Measurement and Model Correlation of Specific

Heat Capacity of Water-Based Nanofluids With

Silica, Alumina and Copper Oxide Nanoparticles

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Citation O’Hanley, Harry, Jacopo Buongiorno, Thomas McKrell, and Lin-wen

Hu. “Measurement and Model Correlation of Specific Heat Capacity
of Water-Based Nanofluids With Silica, Alumina and Copper Oxide
Nanoparticles.” ASME 2011 International Mechanical Engineering
Congress and Exposition (IMECE 2011). In Volume 10: Heat and
Mass Transport Processes, Parts A and B, 1209-1214.

As Published http://dx.doi.org/10.1115/IMECE2011-62054

Publisher ASME International

Version Author's final manuscript

Citable link http://hdl.handle.net/1721.1/84546

Terms of Use Creative Commons Attribution-Noncommercial-Share Alike 3.0

Detailed Terms http://creativecommons.org/licenses/by-nc-sa/3.0/

 Proceedings of the ASME 2011 International Mechanical Engineering Congress & Exposition
IMECE2011
November 11-17, 2011, Denver, Colorado, USA

IMECE2011-62054 DRAFT

MEASUREMENT AND MODEL CORRELATION OF SPECIFIC HEAT CAPACITY OF

WATER-BASED NANOFLUIDS WITH SILICA, ALUMINA AND COPPER OXIDE
NANOPARTICLES

Harry O’Hanley Jacopo Buongiorno

Massachusetts Institute of Technology Massachusetts Institute of Technology
Cambridge, MA, USA Cambridge, MA, USA

Thomas McKrell Lin-wen Hu

Massachusetts Institute of Technology Massachusetts Institute of Technology
Cambridge, MA, USA Cambridge, MA, USA

ABSTRACT As nanofluids are considered for thermal applications, it is

Nanofluids are being considered for heat transfer applications. necessary to be able to predict their thermo-physical properties.
However, their thermo-physical properties are poorly known. Because nanofluids were initially considered for thermal
Here we focus on nanofluid specific heat capacity. Currently, conductivity enhancement, this property has been extensively
there exist two models to predict a nanofluid’s specific heat studied [2]. However, there have been fewer examinations of
capacity as a function of nanoparticle concentration and nanofluid specific heat capacity [3] [4] [5] [6]. It is the
material. Model I is a straight volume-weighted average; objective of this investigation to complement existing research
Model II is based on the assumption of thermal equilibrium by (i) measuring the specific heat capacity of water-based
between the particles and the surrounding fluid. These two silica, alumina and copper oxide nanofluids, and (ii) comparing
models give significantly different predictions for a given the predictions of two popular nanofluid specific heat capacity
system. Using differential scanning calorimetry, the specific models to data.
heat capacities of water based silica, alumina, and copper oxide
nanofluids were measured. Nanoparticle concentrations were NOMENCLATURE
varied between 5wt% and 50wt%. Test results were found to cp,f Specific heat capacity of base fluid (J/g-K)
be in excellent agreement with Model II, while the predictions cp,nf Specific heat capacity of nanofluid (J/g-K)
of Model I deviate very significantly from the data. cp,n Specific heat capacity of nanoparticle (J/g-K)
cp,ref Specific heat capacity of reference (J/g-K)
INTRODUCTION cp,sample Specific heat capacity of sample (J/g-K)
Recent research has indicated that dispersions of nanoparticles mn Mass of nanoparticles (g)
in a base fluid, known as nanofluids, can increase the boiling mH20 Mass of water (g)
critical heat flux and overall performance of thermal systems. mref Mass of reference (g)
Typical nanoparticle concentrations may range from 0.01wt% msample Mass of sample (g)
to 50wt% and common particle materials include silica, Qref Heat flux into reference (Watts)
alumina, copper oxide, zirconia, carbon nanotubes, etc. Water Qsample Heat flux into sample (Watts)
often serves as the base fluid, though other liquids such as Q0 Heat flux baseline (Watts)
ethylene glycol have been used [1]. φ Volume fraction (unitless)
ρf Density of basefluid (g/cm3)
ρn Density of nanoparticles (g/cm3)

1 Copyright © 2011 by ASME

 ρH20 Density of water (g/cm3) The stock nanofluids were obtained from commercial vendors,
VN Volume of nanoparticles (cm3) and diluted with de-ionized water to vary their concentrations.
VH20 Volume of water (cm3) Prior to mixing, the nanofluids were manually agitated to
ensure uniform dispersion. Dilution was performed by weight
percent using a Mettler Toledo XS105 balance. Four unique
concentrations were prepared for each nanofluid and are listed
SPECIFIC HEAT MODELS in the table below. For each concentration, two identical
There are two specific heat models widely used in the nanofluid samples were prepared and tested.
literature. Model I is similar to mixing theory for ideal gas
mixtures [3]. It is a straight average relating nanofluid specific Table 1: Nanofluid sample concentrations
heat, cp,nf, to basefluid specific heat, cp,f, nanoparticle specific
heat, cp,n, and volume fraction, φ. Using these parameters, Nanofluid
Alumina-
Silica-water
Copper
Model I calculates the nanofluid specific heat as, water Oxide-water
Conc. 1 20wt% 34wt% 50wt%
, , 1 , (1) (stock) (6.4vol%) (19.0vol%) (13.7vol%)
15wt% 25.5wt% 37.5wt%
Conc. 2
While it is simple and thus widespread in the literature, Model I (4.6vol%) (13.5vol%) (8.7vol%)
has little theoretical justification in the context of nanofluids. 10wt% 15wt% 25wt%
Conc. 3
(2.9vol%) (8.5vol%) (5.0vol%)
Model II [3] [7] is based on the assumption of thermal 5wt% 8.5wt% 12.5wt%
Conc. 4
equilibrium between the particles and the surrounding fluid. It (1.4vol%) (4.1vol%) (2.2vol%)
is straightforward to show that also the particle and fluid
densities (ρn, and ρf, respectively) must affect the specific heat While nanofluids were diluted and prepared according to their
of the nanofluid, weight fraction, calculations were performed using volume
fraction. Using the nanoparticle volume, Vn, and the water
volume, VH20, the volume fraction can be calculated as,
, (2)

(3)
A rigorous derivation of Equation (2) is presented in [8].

Predictions of nanofluid specific heat capacity were made using
both models and compared to experimental measurements.
Water was the base fluid of all nanofluids used in this
investigation. Therefore, handbook values of temperature-
dependent water specific heat and density were used in
calculating theoretical nanofluid specific heat [9]. Additionally,
the specific heat and density of the nanoparticles were assumed
to be equal to the respective thermo-physical properties of
particle material in bulk form.
Substituting in nanoparticle mass, mn, and density ρn, and water
mass, mH20, and density, ρH20, Equation (3) can be rewritten as,
(4)
Equation (4) can be used to determine the nanoparticle volume
fraction of nanofluid concentrations created by dilution with
de-ionized water.

NANOFLUIDS MEASUREMENT METHOD

The specific heat capacities of three nanofluids were analyzed: A heat-flux type differential scanning calorimeter (TA
alumina-water (Nyacol AL20DW), silica-water (Ludox TMA Instruments Q2000) was used to measure the nanofluid specific
420859), and copper oxide-water (Alfa Aesar 45407). The heat capacities. The differential scanning calorimeter (DSC)
nanofluid properties, as cited by the manufacturers, are measures the heat flux into a sample as a function of
presented in the table below. temperature during a user prescribed heating regime. It
accomplishes this by comparing the heat flux into a pan
Particle Size (nm) or Specific containing the sample with the heat flux into an empty pan.
Nanofluid pH
Surface Area (m2/g) Gravity Hermetically sealed aluminum pans (TA Instruments) were
NYACOL used.
50 nm 4.0 1.19
AL20DW
Ludox TMA 4.0- The classical three-step DSC procedure was followed to
140 m2/g 1.227-1.244
420859 7.0 measure specific heat capacity [10] [11]. Additionally, testing
Alfa Aesar procedures adhered to protocols set forth in the ASTM Standard
30 nm
45407 Test Method for Determining Specific Heat Capacity by
Differential Scanning Calorimetry (E 1269-05).

2 Copyright © 2011 by ASME

 were uused to calculaate the specificc heat capacityy and error barrs
The tthree-step DSC C procedure beegins with desiigning a heatinng indicaate standard devviation.
regim
me, which shou uld contain the temperature raange of interesst.
Next,, a measuremeent is taken with w two emptty sample pan ns RESU ULTS AND DISCUSSION
loadeed into the DS SC. During this measuremen nt, the baselin
ne DSC m measurements of pure ethyleene glycol andd glycerin were
heat flux, Q0, is obtained.
o The results of thiis measuremen nt in goood agreementt with literatuure values off specific heaat
indicaate the bias in the machine, allowing
a for it to be accounteed capaciity. The resultss of these testss, presented in Tables 2 and 3
for duuring data reduuction. below
w, validate the DDSC methodology and machiine calibration..

The second measu urement is of a reference sample,

s with a
knowwn specific heat, cp,ref. A pan p containing g the referencce Table 22: Propylene G
Glycol
sample and an emp pty pan are loaaded into the DSC.
D The heaat
flux iinto the referen
nce sample, Qref, is recorded
d throughout th
he Theoretical cp (J/g- Meeasured cp (J/g-
Tempeerature (°C)
identiical heating reg
gime. K) K)
35 2.56 22.54  0.191
The thhird measuremment is made on n the actual sam
mple of interesst. 45 2.62 22.64  0.185
A pann containing thhe sample and an empty pan are loaded intto 55 2.65 22.65  0.185
the DDSC. The heatt flux into thee sample, Qsammple, is recordeed
durinng an identicaal heating reegime as the previous tw wo Table 33: Glycerin
measuurements. Th he heat flux x curves fro om the threee
measuurements are used
u to comparratively determmine the specifi
fic Theoretical cp (J/g- Meeasured cp (J/g-
Tempeerature (°C)
heat oof the sample, cp,sample, where, K) K)
35 2.39 22.41  0.008
, , (5
5) 45 2.41 22.42  0.002

55 2.42 22.44  0.001
and mref and msample represent the masses
m of the reference
r and
sample, respectively
y. Sample masses were measu ured using a Figurees 1-9 show thhe nanofluids ddata and the cuurves predictedd
Perkin Elmer AD6 autobalance.
a by Moodels I and II. As expected, as nanoparticle concentration n
increaases, the speciffic heat capacitty decreases. H
However, Modeel
In thhese tests, de--ionized waterr was used ass the referencce I largeely underestimmates the decreease, while Moodel II offers a
sample, with specifi
fic heat values obtained
o from a handbook [9
9]. much more accuraate prediction of nanofluidd specific heaat
The DDSC heating prrocedure consisted of three seegments: capaciity. These coonclusions are consistent wiith the alumina
nanofl
fluid results reeported in [3],, and expand the validity ofo
11. Equilibratee and remain isothermal att 25°C for on
ne Modell II to silica annd copper oxidee nanofluids.
minute
22. Ramp to 75 5°C at 10°C/mmin
33. Remain iso othermal at 75°°C for one min
nute

Heat flux measurem ment was con ntinuous from 25°C to 75°C C.
Howeever, for analyysis, specific heat capacities were calculateed
at 355°C, 45°C an nd 55°C. An A uncertainty y analysis waas
performed via the propagation of o error. Unccertainty in th he
measuurement of speecific heat cappacity was fou und to be on thhe
orderr of 10-4 (J//g-K). For each samplee of nanofluiid
conceentration, threee measuremen nts were taken.. These valuees
were then averaged to yield the daata points and related
r standarrd
deviaations presentedd below.

Prior to nanofluid measurement, this DSC meethodology waas

validaated by analyzing two puree fluids, ethyllene glycol an nd
glyceerin. The results obtained fro
om these measurements werre Figu
ure 1: Alumina--water at 35°C
comppared against handbook
h valuues of specificc heat for thesse
liquidds [12]. Nextt, three measu urements weree performed on o
each nanofluid sam mple. The averrages of thesee measurementts

3 Copyright © 2011 by ASME

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Figu
ure 2: Alumina-water at 45°C Figgure 5: Silica-w
water at 45°C

Figu
ure 3: Alumina-water at 55°C Figgure 6: Silica-w
water at 55°C

Fiigure 4: Silica-w
water at 35°C Figure 7: Copper Oxid
de-water at 35°°C

4 Copyright © 2011 by ASME

E
 and gllycerin, whichh were confirm med against haandbook valuess.
The nnanofluid data were used too test the preddictions of two
populaar mixture moodels for speciific heat. Thee results clearly y
sugge st that the model basedd on particlee/fluid thermaal
equilibbrium (Model II) yields moore accurate ppredictions than n
the moodel based on a straight voluume-weightedd average of the
particlle and fluid sppecific heats (M
Model I). G
Given its sound
theoreetical basis, wee believe Moddel II is generaally applicablee,
while Model I shouuld be abandonned. To furthher improve the
accuraacy of Modell II, future innvestigations ccould focus on n
measuuring the acttual density and specific heat of the
nanopparticles in disspersion and coompare them to those of the
bulk mmaterials.

ACKN NOWLEDGM MENTS

The M Materials Reseearch Science and Engineeering Center at a
Harvaard Universityy offered theeir DSC forr use in thiis
Figuree 8: Copper Oxiide-water at 45°°C Kim, Dr. Kosta
investtigation. Withinn this facility, Dr. Philseok K
Ladavvac, and Roxannne Kimo offerred invaluable instruction and d
advicee on the machinne’s operation..

REFE
ERENCES

[1] K Kwak, K., K Kim, C., 20005, “Viscosityy and thermaal

conduuctivity of coppper oxide nannofluid disperssed in ethylene
glycoll,” Korea-Austtralia Rheologyy Journal, 17 (22), pp. 35-40.
[2] Buuongiorno, J., et. al., 2009, “A Benchmarkk Study on the
Therm mal Conductiviity of Nanofluuids”, J. Applieed Physics, voll.
106, isssue 9.
[3] Zhhou, S., Ni, R.., 2008, “Meassurement of thhe specific heaat
capaciity of water-bbased Al2O3 nanofluid,” A Applied Physics
Letterrs, 92.
[4]Sinnha, S., Barjam
mi, S., Iannacchhione, G., and SSinha, S., 2004
4,
“Therm mal propertiees of carbonn nanotube based fluids,”
Proceeedings of the Memphis-Areea Engineeringg and Sciencees
Figuree 9: Copper Oxiide-water at 55°°C Confeerence.
[5]He, Q., Tong, W W., and Liu, Y., 2007 “M Measurement of o
speciffic heat of T TiO2-BaCl2-H2O nano-fluidss with DSC,”
Even for Model II, there appeaar to be smalll discrepanciees Refriggeration & A Air-Conditioninng, vol.7 no. 5, pp. 19-22 2.
betweeen the data an nd predictions. These could co ome from errorrs (Chineese)
in thhe listed stocck nanofluid concentrationss, experimentaal [6] Peeng, X., Yu, X X., and Yu, F., 2007, “Experiment study on n
uncerrtainties in dillution or incon nsistencies in using the bullk the sppecific heat of nnanofluids,” Joournal of Materials Science &
materrial propertiess in the mo odel, instead of the actuaal Enginneering, vol. 255, no. 5, pp. 7199-722. (Chinesse)
nanopparticle properrties. Recent research sugg gests that thesse [7] B Buongiorno, J., 2006, “Convective Transport in n
propeerties may diff ffer if the matterial is in nan noparticle formm Nanofl fluids,” ASME Journal of Heat Transfer,
versuus bulk form [8]. Agglom meration/sedimeentation of th he 128, ppp. 240-250
nanopparticles could d also affect thee results [8]. Investigation of
o [8] Zhhou, L., Wang,, B., Peng, X.,, Du, X., and Y Yang, Y., 20099,
these effects is left for
f future work k. “On thhe Specific Heeat Capacity of CuO Nanofluuid,” Advances
in Me chanical Enginneering, 2010, Article ID 1722085, 4 pages.
[9]Greeen, D., Perryy, R., 2008, P Perry’s Chemiical Engineerss’
CONNCLUSIONS Handbbook (8th Editiion), McGraw--Hill, New Yorrk.
Usingg a heat flux differential
d scaanning calorim
meter (DSC), th he [10] Hohne, G., 22003, Differenntial Scanningg Calorimetry y,
speciffic heat capacities of wateer-based silicaa, alumina an nd Springger, New York,, pp. 148-160.
coppeer oxide nanofl
fluids at variouus nanoparticlee concentration
ns [11] Military Hanndbook - MIIL-HDBK-17-33F, Composite
were measured. The T DSC prrocedure was validated by b Materrials Handbookk, Volume 3 - PolymerMatrrix Composites
measuuring the speccific heat capaccities of pure ethylene glycool materiials Usage, Deesign, and Anallysis, U.S. D.OO.D.

5 Copyright © 2011 by ASME

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[12] Yaws, C., 1999, Chemical Properties Handbook, McGraw-
Hill, New York.

6 Copyright © 2011 by ASME