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A simple method, the -history method, of determining the heat of fusion, specific heat and

thermal conductivity of phase-change materials

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1999 Meas. Sci. Technol. 10 201

(http://iopscience.iop.org/0957-0233/10/3/015)

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Meas. Sci. Technol. 10 (1999) 201–205. Printed in the UK PII: S0957-0233(99)96940-0

A simple method, the T -history

method, of determining the heat of
fusion, specific heat and thermal
conductivity of phase-change
materials
Zhang Yinping, Jiang Yi and Jiang Yi
Department of Thermal Engineering, Tsinghua University, Beijing 100084,
People’s Republic of China

Received 24 August 1998, in final form and accepted for publication 8 December 1998

Abstract. A simple method of determining the melting point, heat of fusion, specific heat
and thermal conductivity of phase-change materials (PCMs) is presented. Compared with
other methods, such as conventional calorimetric methods, differential thermal analysis and
differential scanning calorimetry methods, it has the following salient features: the
experimental unit is simple, able to measure the heat of fusion, specific heat and thermal
conductivity of several samples of PCMs simultaneously and allows one to observe the
phase-change process of each PCM sample. Using the method, the thermophysical properties
of various salt hydrates, paraffin and some PCMs developed by us were measured. For the
PCMs whose thermophysical properties are available in the literature, our results gave fairly
good agreement. The method is especially useful for the selection of lots of candidate PCMs
used for the purpose of engineering and for preparing new PCMs.

Keywords: phase-change materials, heat of fusion, specific heat, thermal conductivity

1. Introduction small container, the degree of supercooling of the PCM is

In recent years latent heat storage systems have gained
importance for many applications in space-based power
plants, in some solar energy systems, in central air-
conditioning systems and in energy-conserving buildings,
because of their high energy density and isothermal
behaviour during charging and discharging. To some extent,
the selection or preparation of a suitable phase-change
material (PCM) for a latent-heat storage system is most
difficult but most important. In any case, measurement
of the thermal physical properties of the PCM is of
importance.
The methods available for determining the heat of fusion,
specific heat and melting point in the field of latent-heat
storage can be classified into three groups, conventional
calorimetry methods, differential thermal analysis (DTA)
and differential scanning calorimetry (DSC) methods [1].
Although DTA and DSC methods are well developed, their
shortcomings are obvious: the samples tested by them are
very small (1–10 mg) so that the thermophysical properties of
samples are usually different from those of the bulk materials
used in practical systems (for example, for liquid–solid
phase-change processes of most composite PCMs, especially
salt hydrates, if the phase-change material is put into a
increased while the degree of phase segregation is decreased
[2]); DTA and DSC measurement rigs are complicated and
expensive; and they cannot measure heats of fusion, specific
heats and thermal conductivities of several PCM samples
simultaneously. Insofar as conventional calorimetry methods
are concerned, almost all of them have the disadvantages
mentioned above except the first one. Besides, the phase-
change process of a PCM sample during a measurement is
hard to observe clearly when using convectional methods.
In view of these facts, we developed a new method; the
T -history method, of determining the melting point, degree
of supercooling, heat of fusion, specific heat and thermal
conductivity of several PCM samples simultaneously. It is
especially useful for the selection of lots of candidate PCMs
or for the preparation of new PCMs for use in practical
systems.
2. The principle of measurement
2.1. Determinations of the heat of fusion, specific heat
and so on of PCMs
If a tube containing a liquid PCM whose temperature is
uniform and equal to T0 (T0 > Tm , Tm is the melting

0957-0233/99/030201+05$19.50 © 1999 IOP Publishing Ltd 201

Zhang Yingping et al

Figure 1. A typical T -history curve of a PCM during a cooling Figure 3. A typical T -history curve of a PCM during a cooling
process (with supercooling). process (without supercooling).

curve is as shown in figure 2. Considering that Bi < 0.1,

similarly, we have

(mt cp,t + mw cp,w )(T0 − Ts ) = hAc A01 (4)

(mt cp,t + mw cp,w )(Ts − Tr ) = hAc A02 (5)

where mw and cp,w are the mass and mean specific heat
R t0
of water, respectively, A01 = 0 1 (T − T∞,a )dt and A02 =
R t20
t1 (T − T∞,a )dt.
In fact, using equation (4), the natural convective heat-
transfer coefficient of air outside a tube (h) can be obtained.
Figure 2. A typical T -history curve of water during a cooling It is about 5–6 W m−2 K−1 , so the condition about Bi 6 0.1
process. can be satisfied when ks > 0.2 W m−1 K−1 (ks of salt hydrates
are all larger than 0.3 W m−1 K−1 ).
temperature of the PCM) is suddenly exposed to an From equations (1)–(5), we obtain
atmosphere whose temperature is T∞,a (which can be time
dependent), the temperature versus time curve of the PCM, mw cp,w + mt cp,t A3 mt
cp,s = − cp,t (6)
i.e. the T -history curve, is as shown in figure 1, where 1Tm mp A02 mp
(=Tm − Ts ) is the degree of supercooling.
When Bi (= hR/(2k), i.e. the Biot number, where R mw cp,w + mt cp,t A1 mt
cp,1 = 0 − cp,t (7)
is the radius of a tube, k the thermal conductivity of PCM mp A1 mp
and h the natural convective heat-transfer coefficient of air
mw cp,w + mt cp,t A2
outside a tube) is less than < 0.1, the temperature distribution Hm = (T0 − Ts ). (8)
in the sample can be regarded as uniform and the lumped mt A01
capacitance method can be used [3]. Hence, we have For PCMs without supercooling (see figure 3, where the
temperature range of the phase-change process is between
(mt cp,t + mp cp,1 )(T0 − Ts ) = hAc A1 (1)
Tm,1 and Tm,2 ), the expressions for cp,l and cp,s are the same
where mp and mt are the masses of the PCM and tube, as those above, but the heat of fusion should be rewritten as
respectively, cp,l and cp,t are the mean specific heats of the follows:
liquid PCM and of the material of the tube, respectively, mw cp,w + mt cp,t A2
Hm = (T0 − Tm,1 )
Rand Ac is the convective heat-transfer area of a tube; A1 = mp A01
t1
0 (T − T∞,a ) dt. We have also mt cp,t (Tm,1 − Tm,2 )
− . (9)
mp Hm = hAc A2 (2) mp

Rwhere Hm is the heat of fusion of the PCM and A2 =

t2
t1 (T − T∞,a )dt (t1 → t2 is the time during which a phase-
change process occurs) and
(mt cp,t + mp cp,s )(Ts − Tr ) = hAc A3
where cp,s is the mean specific heat of the solid PCM,
Rt
A3 = t23 (T − T∞,a )dt and Tr is the reference temperature.
If a tube containing pure water is suddenly exposed to
the same atmosphere as that mentioned above, its cooling
2.2. Determination of the thermal conductivity of PCMs
In order to measure the thermal conductivity of a PCM,
(3) the tube containing the melted PCM whose temperature is
uniform and equal to T0 (T0 is a little higher than Tm ) has to
be suddenly dipped into a cool water bath whose temperature
is T∞,w (T∞,w is lower than Tm ).
If the ratio of the length to the diameter of a tube is
larger than 15, it is justifiable to assume that the heat transfer

202
 Properties of phase-change materials

Table 1. Relative errors of measurements.

1T (◦ C) 0.5 0.1 0.01
1Hm /Hm (%) 30 6 0.6
1cp,s /cp,s (%) 30 6 0.6
1cp,l /cp,l (%) 20 4 0.4
1k/k (%) 80 16 1.6

in whose phase-change process there is one clear interface

between two phases (in fact, for some salt hydrates, this
condition cannot be satisfied) and (ii) hw can be obtained
by using the T -history curve of a tube containing mercury
Figure 4. An illustration of two phases of a PCM in a long tube. and equation (4), where mw should be replaced by the mass
of mercury (because the thermal conductivity of mercury
is approximately one dimensional. For this case, the heat- is very large, the Bi number for this case is smaller than
diffusion equation for the cylinder shown in figure 4 is 0.1; therefore, the lumped capacitance method is applicable).
  From experiments, it was found that, for most cases,
1 ∂ ∂T (r, t) 1 ∂T (r, t)
r = (ξ < r < R, t > 0) tf (Tm − T∞,w ) 1
r ∂r ∂r αp ∂t  .
(10) ρp R 2 Hm hw R
subject to the boundary condition
Therefore, the term 1/(hw R) can be neglected for most cases.

∂T 
ks = hw (T∞ − T ) t >0
∂r r=R 2.3. Error analysis

and the initial condition From equations (6)–(9) and (13), it can be seen that the errors
in measurement of Hm , cp and k of PCMs mainly come from
T (ξ = R) ∼
= Tm t =0 the errors in measurements of temperature. So, we can derive
that
where T (r, t) is the temperature of the PCM sample at radius 1Hm 41T 21T
≈ + (14)
r and instant t, αp is the thermal diffusivity of the PCM; Hm Tm − T∞,a T0 − Tm
ξ is the radius of the interface between the solid and liquid 1cp,s 21T 21T
phases of the PCM and hw is the coefficient for convective ≈ + (15)
cp,s Tm − T∞,a Tr − Tm
heat transfer from the tube to the stirred cool water.
For the interface between the two phases of the PCM, 1cp,l 41T
6 (16)
we have cp,l Tm − T∞,a
T (r = ξ ) = Tm (11) 1ks 41T 21Hm
 ≈ + . (17)
∂T  dξ ks Tm − T∞,w Hm
ks = ρp Hm . (12)
∂r r=ξ dt
Using the perturbation method [4, 5], neglecting the second-
order term of the perturbation expansion, we obtain
    By using equations (6)–(9) and (13), for given errors of the
cp (Tm − T∞,w ) tf (Tm − T∞,w ) 1 related parameters, the deviations of the measured parameters
ks = 1 + 4 −
Hm ρp R 2 Hm hw R
(13)
where ks is the effective thermal conductivity of the PCM in
the solid state, ρp is the density of the PCM, which can be
obtained easily, and tf is the time of full solidification of the
molten PCM.
For equation (13), the relative error in ks caused
by neglecting the second-order term of the perturbation
expansion is smaller than 5% for the condition that Bi > 0.1
and 0 < Ste < 0.5 where Ste is the Stefan number which
equals cp |Tm − T∞ |/Hm [5].
Similarly, for a PCM in the solid state placed in a tube
which is put into a hot water bath whose temperature is a little
bit higher than Tm , the formula for calculating kl (the thermal
conductivity of the liquid PCM) can be obtained.
It should be mentioned that (i) equation (14) can be
used for determining the heat conductivity only for a PCM
Besides this, by using equations (14)–(17), we also
calculated the influences of errors in various parameters on
the precision of measurement. The method is as follows.
can be calculated. The values of errors are almost the same as
those estimated by using equations (14)–(17). The relative
errors of the aforementioned parameters for various errors
in measurement of the temperature 1T are listed in table 1.
From table 1, it can be seen that, if 1T 6 0.1, the required
precision of measurement of the thermophysical properties
is satisfied.
In brief, using equations (6)–(9), the specific heat of
fusion of a PCM can be obtained. For a PCM in whose
phase-change process there is one clear interface between
two phases the thermal conductivity of the PCM can be
measured by using equation (14). Besides this, the melting
point and degree of supercooling can be readily found from
the cooling curve of the PCM and the thermal diffusivity
of the PCM (αp ) can be calculated by using its definition
(αp = kp /ρp cp,p , where p denotes pcm). Therefore,
by using the T -history curves of PCMs and water, almost
203
Zhang Yingping et al

Table 2. Measured results of thermophysical properties of some PCMs (the number in the bracket after value 1 is the number of
measurements).
Tm0 1T cp,l cp,s Hm ks
Material Item (◦ C) (◦ C) (kJ kg−1 K−1 ) (kJ kg−1 K−1 ) (kJ kg−1 ) (W m−2 K−1 )
58.7 wt% Mg(NO3 )2 · 6H2 O Value 1 (2) 58.3 6.52 2.57 1.94 120 0.61
+41.3 wt% MgCl2 · 6H2 O Value 2 58.0 2.43 1.95 132 0.68
37.5 wt% NH4 NO3 Value 1(3) 48.7 8.28 2.56 2.60 118 0.34
+62.5 wt% Mg(NO3 )2 · 6H2 O Value 2 51.0 126
Myristic acid Value 1(3) 49.7–52.7 3.67 2.91 201 0.17
Value 2 52.1 190
Capric acid Value 1(2) 30.1 0.05 1.72 1.95 150 0.16
Value 2 30.1 1.6 158 0.15
Lauric acid Value 1(2) 52.5 0.06 1.75 160 0.17
Value 2 52.1 0.05 1.6 179 0.15
Hexacosane Value 1(2) 54.60–57.69 2.94 3.89 216 0.22
Value 2 56.3 237
CH3 COONa · 3H2 O Value 1(2) 58.0 5.98 3.33 2.26 248
Value 2 58 2.79 226
Na2 S2 O3 · 5H2 O Value 1(2) 48.0 37.6 3.83 206
Value 2 48 201
KD-28a Value 1(3) 27.91 7.48 3.05 203
KD-52a Value 1(2) 52.30 1.28 4.35 104
KD-38a Value 1(5) 38.92 9.37 2.34 150
KD-46a Value 1(3) 29.28–46.35 3.33 368
KD-34a Value 1(2) 34.7 2.93 3.28 81
KD-32a Value 1(2) 32.4 24.4 3.1 193
Heptadecane Value 1(2) 20. 8 0 2.93 2.57 171 0.24
Value 2 21.7 172
Mg(NO3 )2 · 6H2 O Value 1(2) 89. 3 3.3 2.39 1.92 175
Value 2 89.9 2.51 1.84 167 0.57 at 120 ◦ C
a
PCMs developed in our laboratory.

Figure 5. A schematic diagram of the experimental rig.

all thermophysical properties of PCMs can be obtained

simultaneously, which is the reason that this method is named
the ‘T -history method’.

3. The experimental system

An experimental rig based upon the principle was built

(figure 5). In a test run seven samples and pure water are
contained in eight glass tubes diameter is 10.4 mm and length
180.6 mm.
A thermoprobe 108 mm in length and 0.7 mm in diameter
is placed along the axis of each tube. Data acquisition is
accomplished with a PC-based data-logger system.
The advantages of this kind of experimental system are Figure 6. Measured T -history curves of PCMs during cooling
processes.
as follows. (i) Using conventional tubes as PCM sample
containers makes measurement convenient and means that
the phase-change process of each sample can be clearly 4. Measured results
observed. (ii) One is able to measure several samples during
a test (the number of samples measured in a test run depends Figure 6 shows measured T -history curves of some PCMs.
upon the number of channels of the data acquisition system). The thermophysical properties of the PCMs measured are

204

listed in table 2. It can be seen that the relative deviations
between the measured results (value 1) and those in the
literature [4, 6, 7] (value 2) are less than 10%.
5. Conclusion
Compared with methods available such as conventional
calorimetry methods and DSC methods, the method
presented in this paper has the following salient features:
the experimental system is simple; it is able to measure lots
of samples and obtain several thermophysical properties of
each PCM sample through a group of tests; the precision of
measurement satisfies the need for engineering applications;
and the phase-change process of each PCM sample can be
observed clearly. Using the method, the thermophysical
properties of several salt hydrates, paraffin and some PCMs
developed in our laboratory (salt hydrates) were measured.
The results agree well with those in the literature. This
method is useful for rapid measurement of PCM candidate
for use in engineering applications of latent thermal storage.
The method is applicable to a larger range of temperature if
an oil bath or other suitable liquid bath were used instead of
a water bath.
Properties of phase-change materials
Acknowledgment
This work was supported by the Nature Science Foundation
of the People’s Republic of China.
References
[1] Chen Zeshao, Ge Xinshi and Gu Yuqing 1991 Measurement of
Thermophysical Properties (Hefei: Publishing Company of
USTC) pp 36–81 (in Chinese)
[2] Abhat A 1981 Low temperature latent heat thermal energy
storage Thermal Energy Storage ed C Beghi (Dordrecht:
Reidel)
[3] Incropera F P and Dewitt D P 1996 Fundamentals of Heat and
Mass Transfer 4th edn (New York: Wiley) pp 212–17
[4] Zhang Yinping, Hu Hanping and Kong Xiangdong 1996
The Theory and Application of Heat Storage Phase-Change
Materials (Hefei: Publishing Company of USTC)
pp 339–41 (in Chinese)
[5] Song Y W 1981 The solution of the solidification of PCMs in
a cylindrical container by using the perturbation method
J. Engng Thermal Phys. 2 211–6 (in Chinese, with English
abstract)
[6] George A L 1983 Solar Heat Storage: Latent Heat Material
vol 2 (Boca Raton, FL: CRC) pp 4–67
[7] Garg H P 1985 Solar Thermal Energy Storage (Dordrecht:
Reidel) pp 183–206
205