Sei sulla pagina 1di 7
See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/261334891

See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/261334891

Conference Paper · March 2013

DOI: 10.1109/IRSEC.2013.6529719

CITATIONS

4

READS

57

4 authors, including:

CITATIONS 4 READS 57 4 authors , including: Anissa Eddhahak-Ouni Sarra Drissi Ecole Nationale

28 PUBLICATIONS

185 CITATIONS

10 PUBLICATIONS

89 CITATIONS

Some of the authors of this publication are also working on these related projects:

non reactive rotational molding View project View project

SMART NANOCONCRETES AND CEMENT-BASED MATERIALS: PROPERTIES, MODELLING AND APPLICATIONS View project View project

All content following this page was uploaded by Sarra Drissi on 13 February 2017.

The user has requested enhancement of the downloaded file.

Analysis by Differential Scanning Calorimetry of concrete modified with microencapsulated phase change materials

Anissa Eddhahak-Ouni*

Universite Paris Est, Institut de recherche en constructibilite ESTP, F-94234, Cachan, France. aeddhahak@adm.estp.fr

Johan Colin

Universite Paris Est Institut de recherche en constructibilite ESTP, F-94234, Cachan, France. jcolin@adm.estp.fr

Abstract: In this work, a thermal experimental investigation by Differential Scanning Calorimetry (DSC) of a Portland cement concrete modified with microencapsulated phase change materials labeled "PCM-concrete" is presented. First, the DSC technique was used for the thermal characterization of the micro­ PCMs considered in this study. Accordingly, several thermal properties were determined such as the melting and freezing temperatures, the specific heat capacity and the change phase enthalpies. After, concrete mixtures with different PCM amounts were manufactured in laboratory and then the compressive strength was measured. Then, the PCM-concrete thermal performance was studied by DSC. Also, artificial accelerated ageing was performed on the PCM concrete mixtures in order to investigate the PCM stability in the concrete. Next, the thermal properties of the artificial aged PCM-concrete were determined by DSC and compared with the non-aged PCM concrete properties. Finally, the microstructure of the PCM concrete mixtures was analyzed by Scanning Electronic Microscopy (SEM) to check the PCMs state after their incorporation in the concrete. The results highlighted an improvement of the specific heat capacity of the PCM-concrete with the addition of PCMs. A slight loss of the mechanical strength was noted. Also, the thermal storage of PCM-concrete mixtures after the artificial ageing was enhanced with comparison with the reference non­ aged one.

Keywords: Phase change materials; PCM-concrete; DSC; specific heat capacity; energy saving

Sarra Drissi

Universite Tunis El Manar- Laboratoire de Materiaux d'Optimisation et d'Energie pour la Durabilite, LAMOED- Ecole Nationale d'Ingenieurs de Tunis, BP 37, Le Belvedere, lO02, Tunis - Tunisia. sdrissi@adm.estp.fr

Jamel Neji

Universite Tunis EI Manar- Laboratoire de Materiaux, d'Optimisation et d'Energie pour la Durabilite, LAMOED- Ecole Nationale d'Ingenieurs de Tunis, BP 37, Le belvedere, lO02, Tunis - Tunisia. jamel.neji@enit.rnu.tn

I.

INTRODUCTION

For many years, the use of smart materials called "Phase Change Materials" (PCMs for short) in building construction

has been an attractive solution aiming to reduce the energy consumption and to provide more thermal comfortable conditions for people [1,2]. Thanks to their latent heat storage (LTH) ability, the PCMs development contributes positively to the sustainable construction program thanks to the numerous environmental impacts it has offered. Furthermore, it was highlighted that many combinations between PCMs and construction materials (concrete, gypsum, etc) are potential and greatly advantageous especially when the appropriate and suitable PCMs are used. As known, there is a wide range of PCMs generally classified in three main families: organic, inorganic and eutectic PCMs. For an extensive description of the merits and de-merits of the different PCMs families, the readers could consult the review of [3]. The choice of the suitable PCMs to be incorporated into the construction material depends on several criteria mostly linked to their thermal properties (latent heat capacity, change phase temperature

range

shell structure, density

material (matrix), the possibility to exhibit supercooling or incongruent melting phenomena and also to their costs and availability [4]. For instance, the earlier works of [5,6] have focused on the use of organic PCMs in building materials and

),

their physical characteristics (volume change, core­

),

their chemical stability into the base

978-1-4673-6374-7/13/$31.00 ©2013 IEEE

the study of their effects on thermal and mechanical properties of the PCM-material (mixture PCM + base material). Recently, Hunger et al. [7] investigated the behavior of self-compacting concrete modified with organic microencapsulated PCMs (micro-PCMs) named Micronal DS 5008 X composed with a paraffin wax contained in polymethyl methacrylate micro­ capsules. Different amounts of PCMs were considered with regards to the mass of concrete and it was highlighted in fme the significant improvement of the thermal performance of the PCM-concrete by the addition of PCMs in a hand, and the decrease of the compressive resistance due to the porosity increase with the PCMs addition on the other hand. More recently, Meshgin et al. [8] used also organic PCMs with paraffm core material (MPCM-28 wet cake) to be embedded in concrete and then distinguished two methods for the PCMs incorporation: the addition and the sand substitution (replacement) methods. In this work, it was shown that the substitution method doesn't imply a significant loss of the mechanical resistance as the additive method and that the specific heat capacity of the PCM-concrete is notably enhanced by the implementation of the PCMs. Zhang et al. [9] used micro-PCMs composed with n-octadecane core material encapsulated in melamine-formaldehyde copolymers shell. The core-shell structure of their PCMs was useful to simply blend them with gypsum powder. In this research, the authors studied the thermal performance of gypsum boards incorporated with micro-PCMs and glass fibers for mechanical reinforcement and concluded the good thermal stability of the PCM-gypswn boards after 60 melting-freezing cycles. Although the nwnerous researches performed in this frame work, it is worth noticing that there is a lot of dispersion regarding the expected equivalent (apparent) properties of the PCM-material. These uncertainties are especially due to the variability of the base material mix design, the PCM amount, the manufacture procedure, the different experimental techniques used for the thermal and mechanical characterization of the PCM-material, etc. In this context, the present research work is a contribution aiming to present an experimental methodology based on the differential Scanning Calorimetry (DSC) technique for the identification of both PCM and PCM-concrete thermal properties.

II.

MATERIALS

A. Phase change materials (PCMs)

The micro-PCMs used in this study are Micronal PCM from basf in dry powder labeled "Micronal DS 5001 X". These PCMs are composed with paraffin wax encapsulated in polymer shell with a melting temperature of 26°C and a latent heat capacity of approximately 110 KJ/Kg. According to the supplier data, the range average diameter of the PCM capsules is about 100 - 300 f!m. The figure 1 presents the morphology of the PCM observed by SEM. Note that the PCM were observations were performed before and after the melting temperature at respectively 10°C and at 30°C. No significant differences were noticed between the 2 configurations.

addition, one can notice that thousands of micro-PCMs are bounded together to form macro-capsules of about 200 f!m of

bounded together to form macro-capsules of about 200 f!m of Figure 1. SEM observations of the

Figure 1. SEM observations of the micro PCMs: degraded state and micro-PCM agglomeration.

This agglomeration feature is probably due to the PCM production process which is based on the polymerization mechanism. Furthermore, it was observed some broken PCMs at the initial state highlighting the brittle characteristic of these materials.

B. Miw design ofPCM-concrete mixtures

The manufacture of PCM-concrete mixtures in the following named Mix 1, Mix 2 and Mix 3 was performed using respectively 1%, 3% and 5% of PCMs amounts with regards to the concrete volume. These amounts were considered such as the sieve curves of the different PCM-concrete mixtures are close. In addition, a reference concrete without PCMs was prepared to allow comparison with the modified concrete. The mix

design of the reference and modified concrete is given in table

l. For sake of simplicity and in order to ensure a good

workability of the mix, the micro-PCMs were simply added in

the concrete.

DSCsample-DSCBase

line

Msamp le.dT/dt. E

Three specimens were manufactured for each PCM amount so that averaged results can be gathered. During the manufacture process, the dry materials (cement, sand and gravels) were mixed together before adding water.

TABLE/,

MIx DESIGN OF peM-CONCRETE MIXTURES

Portland Fine Coarse PCM cement 11 aggregates aggregates EIC 32.5R (sand) (gravels) (Kg) (K/!lm3) (K/.!lm3)
Portland
Fine
Coarse
PCM
cement 11
aggregates
aggregates
EIC
32.5R
(sand)
(gravels)
(Kg)
(K/!lm3)
(K/.!lm3)
(K/.!lm 3)
Reference
350
630
1100
0.5
0
Mix1
350
630
1100
0.5
9.5
Mix2
350
630
1100
0.5
28.5
Mix3
350
630
1100
0.5
47.5

Once the reference concrete preparation is obtained, different fractions were collected in order to prepare the PCM-concrete mixtures. In each concrete fraction, the required PCMs amount was incorporated and then blended manually in order to avoid the damage of the micro capsules. Next, the PCM-concrete mixtures were placed in prismatic molds of 7 x 7 x 28 cm 3 of dimensions before to be subjected to dynamic vibration for a better dispersion and homogenization of the PCMs in the concrete. Also, small cylindrical specimens (3 x 3 cm 2 ) of PCM-concrete mixtures were casted to allow the DSC analysis. In fact, it is well known that the DSC test requires the use of small samples in compatibility with the crucible size. Accordingly, the sample to be tested has to be sufficiently representative of the overall material heterogeneities. The different specimens were demolded 24 hours later and then conditioned in a temperature test chamber under a temperature of 20°C and a relative humidity (H.R) of 95% during 28 days.

III. Mechanical resistance

The compressive strengths of the PCM-concrete mixtures were measured after a curing age of 28 days. The experimental results are depicted in figure 2.

25 25 20 o +------,-----�---
25
25
20
o +------,-----�---

Figure

PCMs.

2.

0%
0%

Evolution

1%

of

3%

PCM in%

the

compressive

5%

strength

with

the

It can be noticed from figure 2 a loss of the compressive strength with the increase of the PCM amount. This fmding is due to the weak mechanical resistance of PCM capsules added into the concrete. The bad strength of these materials deteriorates the mechanical response of the modified concrete. The experimental results were interpolated by a linear equation of a negative slope. The decrease of the mechanical strength was recorded to 32% between the reference concrete and the modified concrete with a PCM amount of 5%.

IV. Thermal analysis by Differential Scanning Calorimetry

The thermal properties of both PCMs and PCM-concrete mixtures were analyzed by differential scanning calorimetry using a DSC 204 Fl Phoenix from Netzsch. The tests were carried out under nitrogen atmosphere and by considering different scanning rates (0.5 Klmin - 20 Klmin). In the first scan, a cooling dynamic segment is programmed from 20°C to -lO°e. Then an isothermal period of 5 min was considered so that an isothermal equilibrium state can be reached. After, the specimen is heated from -lOoC to 55°C before to be maintained at 55°C during 5 min. Next, a cooling segment was arranged from 55°C to -lOoC so that one can check the DSC signal reversibility. To finish, a heating segment was performed from -lOoC to 20°e. The temperature range considered for the DSC program was chosen such as to be in correlation with the expected building temperature conditions.

In addition, the DSC experiment was used for the measurement of the specific heat capacity of the micro-PCMs. To achieve this purpose, three DSC runs were performed related, in the order, to the base line, the standard (sapphire) and the sample. The first two runs (base line + standard) allow the determination of the DSC calorimetric sensitivity or the calibration constant which can be expressed as:

=
E

DSCsapphire-DSCBase

line

Msapphire·dT/dt.CPsapphire

(1)

where:

Msa pp hire denotes the mass of the sapphire sample and dTldt represents the scanning rate. The third last run is devoted to the sample and leads to deduce its specific heat capacity denoted Cps via the ratio method:

CPs =

(2)

Besides, some PCM-concrete mixtures were artificially aged in a climate test chamber during 50 days and were subjected to the same thermal program used in DSC experiment with a heating rate of 10 K/min. The DSC measurements were performed on the PCM materials but also on samples extracted from the PCM concrete mixtures before and after artificial ageing.

v. RESULTS AND DISCUSSION

Figure 3 presents the DSC signal of the PCM materials with different tested scanning rates. Only the exothermic segment is presented in the graph. The different DSC tests were performed using the same sample mass as well as the same experimental procedure so that only the scanning rate influence can be analyzed. In addition, for each scanning rate 3 tests were similarly performed and the averaged DSC result is presented here. Plots of figure 3 highlight the effect of the heating rate on the DSC signal. In fact, the more the heating rate increases, the more important is the DSC signal. This is an expected result since the DSC signal represents the heat flux absorbed or restituted by the material being tested in order to maintain the same temperature between the empty and the filled crucibles. In the definition, the heat flux is proportional to the heating rate and is linked to the energy by:

-10,00 0.00 0 .(l.s ., � -1,5 .Eo � . -lK/min c ., 3K/min SK/min
-10,00
0.00
0
.(l.s
.,
-1,5
.Eo
. -lK/min
c
.,
3K/min
SK/min
······10K/min
-2,5
- - 15K/min
-20IC/min
·3

Figure 3. DSC results of PCM materials with different scanning rates (exothermic signal)

materials with different scanning rates (exothermic signal) (3) where Q is the energy per unit mass

(3)

where Q is the energy per unit mass in J/Kg, Tel and Te2 are the temperature range of the phase change which can occurs in the material such as Tel<Te2' L1Ht is the total energy storage or also the overall specific heat combining both sensible heat and the enthalpy of the phase change (latent heat). The total energy storage is computed by the integration of the specific heat over the temperature range [Tel Td, Cp l and Cp 2 denote respectively the specific heats of the material before and after the transformation and TI and T2 are respectively the lower and upper bounds of the temperature range considered in the experiment defined such as TI<Tel<Te2<T2.

In figure 3, one can distinguish 2 peaks; the smaller one is probably due to the polymer shell transition of the PCM

material as it was noticed in [7] whereas the larger one represents the phase change (freezing) of the paraffin active material. Also, it can be noticed that when the heating rate increases, the freezing range becomes broader and the peak maximum shifts towards the higher temperatures.

The specific heat capacity was also measured during heating and cooling processes in the temperature range -10°C-55°C with a dynamic rate of 1 K/min. The exothermic and endothermic curves are plotted in figure 5. One can see that the 2 signals are quietly similar but not exactly symmetric with regards to the temperature axis. A slight thermal shift of maximum 2°C was noticed between the upper and lower curves i.e. the sample was still in a liquid state although the temperature of the phase change has been reached. This phenomenon known as the supercooling is often attributed to inorganic PCM but can also affect the paraffin PCM while remaining negligible.

l

The table 2 summarizes the specific heat averaged values Cp and Cp 2 recorded respectively in the temperature ranges o°c- 10°C and 30°C-50°C. The melting and freezing enthalpies

TABLE I\,

SPECIFIC HEAT CAPACITY OF PCM ISSUED FROM DSC MEASUREMENTS.

Cp Cp " &(KJIKg) (KJIKg.K) (KJIKg.K) I Endothermic 2.211 136.55 1.793 I Exothermic 2.8\ 146.36
Cp
Cp "
&(KJIKg)
(KJIKg.K)
(KJIKg.K)
I Endothermic
2.211
136.55
1.793
I Exothermic
2.8\
146.36
2.269

were computed by the integration of the Cp curve over the temperature range 10°C-30°C that is the sum of the sensible and latent heats in the considered temperature range. Note that according to the technical data supplied by the PCM manufacturer, the overall specific heat computed in the range 10°C-30°C is equal to 145 KJ/Kg. The DSC results are in a good correlation with this data excepted for the endothermic case where the error in the enthalpy estimation was less than

7%.

40 30 20 10 ) - 0- - - - -cr - - iO'"' .,
40
30
20
10
)
- 0-
-
-
-
-cr -
-
iO'"'
.,
20
,- - - :30 - - - - -40 - - - - 50-
-
-
-
,
,
,
,
,
T I"Cl
·10
"
,
,
"
,
I
,
,
·20
,
,
,
1--
1
\',
,
,
·30
- Exothermic :
"
\
-Endothermic
·40

Figure 4. Specific heat measurements and comparison between exothermic and endothermic signals.

In addition, DSC measurements were performed on the PCM­

concrete

of dimensions. For every PCM­

mixture, three samples were at least extracted from the

consid red specime

tested IS representative of the overall heterogeneous material. Note that no grinding process was used for the extraction of the

samples from the mixture so that the intrinsic properties of the material are not altered.

cylindrical

specimens of 3 x 3 cm

mixtures

previously

2

prepared

in

small

in order to ensure that the sample being

As said previously, accelerated ageing test was performed on the PCM-concrete mixtures and then their thermal properties were analyzed by DSC measurements. The experimental results showed no significant differences between the aged and non-aged PCM concrete. In figure 6, the overall heat capacity results of the aged PCM concrete are presented and compared with the non-aged mixtures.

, ------------------- -, 3,0 1\ 2,5 I I 2,0 �.' I . _ . ,.
, ------------------- -,
3,0
1\
2,5
I
I
2,0
�.'
I
.
_
.
,.
1,5
��.--
-.
--
-.
---
.
--
�.-- -.---.�-
-.
�-�.
/".
-
_- ------
-------
1,0
0,5
-. -
-- Reference
- - Mix 1
-- Mix 2
Mix 3
0,0 �=;:==;:=���=;=�=:;:::=:;:::��=:::;=�

0,00

10,00 20,00 30,00 40,00 50,00 60,00
10,00
20,00
30,00
40,00
50,00
60,00

40

35

30

25

0,00 10,00 20,00 30,00 40,00 50,00 60,00 40 35 30 25 0% 1% 3% 5% ,.

0%

1%

3%

5%

,.

'"
'"

g

g

�-�.�-�.�- �.=-

20

:I:

<i

15

10

5

°

Il. u -1 0,00
Il.
u
-1 0,00

T I"c)

PCMin%

Figure 5. Specific heat measurements of PCM-concrete mixtures.

Plots of figure 5 present the specific heat results of the PCM­ concrete mixtures compared to the reference concrete in the temperature range -lOoC - 55°C with a heating rate of I Klmin. It can be noticed that an improvement of the thermal capacity is

gained by the PCM addition. As expected, the reference concrete doesn't present any peak in the region of interest and the specific heat evolution is quietly constant and is about 0.83 KJlKg K. On the contrary, the curves of the PCM mixtures present peaks due to the PCM inclusion. The higher is the PCM amount in the concrete, the more important is the area below the peak. This fmding highlights the efficient role the PCM

mat

rials play for the thermal reinforcement of the concrete by

the mcrease of the heat storage capacity.

By analogy to the PCM materials, the table 3 summarizes the specific heat results for the different mixtures and their comparison with the reference concrete. The values of Cp i , Cp 2 and .MIt are computed in the same temperature ranges as the

PCM materials. It can be noticed that

and Cp 2

computed respectively before and after the PCM phase change

concrete mixture, the specific sensible heats Cp

for a given PCM­

l

are very close.

TABLE III.

SPECIFIC HEAT CAPACITY OF rCM-CONCRETE MIXES ISSUED FROM DSC MEASUREMENTS.

Cp Cp z &i(KJIKg) (KJIKJ!IK) (KJIKJ!IK) Reference 0.82 17.06 0.84 Mix1 1.03 22.32 1.09 Mix2
Cp
Cp z
&i(KJIKg)
(KJIKJ!IK)
(KJIKJ!IK)
Reference
0.82
17.06
0.84
Mix1
1.03
22.32
1.09
Mix2
1.39
30.23
1.39
Mix3
1.5
36.64
1.42

Figure 6. Comparison of the overall heat storage of the PCM­ concrete mixtures before and after ageing.

Although a slight improvement of the heat storage capacity is noticed after the ageing, one cannot be affirmative regards to the conclusion on the real influence of the ageing process on the PCM stability in the concrete. These first fmdings could probably be associated with the experimental dispersion due to he difficulty encountered to gather the averaged information Issued from the multiple DSC experiments. Furthermore, the ageing program considered in this study was conducted during only 50 days. This period may be not sufficiently long so that

one can easily see the effect of ageing on the thermal behavior of the PCM-concrete. Moreover, when we focus on the PCM­ concrete as a porous medium in saturated or non-saturated configurations and given the PCM capsules fragility, some questions can be raised such as the water evaporation process

ke p lace in the concrete capillary networks leading

by the gas diffuSion to the PCM capsules ejection.

which can t

.

The microstructure of the PCM-concrete mixtures was observed by Scanning Electronic Microscopy (Figure 7). It was

shown from the observations that the PCM capsules are well dispersed in the concrete matrix, thus the heterogeneous PCM­ concrete can be assumed to be homogeneous at the macro scale. Besides, it was noticed a damage of some PCM capsules and some fragments of broken PCM shells probably due to the shear forces of the mixing process during the manufacture of the PCM-concrete mixes or also to the thermo-hydro behavior of the concrete porous medium. This last fmding raises a problem for at least 2 reasons:

- The sh ell-made polymer of the PCM capsules plays the role

of contamer for the paraffin wax and improves accordingly the

heat transfer mechanism between the PCM and the surrounding concrete.

.

- The wax paraffin can be lost during melting when the PCM shell is damaged and thus the heat storage quality could be affected.

and thus the heat storage quality could be affected. Figure 7. SEM observations of the PCM-concrete.
and thus the heat storage quality could be affected. Figure 7. SEM observations of the PCM-concrete.

Figure 7. SEM observations of the PCM-concrete.

VI.

CONCLUSIONS

In this paper, an experimental investigation by Differential Scanning Calorimetry of the thermal properties of PCM concrete was presented. The specific heat capacity of both PCM materials and concrete modified with different amounts of PCM was estimated. The experimental results highlighted a significant enhancement of the heat storage capacity of the PCM-concrete compared with the reference one. Nevertheless, a loss of the mechanical strength was noticed with the addition of the PCM but the obtained values are still acceptable for some applications. The SEM observations showed some damage in the PCM capsules in the concrete. This phenomenon has the merit to be studied and investigated further since the leakage of the paraffin active agent of the PCM capsule may compromise the energy efficiency of the PCM-concrete in long term. Accordingly, it would be interesting in the future to explore deeply many research tracks such as to develop a more rigorous ageing program in order to investigate the long term thermal efficiency of the PCM-concrete. In addition, the

analysis of the thermo-hydro behavior of the PCM-concrete has to be studied in order to better improve our understanding of the complex interactions and coupled phenomena involved which can take place in the saturated concrete porous medium. Furthermore, given the random uncertainties linked to the experimentation, a parametric probabilistic analysis is required for the stochastic modeling [10] of the experimental uncertainties so that to have a safe prediction of the thermal properties of the PCM-concrete.

ACKNOWLEDGMENT

The authors would like to thank Laurence LESTUM from Basf Company for the Micronal PCM supply and the technical data and Frederic VALLES, research engineer, from the Arts et Metiers Paris Tech for his help for the SEM observations.

REFERENCES

[I] L.F. Cabeza, C. Castellon, M. Nogues, M. Medrano, R. Leppers, O. Zubillaga,"Use of microencapsulated PCM in concrete walls for energy savings",Energy and Buildings,vol. 39,pp.113-119, 2007.

[ 2 ] F. Kuznik, 1. Virgone, K. Johannes, "In-situ study of thermalcomfort enhancement in a renovated building equipped with phasechangematerial wallboard", Renewable Energy, vo1.36, pp.I458-

1462,2011.

[3]

A. Pasupathy, R. Velraj and R.V. Seeniraj, "Phase change material based building architecture for thermal management in residential and commercial establishments", Renewable and Sustainable Energy Reviews,vol. 12,pp. 39-64,2008.

[4]

D.W. Hawes, D. Banu and D. Feldman, "The stability of phase change materials in concrete",Solar Energy Materials and Solar Cells,vol. 27, pp. 103-118,1992.

[5]

D. Feldman,M.M. Shapiro, P. Fazio, D.W.Hawes and S. Sayegh, "The compressive strength of cement blocks permeated with organic phase change material",Energy and buildings,vol.6,pp.85-92,1984.

[6]

R.Leppers, "Development of Smart Microencapsulated Organic Phase­ Change-materials for enhancing heat storage capacities of concrete", WP4: Design and construction of concrete (concrete compositions), Intronreport R20040092,2005.

[7]

M.Hunger,AG.Entrop,I.Mandilaras,H.J.H.Brouwers,M.Founti, 'The behavior of self-compacting concrete containing micro-encapsulated Phase Change Materials", Cement and Concrete Composites, vol. 31, pp. 731-743,2009.

[8]

P. Meshgin and Y. Xi,"Effect of Phase-Change Materials on Properties of Concrete",ACI Materials Journal,vol. 109,No. I,pp. 71-80,2012.

[9]

H. Zhang,Q. Xu,Z. Zhao,1. Zhang, Y. Sun,L. Sun, "Preparation and thermal performance of gypsum boards incorporated with microencapsulated phase change materials for thermal regulation",Solar Energy Materails & Solar Cells,vol. 102,pp.93-102,2012.

[10]

A Eddhahak,A Dony and J. Colin,"Prediction of the rutting potential of bituminous binders using a stochastic approach", Road Material and pavement Design,voU3,pp. 38-48,2012.