Energy Conversion and Management 82 (2014) 229237

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Thermophysical properties estimation of parafn/graphite composite

phase change material using an inverse method
Mohamed Lachheb a,, Mustapha Karkri b, Fethi Albouchi a, Foued Mzali a, Sassi Ben Nasrallah a
a
b

Ecole Nationale dIngnieurs de Monastir, Laboratoire dEtudes des systmes Thermiques et Energtiques (LESTE), Avenue Ibn El Jazzar, 5019 Monastir, Tunisia
Universit Paris-Est, Centre dEtude et de Recherche en Thermique, Environnement et Systmes (CERTES), France

a r t i c l e

i n f o

Article history:
Received 21 November 2013
Accepted 8 March 2014
Available online 31 March 2014
Keywords:
Phase change material (PCM)
Graphite
Periodic temperature method
Thermal conductivity
Thermal diffusivity
Inverse technique

a b s t r a c t
In this paper, two types of graphite were combined with parafn in an attempt to improve thermal conductivity of parafn phase change material (PCM): Synthetic graphite (Timrex SFG75) and graphite waste
obtained from damaged Tubular graphite Heat Exchangers. These parafn/graphite phase change material (PCM) composites are prepared by the cold uniaxial compression technique and the thermophysical
properties were estimated using a periodic temperature method and an inverse technique. Results
showed that the thermal conductivity and thermal diffusivity are greatly inuenced by the graphite
addition.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Thermal energy storage plays an important role in an effective
use of thermal energy and it has applications in various areas, such
as building heating/cooling systems, solar energy collectors and
industrial waste heat recovery [1]. Thermal energy can be stored
as a change in internal energy of a material as thermo-chemical
reaction, sensible heat or latent heat [2].
In this work, we are interested in the latent heat storage method through phase change materials (PCM). Recent studies have
been focused on the solidliquid phase change because of its high
storage capacity and nearly isothermal heat storage/retrieval process [36]. Phase change materials for latent heat storage can be
classied into three major categories as organic material, inorganic
material and eutectic PCMs [7,8]. Parafn is taken as the most
promising phase change material because it has a large latent heat,
low cost, little or no super cooling, low vapor pressure, good thermal and chemical stability, nontoxic and noncorrosive [1,9,10].
However, parafn suffers from a low thermal conductivity (0.21
0.24 W m1 K1) [11]. These drawbacks reduce the rate of heat
storage and extraction during the melting and solidication cycles
and restrict their wide applications, respectively. Consequently,

Corresponding author.
E-mail address: lachheb_med@yahoo.fr (M. Lachheb).
http://dx.doi.org/10.1016/j.enconman.2014.03.021
0196-8904/ 2014 Elsevier Ltd. All rights reserved.

more working effort has been focus to improve the thermal conductivity of PCMs, by dispersing of high conducting particles within the PCM [1215], impregnation of PCM into high thermal
conductivity material with porous structures [1618].
The use of graphite particles has advantages such as high thermal conductivity, low density in contrast to metals and high resistance to corrosion. The scope of this study is to make an
experimental investigation on the effect of graphite on thermal
conductivity, diffusivity and specic heat of parafn/graphite
composites. Two kinds of graphite were used to enhance thermal
conductivity of the parafn: Synthetic graphite (Timrex SFG75)
and graphite waste obtained from damaged Tubular graphite Heat
Exchangers. Parafn/graphite phase change composites with the
masse fraction of 5%, 10%, 15% and 20% were prepared by cold
uni-axial compression method. A periodic measurement method
was used to determine simultaneously the experimental thermophysical properties of parafn/graphite composites at room temperature. Composite sample is xed between two metallic
plates, the front side of the rst metallic plate is heated periodically using a sum of ve sinusoidal signals and the temperature
at the front and rear sides of both plates is measured and the
experimental transfer function is calculated. The theoretical thermal heat transfer function is calculated by the quadrupole method. Then, thermal conductivity and diffusivity are simultaneously
identied by comparison of experimental and theoretical heat
transfer function.

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M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

Nomenclature
e
D
m
t
f
I
a
Cp
V
b
H
T
T~

thickness (m)
conductivity ratio between the two phases
measured mass (kg)
time (s)
frequency (Hz)
thermal conductivity intensication
thermal diffusivity (m2 s1)
specic heat capacity (J kg1 K1)
volume of composite (m3)
thermal effusivity (W s1/2 m2 K1)
heat transfer function
temperature (K)
Fourier transform of the temperature

Greek symbols
k
thermal conductivity (W m1 K1)
/
ux, ller fraction
q
density (kg m3)
x
pulsation
Subscripts
eff
effective (composite)
m
matrix, mass
f
ller
c
composite, contact
v
volume fraction
exp
experimental
th
theoretical

2. Experimental investigation

2.2. Thermophysical property measurements

2.1. Investigated materials

2.2.1. Experimental set up

A periodical method was used to estimate simultaneously thermal conductivity, diffusivity and specic heat of parafn/graphite
composite materials at room temperature (Fig. 3). This method is
based on the use of a small temperature modulation in a parallelepiped-shape sample (42  42  5mm3). The advantage of this
method is that allows estimating simultaneously the effective
thermal conductivity and diffusivity with their corresponding statistical condence bounds [19]. It is well suited for polymers and
composite materials with a thickness between 1 and 10 mm.
In the conguration used (which is presented in Fig. 3), the
sample is sandwiched between two metallic plates. A thermal
grease of high conductivity is applied on the contact surfaces between the sample and the metallic plates to ensure good thermal
exchange between the various elements.
The front side of the rst metallic plate (brass) is also xed to
heating device (thermoelectric cooler) and heated periodically
using a sum of ve sinusoidal signals. The whole device is placed
in a vacuum chamber connected to a pumping system. The rear
side of the second metallic plate (copper) is in contact with air at
ambient temperature and high vacuum. The temperature is measured with thermocouples placed inside both front and rear metallic plates.

2.1.1. PCM and graphite selection

The PCM tested in the present work is: parafn with melting
temperature of 5658 C and with specic density of 900 kg m3.
The thermal conductivity enhancement is obtained by addition of
conductive graphite particles. Two different kinds of graphite were
used in this study:
 One type of graphite is the Timrex (SFG75) powder supplied by
Timcal Graphite & Carbon at a bulk density of 2240 kg m3. It is
a synthetic graphite with spherical shape and an average size of
75 lm, it is characterized by a well-aligned crystal structure
and by a high thermal conductivity in plane [3].
 The second kind that has been tested is an industrial graphite
graphite waste. It was obtained from damaged Tubular graphite Heat Exchangers. It is a form of carbon with crystalline structure; it has good thermal and mass transfer characteristics that
have led to its use for thermal conductivity enhancement. The
measured bulk density is 1936 kg m3 with an average size of
85 lm. Moreover, graphite has strong resistance to corrosion
and chemical attacks which makes it compatible with most
PCM. The recycling of graphite has a lot of benets, it can preserve natural resources of graphite for future generations i.e.
recycling graphite reduces the need for raw materials; it also
uses less energy, and it have economic benets.
2.1.2. Parafn/graphite material elaboration
The elaboration method developed in the present study is based
on the cold uni-axial compression, in this method parafn powders
and graphite particles are mixed together, then the obtained mixture (parafn + graphite) is poured into a stainless steel mould followed by a uni-axial compression (80 bar) at ambient temperature
(Fig. 1).
This technique leads to an anisotropic composite structure
whose porosity is partially occupied by parafn grains. Cylindrical
parafn/graphite samples were prepared under the same manufacturing conditions by the cold uni-axial compression method with
mass fraction of 5%, 10%, 15%, and 20%. The thickness and the
diameter of all this specimens were 5 mm and 60 mm respectively
(Fig. 2).
Then, neatly cut of the cylindrical samples (Fig. 2b) to obtain a
parallelepiped-shape specimens (Fig. 2c), with dimensions
(42 mm42 mm5 mm)
for
thermophysical
property
measurements.

2.2.2. Theoretical model

The system under study is composed of several layers with different thermophysical properties. A heat transfer function is dened at each frequency as the ratio between the Fourier
transforms of temperature at the xr and xf point of the x-axis
(Fig. 4). We assume that the temperature of the front side of the
metallic plate is modulated. The heat transfer exchanges on the
rear face are taken into account trough a global exchange coefcient, which is considered constant during the experiment and
the thermal properties of the sample are supposed constant.
By assuming a one-dimensional heat transfer in the x-direction,
the conservation of energy equation in each layer can be written
as:

@ 2 T 1 @T

@x2 a @t

8t > 0

In the case in periodic heating, the heat transfer equation is dened by [20]:

@ 2 T~ j  w ~

 T a2  T~
@x2
a

M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

231

Fig. 1. Cold uni-axial compression technique.

This system is modeled with one dimensional quadrupoles theory i.e. matrices with two inputs and two outputs. It is also possible
to obtain the expression of the theoretical heat transfer function
using the quadrupoles method. Let (Tk(s), uk(s)) be the temperature
and ux at the rear side of the k-th layer of homogeneous material.
With this k-th layer is associated a quadupole matrix (Fig. 5).
A quadrupole matrix [Q] is dened by:

Fig. 2. Example of parafn/graphite composite samples: (a) parafn, (b) parafn/

graphite and (c) parallelepiped-shape specimen for thermophysical property
measurements.

With; a

p
jw
; w 2p  f
a

T~ is the Fourier transform of the temperature.

p
p 3
RK

p
cosh sk  S
sk s  sinh sk  S
5
Q  4 p
p
p
sk S
 sinh sk  S cosh sk  S
R

where; s ea : the Fourier time, R ke: the thermal resistance.

So that:

"

T~ k1 s
~ k1 s
/

"
Q  

Fig. 3. Experimental set-up of periodic method.

T~ k s
~ k s
/

#
4

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M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

~ is calculated at
complex experimental heat transfer function H
each excitation frequency [20].


~ exp FFTTxr  FFTTxf

H
FFTTxf 2

where FFT (T(xr)), FFT (T(xf)) are the Fast Fourier Transfer of the temperature in the rear and in the front face respectively and FFT (T(xf))
is the complex conjugate of FFT (T(xf)).
The experimental heat transfer functions amplitude and phase
~ modulus and argument for each excitation freare given by the H
quency respectively.
2.2.3. Parameter identication procedure
In this study, a parameter estimation technique was applied to
estimate the optimal values of both thermal conductivity and diffusivity. The identication procedure consists in nding the set of
parameters b that minimize the squared difference between the
theoretical and experimental heat transfer functions. The minimization function is given by:

Fig. 4. Schematic view of the experimental exchange model.

Sbk;a

N h
X

~ real fi  Hreal fi 2 H
~ imag fi  Himag fi 2
H

10

i1

Fig. 5. Model of the set-up: each of the ve layers is modeled using a quadrupole
matrix.

This form is used for thermal modeling of plates of brass and

copper, and for the sample.
The grease layer at each interface is represented by a thermal
contact resistance.


Q Grease 

1 R
0


5

The equivalent quadrupole of N layers in series is the product of

N quadrupole thermal relative to each layer.

Q

N
Y

Q i

i1

The relationship between input variables and output is written

as follow [20]:

"

T~ front
~ front
/

"

T~ 0
Q Brass  QGre  Q Sample  Q Gre  Q Copp 
h  T~ 0

"

T~
And; rear
~ rear
/

"

T~ 0
Q Copp 
2
h  T~ 0

#
7

T~ rear f
~
T front f

bk1 bk X k  X k uk  I

1

~ exp  Hthe b; k
 X k  H

11

The variancecovariance matrix of the estimated thermal prop^ can be approximated as:
erty vector B

covb r2 X  X T
where X

 
^
@H
@b

1

12
T

represents the Jacobian matrix and X the Jacobian

transpose and r represents the standard deviation of the

measurements.
We assume a normal distribution for the measurement errors.
The approximate statistical condence bounds for the estimated
thermal conductivity and diffusivity values bk;a are at a condence
level of 95%.
2.3. Analytical models for thermophysical properties

where Q Brass ; Q Gre ; Q Sample ; Q Copp ; are the quadrupoles associated

to brass, grease, sample and copper respectively.
Thus, a theoretical heat transfer function can be obtained as:

Hth f ; b

~ real fi ) and Hreal fi are, respectively, the real parts of the

where (H
~ imag fi
experimental and the theoretical heat transfer function, H
and Himag fi are, respectively the imaginary parts of the experimental and the theoretical heat transfer function and b is the vector of
the estimated parameters kc and ac .
The identication of the thermo-physical parameters is a nonlinear optimization problem that is solved iteratively using the
LevenbergMarquardt method given by:

where the parameter vector b includes two unknown parameters,

thermal conductivity and diffusivity of the sample and f is the
frequency.
The knowledge of the experimental heat transfer function is
very important to nd the sample thermal parameters. The

2.3.1. Specic density, volume fraction

The determination of the composite density is important not
only for the specic thermal capacity estimation but for checking
the quality of the samples. It is clear that if composite samples
are well processed, i.e., good homogeneity is reached without air
bubbles in the sample as well as without unlled pores at the parafn/graphite interface, the specic density of the composites
should have a linear dependence upon the volume fraction, according to the simple rule of mixtures given by:

qeff qf /f qm /m

13

where qm and qf are the densities of the parafn matrix and the
graphite ller, respectively.

M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

Then, by using the values of qm and qf , it is possible to compute

the volume fraction of each compound knowing the graphite mass
fraction /m and using the classical relationship.



qf 1  /m
;
/v 1= 1

/m
qm

/m 1  /v

14

Two methods were adopted for measuring the densities of parafn/graphite composite:
 The rst one is the pycnometer method, in this method the
measurements are carried out with a balance and a pycnometer
for small quantities of different composites. The density of the
composite qc1 can be obtained by using the following
equation:

m1
q
m1 m2  m3 water

15

where m1 is the sample weight, m2 is the weight of the pycnometer lled with water and m3 is the weight of the pycnometer
containing the sample and lled with water.
 In the second method, the density measurements were
achieved using square-plate samples. A MettlerToledo
AT61 delta range balance was used to measure the mass of
the samples and the sample sizes were measured using a caliper
square. Then, the density of square-plate samples qc2 is
dened as mass divided by volume of the composites. The
uncertainty on the density u(q) measurement is obtained from
the following equation:

parameter ALN: in the case of llers with spherical shape, ALN = 1.5
[21]. Eqs. (17) and (18) can be re-written in order to introduce a
non-dimensional parameter D km =kf : Thus, we obtain

keff =km

1 ALN BLN /
1  BLN w/
(

With :

BLN

19
1
D

 

 1 = D1 ALN

w 1 1  umax /=u2max

20

2.3.2.2. Model of Bruggeman. Unlike Maxwell formula, the model

proposed by Bruggeman takes care of the shape factor of the second phase inhomogeneities [22]. Moreover, it has been showed
that this model can be used to estimate the effective thermal conductivity. This model is written as follows:

1/

kf  keff
kf  km



km
keff

1
d

21

d = 2 for cylinders oriented perpendicular to heat ow and

d 1 d=d
for
oriented
ellipsoids
inclusion,
where:
d r  1=x=1=y 1=z and x is the ellipsoidal axis parallel
to heat ow, y and z are the other two ellipsoid axes, and r is a surface roughness factor (1). For spherical inclusion, d 3 and the
effective thermal conductivity is dened by the following equation.


33
2
k
1  / kmf  1
keff 4
5 ;
u
km
3u
v31=3
u

3
u 2
k
uk
1  /3 kmf  1 7
6 keff
t eff
7
u6
42km 4k2
5
27
m
2

s
D2 m D2 V

2
q
m2
V

Dq

Or;

233

16

22

DV 2 D2 L1 D2 L2 D2 e

2
e
V
L21
L22
3. Results and discussion

2.3.2. Effective thermal conductivity

Many analytical models were proposed to predict thermal conductivity of composite materials. However, only few models take
into account the size of llers and the thermal contact resistance
between llers and matrix.
In this study, the effective thermal conductivity of parafn lled
with graphite can be investigated using two theoretical models:
the model of Lewis and Nielsen and the model of Bruggeman.
2.3.2.1. Model of Lewis and Nielsen. This model is originally used for
the prediction of mechanical properties of composites [21]. It was
also applied to the prediction of the effective thermal conductivity
of composites [21] by taking into account different parameters
such as the shape, distribution and orientation of llers into the
matrix and also the thermal conductivity values of ller and matrix. The main interest for the use of such model is that predictions
also consider the value of the maximum packing fraction of llers
/max . This model is dened by [21]:

keff km

With :

1 ALN BLN /
1  BLN w/

17



8
< BLN kkf  1 = kkf ALN
m
m
:

max /
w 1 1/
/2

18

max

where /max is the maximum packing fraction of llers. The shape,

distribution and orientation allow dening the value of the

3.1. Microstructure of the parafn/graphite composites

Scanning electron microscopy (SEM) was used to observe the
morphology of parafn/graphite composites also pure parafn
and graphite (SFG75 and graphite waste), as shown in Fig. 6ah.
The morphology of graphite SFG75 is illustrated in Fig. 6a and b.
From these gures, the structure of SFG75 can be observed, it is
characterized by a well-aligned crystal structure and by many inter-lamellar pores (especially in Fig. 6b), there is clearly shown
the characteristic graphene layers. The characteristics of the microstructure of a material are determined by its nature. Fig. 6c and d
show the SEM photographs of the used graphite waste and the parafn respectively.
Fig. 6e and f illustrated composite with 10 wt.% and 20 wt.% of
SFG75 respectively. Also, the morphology of the parafn/ graphite
waste composite with 10 wt.% and 20 wt.% of graphite waste are
demonstrated in Fig. 6g and h respectively. This gures exhibit different type of morphology and shows the presence of two different
regions represents two different materials, namely parafn and
graphite (SFG75 or graphite waste).
It can be observed that the graphite (SFG75 and graphite waste)
is dispersed into the parafn used as matrix material. We can easily recognize the graphite dispersed in the parafn by the darker
region and by its uniform shape, this dispersion enhances the thermal properties of the matrix.
Observed phase separation in composites was caused due to
unlike chemical nature of parafn and graphite.

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M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

SFG75

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

Graphite waste

And Paraffin

Paraffin/SFG75

Paraffin/graphite
waste

Fig. 6. Scanning electron microscopy images: (a) graphite SFG 75 200050 lm, (b) SFG 75 120,0001 lm, (c) graphite waste 200050 lm, (d) parafn 60,0003 lm, (e)
composite 10 wt.% of graphite SFG75 with parafn 200050 lm, (f) composite 20 wt.% of SFG75 with parafn 200050 lm, (g) composite with 10 wt.% of graphite waste with
parafn 200050 lm and (h) composite with 20 wt.% of graphite waste with parafn 200050 lm.

3.2. Thermal conductivity of composites

Thermal conductivity (keff ) of the PCMs composite with different graphite mass fraction was measured at room temperature,

using the previously mentioned method. The results obtained for

the two types of composites (parafn/SFG75 and parafn/graphite
waste) and their associated uncertainties are respectively plotted
in Fig. 7.

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M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

1,0

paraffin/SFG75
paraffin/graphite waste

paraffin/SFG75
paraffin/graphite waste

0,8
0,7

aeff x 10-7(m2.s-1)

Thermal conductivity ( W.m-1.K -1 )

0,9

0,6
0,5
0,4

0,3

0,2
0,1
0

10

15

20

Mass fraction m (%)

Fig. 7 shows that the measured thermal conductivity of parafn/graphite composite is greatly inuenced by the graphite addition and increased with increasing the mass fraction of graphite.
This increase is due to the higher thermal conductivity the graphite. In the case of parafn/SFG75, we observe a non linear increase
of the thermal conductivity with increasing synthetic graphite
(SFG75) mass fraction. The results of the thermal conductivities
of parafn/graphite composites and their intensications are
shown in Table 1.
We can observe that the thermal conductivity intensication
(Ikeff ) of parafn/SFG75 samples increase from 35.6%, to 288.4%,
with increasing of mass fraction (5% to 20%). A smaller increase
was observed for parafn/graphite waste with a maximum
Ikeff 83:6%:
For the same graphite amount, thermal conductivity intensication in the case of parafn/SFG75 composites is more important
than the case of the parafn/graphite waste; this can be explained
by the fact that thermal conductivity of the SFG75 is much higher
than graphite waste.

3.4. Thermal diffusivity and thermal effusivity

The thermal diffusivity of the large samples was measured
using the previously mentioned method. The behavior of thermal
diffusivity (aeff ) of parafn/graphite composite is depicted in
Fig. 8 as function of the graphite mass fraction.

20

Fig. 8. Thermal diffusivity of parafn/graphite composites versus mass fraction of

graphite.

We note, as in the thermal conductivity, a non linear raise in the

composite thermal diffusivity by increasing the graphite mass fraction for the two kinds of composites parafn/SFG75 and parafn/
graphite waste. As compared with thermal diffusivity of pure parafn (1.309  107 m2 s1), we can see that thermal diffusivity of
the parafn/graphite composite increase from 47.1% to 382.5%,
with increasing of the mass fraction of graphite Timrex (SFG75)
and a smaller increase can be seen for graphite waste composite
with an increasing rate from 51.3% to 157.4%. On the other hand,
a similar behavior can be seen for the two curves for low mass fraction (010%). The third parameter is the thermal effusivity of the
composites samples. It can be calculated using the thermal conductivity and diffusivity values as follows:

beff

q
keff
k:q:C P eff p
aeff

23

s
u2 k 1 u2 a
ub b 
: 2
2 a
k2

24

where uk and ua are the uncertainty of the sample thermal conductivity and diffusivity respectively. This is an important thermophysical property that can be dened as a comfort of contact; this
property determines the interfacial temperature when two objects
at different temperatures touch each other. Thermal effusivity and
diffusivity are summarized in Table 2.

Parameters

aeff (m2 s1)107

beff (W s1/2 m2 K1)

Samples
Parafn

1.309 0.086

644.001 20.737

0.316 0.005
0.409 0.01
0.569 0.023
0.906 0.026

35.6
75.5
144.2
288.8

Parafn/SFG75 composite
Mass fraction /m (%)
5
10
15
20

1.926 0.06
2.463 0.107
4.287 0.307
6.317 0.508

720.043 11.742
824.121 20.927
869.031 37.356
1139.915 36.398

0.289 0.012
0.342 0.012
0.383 0.008
0.428 0.021

24.0
46.7
64.4
83.7

Samples

keff (W m1 K1)

Ikeff (%)

Parafn

0.233 0.007

Parafn/graphite waste composite

Mass fraction /m (%)
5
10
15
20

15

Table 2
Thermal properties of parafn/graphite composite.

Table 1
Thermal conductivity intensication values of parafn/graphite composite.

5
10
15
20

10

Mass fraction m (%)

Fig. 7. The thermal conductivity of parafn/graphite composite versus mass

fraction of graphite.

Parafn/SFG75 composite
Mass fraction /m (%)

Parafn/graphite waste composite

Mass fraction /m (%)
5
1.981 0.11
10
2.214 0.148
15
2.781 0.26
20
3.37 0.383

649.315 27.962
726.837 27.127
726.270 18.344
737.273 40.936

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M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

Table 3
Mixture rule and measured density parafn/graphite composite.
Composite densities (kg m3)

Samples

qc1 qc2

Method (1) qc1

Method (2) qc2

0.896 0.017

0.897 0.017

0.895 0.017

5
10
15
20

0.941 0.016
0.997 0.018
1.092 0.02
1.107 0.018

0.951 0.019
1.0105 0.019
1.093 0.022
1.159 0.021

Parafn/graphite waste composite

Mass fraction /m (%)
5
10
15
20

0.944 0.018
0.990 0.017
1.031 0.019
1.1012 0.02

0.949 0.019
0.991 0.019
1.050 0.021
1.107 0.22

Parafn
Parafn/SFG75 composite
Mass fraction /m (%)

We can note that the thermal effusivity varied from a parafn/

graphite composites to another due to their differing ability to
transfer heat. This is due to differences in heat transfer through
and between particles, and is therefore a function of density and
morphology.

/v (%)

0.9

100

0.946 0.0175
1.003 0.0185
1.0925 0.021
1.133 0.0195

0.967
1.034
1.101
1.168

2.07
4.27
6.62
9.12

0.9465 0.0185
0.9905 0.018
1.0405 0.02
1.1041 0.021

0.952
1.003
1.055
1. 107

2.39
4.91
7.58
10.41

2100
paraffin/graphite waste
paraffin/SFG 75

2000
1900
1800

Cp eff (J. kg-1.K-1)

3.5. Specic density

qeff (Mixture rule)

qc

1700
1600
1500
1400
1300

These experimental density values of the parafn/graphite

composites are also compared to a theoretical curve computed
according to the rule of mixture (Eq. (13)) using density values of
parafn (qm = 900 kg m3) and the graphite (qSFG75 = 2240 kg m3)
or the graphite waste density: qgw = 1936 kg m3. The values of
experimental and theoretical densities, graphite mass fraction
and graphite volume fraction are summarized in the Table 3.
The measured values and the theoretically calculated density
versus volume fraction of graphite are plotted in Fig. 9 for parafn/graphite waste and parafn/SFG75 composites.
It can be seen from this gure a linear dependence of the density upon the graphite mass fraction and that as the mass fraction
of graphite increased the density of the composite increased, and a
good agreement between experimental and theoretical values can
be observed.
1,20

mixture rule

1,15

mixture rule
paraffin/SFG75

(g.cm-3 )

1,10

1,05

1,00

0,95

0,90

0,85
5

1100
1000
0

10

15

20

m (%)
Fig. 10. The specic heat capacity of parafn/graphite composites.

3.6. Specic heat capacity

The specic heat capacity (C peff ) values of composite samples is
determined using the following equation:

C peff keff =qc  aeff J kg

1

K1

25

Fig. 10 represents the evolution of the specic heat capacity of

the two kind of composite parafn/graphite waste and parafn/
SFG75 as a function of graphite mass fraction. It can be seen that
the specic heat of the test materials was inuenced by the graphite addition. There is a non-linear decrease in the specic heat
capacity with increasing the graphite mass fraction for the two
kinds of composites. This was attributed to the low heat capacity
of the graphite. Second, we can observe that the heat capacities
values of the parafn/SFG75 are superior to those of the composite
parafn/graphite waste in the 5%, 10%, and 20% mass fraction (expect in the case of 15%), it is possible that this variation unexpected
in the case of 15% mass fraction may be due to the nonhomogeneity of the composite sample which directly affects heat capacity. As
seen from this gure, for high ller volume fraction /m P 10%; the
calculated effective heat capacity increase linearly with decreasing
mass fraction.

paraffin/graphite waste

1200

10

15

20

Graphite mass fraction %

Fig. 9. Specic density of the composite versus mass fraction.

3.7. Comparison of the experimental data with the analytical models

A comparison between experimental values of thermal conductivity of parafn/graphite waste composites and some theoretical

M. Lachheb et al. / Energy Conversion and Management 82 (2014) 229237

the case of graphite waste was observed for /m 6 20%. Two experimental methods were adopted for measuring the densities of parafn/graphite composites. A good agreement between
experimental and theoretical values according to the rule mixture
is obtained.

10
9

Bruggeman
Lewis-Nielsen

max = 62,5%
max = 74%

8
7

eff / m

Graphite waste

References

6
5
4
3
2
1
0

10

237

20

30

40

50

m (%)
Fig. 11. Experimental and analytical thermal conductivities.

models are presented in Fig. 11. All data are plotted versus the
graphite waste mass fraction. Computations were performed using
the experimental value of the parafn thermal conductivity
(km 0:233 W  m1 K 1 ).
The examination of these results shows that a non-linear ink
crease of keffm with increasing graphite waste content was observed.
This increase of keff is foreseeable, because the graphite waste has a
signicantly higher thermal conductivity than the parafn. The calculated values agree well with the experimental data, as shown in
Fig. 11, which indicates that the Bruggeman and Lewis & Nielsen
models are suitable for predicting the thermal conductivity of parafn/graphite waste composite PCMs for a lower fraction of llers
/m 6 20%. It may be seen that the difference between Lewis &
Nielsen model and the measured effective thermal conductivity
lies between 0.3% and 6%. However, the difference between Bruggeman, and the measured effective thermal conductivity lies between 6% and 10%, respectively. Deviation start at /m P 30%
[23], but the current paper presents no such results. Further, new
parafn/graphite composites with high mass fraction more than
20% will be elaborated and then an experimental study will be
done to measure the thermal properties of these composites.
4. Conclusion
In this work, composites based on a phase change material
(PCM) and graphite were elaborated using cold uniaxial compression method. In such a composite, the parafn serves as a latent
heat material and the graphite as an effective heat transfer promoter. Two types of graphite were compared: graphite waste
and graphite synthetic Timrex (SFG75). The thermophysical properties of composites are characterized using the periodic temperature method and the values are compared to the results of different
analytical models. Results show that, increasing the mass fraction
of graphite from 0% to 20% gradually increased the thermal conductivity and diffusivity of parafn/graphite composite. A non linear increase of the thermal conductivity and diffusivity with
increasing graphite synthetic (SFG75) and a linear increase for

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