNP nanofluid with

time (days)

Figure 4 Particle size distribution of 500 SSA 0.05 wt% kerosene- GNP nanofluid with

time (days)

Figure 5 Effect of particle size (SSA) on thermal conductivity of kerosene- GNP

nanofluid at various mass concentrations at 30 ⁰C

Figure 6 Comparison of measured thermal conductivity of kerosene-GNP nanofluid

with theoretical models

Figure 7 Effect of temperature on thermal conductivity ratio of kerosene-GNP

nanofluids to kerosene at various particle concentration and sizes

Figure 8 Thermal conductivity of 750 SSA kerosene- GNP nanofluid with time (days)

Figure 9 Effect of particle size on dynamic viscosity of kerosene-GNP nanofluid at

various particle mass concentrations at 30⁰C

Figure 10 Effect of temperature on dynamic viscosity of kerosene-GNP nanofluid at

0.2wt %

Figure 11 Variation in convective heat transfer coefficient with Reynolds number

Figure 12 Variation in ratio of heat transfer coefficient of nanofluid to base fluid with

Reynolds number for various particle size and concentrations

Figure 13 Variation in friction factor of nanofluids with Reynolds number at various

particle size and concentrations

Figure 14 Variation in Merit number with Reynolds number for various particle size and

concentrations of nanofluids
37
Figure 15 Variation in heat transfer coefficient with pressure drop for various particle

size and concentrations of kerosene-GNP nanofluids

List of Tables

Table 1 Thermal properties of kerosene and GNP

Table 2 Maximum uncertainty in experimental parameters

Table 3 Matrix of experiments

Table 4 Stability using various surfactant

Table 5 Percentage increases in pressure drop of kerosene-GNP nanofluid with

temperature

38
 Table 1

ρ (kg/m3) Cp (J/kgk) k(W/mk)

Kerosene 809 2093 0.104
GNP 2300 420 2000

39
 Table 2

Parameter Maximum uncertainty (%)

k 5

µ 4

Re 4.9

Pr 7.1

h 6.8

ΔP 5

Merit
8.5
Number

f 5.2

40
 Table 3

Measurement
Weight % SSA (g/mm2) Temperature, ⁰C Re
parameters
Thermal 0.005, 0.02,0.05,
750, 500, 300 20, 30, 50, 70 --
conductivity 0.1, 0.2
0.005, 0.02,0.05,
Viscosity 750, 500, 300 20, 30, 50, 70 --
0.1, 0.2
Convective 6700-
0.005, 0.05, 0.2 750, 500, 300 ---
heat transfer 28000
Friction 6700-
0.005, 0.05, 0.2 750, 500, 300 ----
factor 28000

41
 Table 4

Surfactant Observation in stability

Stable for few hours (4-5 hrs) for lower concentration
Oleic acid
Poor stability (within a 1 hrs) for higher concentration

TritonX100, Tween20, Sticks on Probe and Cylinder surfaces

MERPOL Stability very poor
Hexadecyl trimethyl
Stable for few hours in all concentrations
ammonium bromide
Cetylpyridinium chloride,
Poor stability even for lower concentrations ( <1 hrs)
Kolliphor
Stable for few hours (1-2 hrs) at lower concentration
Sorbitan monooleate
Poor stability (within a 20-30 min) at higher concentration
Highly stable for more than 2 month for 0.005% solution
Oleyamine
Stability for few days at higher concentrations.

42
 Table 5

Concentration Percentage
GNP size
(wt%) increment
300 0.005 0-8
300 0.05 8-12
300 0.2 11-13
500 0.005 2-10
500 0.05 10-15
500 0.2 15-18
750 0.005 3-11
750 0.05 14-18
750 0.2 16-21

Highlights

1. Effect of various surfactants on stability of GNP/ kerosene nanofluid and

determination of suitable surfactant with optimum quantity.
2. Determination of its stability by DLS and thermal conductivity measurements
with time.
3. Discussion on the mechanisms responsible for temperature dependency on
thermal conductivity of nanofluids.
4. Effect of GNP size and mass concentration on thermo-physical properties of
these nanofluids.
5. Determination of convective heat transfer performance along with pressure drop
characteristics of these nanofluids at turbulent flow regime.

43
Figure1

Fig. 1
Figure2

Fig. 2
Figure3

10

1st day
8
30th day

Intensity (%)
6 60th day

4 Z-Average (d,mm)
1st day 184.6
30th day 190.1
2 60th day 192.4

0
0 500 1000 1500 2000
Size (d, nm)
Figure4

14
1st day
12
30th day
10 60th day

Intensity (%)
8 Z-Average (d,mm)
1st day 442.2
30th day 456.8
6 60th day 463.0

0
0 500 1000 1500 2000
Size (d, nm)
Figure5

1.3

Thermal Conductivity Ratio

1.2

1.1
SSA 750
1 SSA 500
SSA 300
0.9
0 0.05 0.1 0.15 0.2 0.25
Φ (wt%)
Figure6

1.3
SSA 750

Thermal Conductivity Ratio

1.25 SSA 500
SSA 300
1.2
SSA-750 (Nan et al [35])
1.15 SSA-500 (Nan et al [35])
SSA-300 (Nan et al [35])
1.1
SSA-750 (Yamada-Ota [36])
1.05 SSA-500 (Yamada-Ota [36])
SSA-300 (Yamada-Ota [36])
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Φ (wt%)
Figure7

1.35

Thermal Conductivity Ratio

1.3
SSA 750, 0.005wt%
1.25 SSA 750, 0.05wt%
SSA 750, 0.2wt%
1.2
SSA 500, 0.005wt%
1.15 SSA 500, 0.05wt%
SSA 500, 0.2wt%
1.1
SSA 300, 0.005wt%
1.05 SSA 300, 0.05wt%
SSA 300, 0.2wt%
1
0 20 40 60 80 100 120 140
Temperature ⁰C
Figure8

0.1350

Thermal Conductivity (W/mk)

0.1280
0.005 wt%
0.1210 0.02 wt%
0.05 wt%
0.1140
0.10 wt%

0.1070 0.2 wt%

0.1000
0 10 20 30 40 50 60 70 80 90 100
Number of Days
Figure9

1.08

Dynamic Viscosity Ratio

1.06

1.04
SSA 750
1.02 SSA 500
SSA 300
1
0 0.05 0.1 0.15 0.2 0.25
Φ (wt%)
Figure10

1.8
Kerosene
1.6 SSA 750

Dynamic Viscosity (cP)

1.4 SSA 500
SSA 300
1.2

0.8

0.6
10 30 50 70
Temperature ⁰C
Figure11

5000
4500
4000
3500 SSA 300, 0.2%
SSA 300, 0.05%

h (w/m2K)
3000 SSA 300, 0.005%
2500 SSA 500, 0.005%
2000 SSA 500, 0.05%
SSA 500, 0.2%
1500 SSA 750, 0.05%
1000 SSA 750, 0.005%
500 SSA 750, 0.2%
Pure Kerosene
0
0 10000 20000 30000 40000 50000
Re
Figure12

2
1.8
SSA 300, 0.2%
1.6
SSA 300, 0.05%
1.4
SSA 300, 0.005%
1.2

hnf/hbf
SSA 500, 0.2%
1
SSA 500, 0.05%
0.8
SSA 500, 0.005%
0.6 SSA 750, 0.2%
0.4 SSA750, 0.05%
0.2 SSA750, 0.005%
0
0 10000 20000 30000 40000 50000
Re
Figure13

0.05
Current Correlation
0.045 SSA 300 0.2%
SSA 500 0.2%
0.04
SSA 750 0.2%

Friction Factor
0.035 SSA 300 0.05%
SSA 500 0.05%
+11%
0.03 SSA 750 0.05%
SSA 300 0.005%
0.025
- 11%
SSA 500 0.005%

0.02 SSA 750 0.005%

Pure Kerosene
0.015
0 15000 30000 45000 60000 75000
Re
Figure14

1.6

1.4 SSA 300 0.05%

SSA 500 0.05%

Merit Number
1.2
SSA 750 0.05%
1 SSA 300 0.2%
0.8 SSA 500 0.2%
SSA 750 0.2%
0.6

0.4
0 20000 40000
Re
Figure15

5000
4500

Heat Transfer Coefficent (W/m2K)

4000
3500 750 SSA 0.2%
3000 SSA 500 0.2%
2500 300 SSA 0.2%
2000 750 SSA 0.05%
1500 500 SSA 0.05%
1000 300 SSA 0.05%
500 Pure Kerosene
0
0 100 200 300
Pressure Drop (mbar)