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Solar Energy 78 (2005) 471–480

www.elsevier.com/locate/solener

Granular phase changing composites for thermal


energy storage
a,*
Dong Zhang , Jianming Zhou a, Keru Wu a, Zongjin Li b

a
School of Materials Science and Engineering, Tongji University, Shanghai, China
b
Department of Civil Engineering, Hong Kong University of Science and Technology, Hong Kong, China

Received 12 January 2004; received in revised form 26 March 2004; accepted 19 April 2004
Available online 21 September 2004

Communicated by: Associate Editor Erich Hahne

Abstract

Granular phase changing composites for thermal energy storage were made of granular porous materials and
organic phase changing materials by means of vacuum impregnation method. Experimental studies on the vacuum
impregnation method, phase changing behavior, chemical compatibility between porous materials and phase changing
materials, and sealing performance of coating materials arrived in the following conclusions. Firstly, the vacuum
impregnation method is effective in loading porous materials with phase changing materials; and its setup is simple,
cheap and easy of scale-up. Secondly, organic phase changing materials (including fatty acids and their derivatives,
and paraffin) and inorganic porous materials (including expanded clay, expanded fly ash and expanded perlite) are suit-
able raw materials for the phase changing composites with respect to chemical compatibility, large thermal energy stor-
age density, and feasibility of large scale processing. Thirdly, thickened latex is the best choice of coating materials for
the porous material granules, whose sealing performance is about 40-fold higher than that of normal cement paste and
about sevenfold higher than that of the best polymer modified cement paste in this paper.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Phase changing material; Porous materials; Thermal energy storage; Composite; Vacuum impregnation; Chemical
compatibility

1. Introduction to high developing speed. Solutions to these problems


include improvement of the efficiency of energy systems
Energy shortage and environmental pollution are and the utilization of renewable energy sources, such as
two global issues. Especially in the developing countries, solar energy. Thermal energy storage is essential for
like China, the situation is much more serious partly due these two solutions (Dincer and Rosen, 2002). Compar-
ing to sensible thermal energy storage, latent thermal en-
ergy storage based on phase changing material (PCM) is
*
Corresponding author. Tel.: +86 21 6598 0527; fax: +86 21 preferred due to its high energy storage density and nar-
6598 0530. row operating temperature range (Zalba et al., 2003;
E-mail address: zhangdng@mail.tongji.edu.cn (D. Zhang). Khudhair and Farid, 2004). These two advantages lead

0038-092X/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2004.04.022
472 D. Zhang et al. / Solar Energy 78 (2005) 471–480

List of abbreviations and symbols

DSC differential scanning calorimetry TE ending temperature of the exothermic peak


Exo exothermic in DSC curve; [°C]
Endo endothermic TETS phase changing temperature span; [°C]
XRF X-ray fluorescence spectrometry HV thermal energy storage density, thermal
MIP mercury intrusion porosimetry energy stored in unit volume of material;
IA image analysis [J/ml]
FTIR Fourier transformation infrared spectrum Hm thermal energy stored in unit weight of
analysis material; [J/g]
PCM phase changing material HDSCcurve the integrated area between base line and
PMC polymer modified cement paste DSC curve; [J °C/(g s)]
NC normal cement paste dT temperature increment; [°C]
FL expanded fly ash granules dt time increment; [s]
SZ expanded clay granules of small size h temperature-increasing rate in the DSC test;
SL expanded clay granules of large size [°C/s]
PE expanded perlite granules q density; [g/ml]
TP peak temperature of the exothermic peak in Vf volume fraction of PCM in the composite
DSC curve; [°C] DT phase changing temperature shift; [°C]
TS starting temperature of the exothermic peak r pore radius; [lm]
in DSC curve; [°C] t thickness of PCM film in pores; [lm]

to small volume and less heat loss, which attract atten- The existing methods for encapsulating PCM in
tion of researchers in different fields (Ismail and Castro, building materials can be divided into two kinds: direct
1997; Jalalzadeh-Azar et al., 1997; Lee et al., 2000; Nee- incorporation (Feldman et al., 1991; Mehling et al.,
per, 2000; Arkar and Medved, 2002). 2002) and immersion methods (Feldman et al., 1995;
One of the important application fields of PCM is Kissock et al., 1998). The first method incorporates
building energy conservation (Khudhair and Farid, PCM during fabrication process of building materials.
2004), where PCM is used for two purposes. One is to The second method incorporates PCM into building
store the time-dependent and intermittent solar energy materials by means of natural immersion. These two
that does not necessarily match the energy need for kinds of methods are simple and easy of use. But their
building space heating at all times (Lane, 1983). The incorporation quantity of PCM in porous materials is
other is to shift building heating or cooling load from small, resulting in low thermal energy storage level.
peak to off peak electricity periods (Yamaha, 2001; In our recent research, vacuum impregnation method
Zhang et al., 2003), which is helpful in improving the was developed for incorporating PCM into granular
power generation management and can achieve signifi- porous materials. Experimental results show that large
cant economic benefit. quantity of PCM can be incorporated into porous space
It is interesting to combine building materials and with pore diameter from less than one micrometer to
PCM to render architectural components large thermal several hundred micrometers by this method, which ren-
energy storage capacity. One of the combination forms ders the granular composite large thermal energy stor-
is encapsulating PCM in porous building materials, such age capacity. The granular phase changing composites
as gypsum wallboard (Feldman et al., 1995) and porous can be added into different types of building compo-
concrete (Hadjieva et al., 2000), which are suitable ma- nents, such as wall, floor and ceiling, to increase their
trix materials for PCM. The porous building materials thermal energy storage capacity. They can also be used
have advantages of low cost, ease of fabrication and as cold storage media in the cooling system of buildings.
widespread application in building industries. Consider-
ing the possible problem of chemical compatibility with
matrix materials, most researchers selected organic 2. Experimental
PCMs, like fatty acids and their derivatives, alkanes
and their mixtures, which have been proven to have 2.1. Materials
good compatibility with inorganic porous building
materials (Feldman et al., 1991, 1995; Kissock et al., 2.1.1. Phase changing materials
1998; Lee et al., 2000; Arkar and Medved, 2002; Meh- Organic PCMs, including paraffin (alkane mixtures),
ling et al., 2002). fatty acids and their derivatives, were used. Their phase
D. Zhang et al. / Solar Energy 78 (2005) 471–480 473

changing temperature ranges between 0 °C and 70 °C, als that have been used in construction field for long
suitable for solar energy storage and other applications time are suitable for this purpose, such as expanded
in the field of building energy conservation. Figs. 1 perlite, expanded clay, and expanded fly ash granules.
and 2 shows their DSC curves and viscosity. Their vis- They have well interconnected pore structure with
cosity in liquid state lies in the range between 2 and porosity in the range between 30% and 80%. The chem-
10 mPa s, suitable for the vacuum impregnation process. ical neutrality within their porous environment guaran-
Their viscosity decreases gradually with temperature, tees them good chemical compatibility with the organic
which suggests that the impregnation results can be im- PCM. In addition, they are cheap and have abundant
proved by elevating the temperature of PCM and porous resources.
materials. Additionally, these PCMs are chemically sta- Fig. 3 shows pore diameter distribution of these por-
ble and non-toxic. Their price is low and feasible for ous materials, where FL, SZ and SL, and PE stand for
large-scale use in buildings. the expanded fly ash granules, two kinds of expanded
clay granules and expanded perlite granules, respec-
2.1.2. Porous materials tively. Fig. 4 gives some examples of the microscopic
Geometrical features of pore structure (including images of the porous material SZ. In the images, the
porosity, pore diameter distribution, pore connectivity dark colored area is pore and the light colored area is
and pore shape), chemical compatibility, and price pore skeleton. It is easy to see that the pore structure
are important factors in selection of porous materials is well interconnected. Similar microscopic images were
for encapsulating organic PCM. Many porous materi- also observed in other porous materials.

0.0
Exo
Mixture of fatty acids
Caprylic acid
-0.5
Capric acid
Lauric acid
Specific heat flow (W/g)

-1.0 Myristic acid


Butyl stearate
Paraffin 1
-1.5 Paraffin 2

-2.0

-2.5

Endo
-3.0
0 20 40 60 80

temperature (°C)

Fig. 1. DSC curves of organic phase changing materials.

16
Mixture of fatty acids
14 Caprylic acid
Capric acid
Lauric acid
12
Myristic acid
Viscosity (mPa.s)

Butyl stearate
10 Paraffin 1
Paraffin 2
8

2
0 20 40 60 80
temperature (°C)

Fig. 2. Viscosity of organic phase changing materials as function of temperature.


474 D. Zhang et al. / Solar Energy 78 (2005) 471–480

0.10 1.0

FL 0.9 FL
SZ SZ

Cumulative pore volume (l/l)


Incremental pore volume (l/l)

0.08 SL 0.8 SL
PE PE
0.7

0.06 0.6

0.5

0.04 0.4

0.3

0.02 0.2

0.1

0.00 0.0
0.01 0.1 1 10 100 0.01 0.1 1 10 100
(a) Pore diameter ( m) (b) Pore diameter ( m)

Fig. 3. Pore diameter distribution of the porous materials.

Fig. 4. Microscopic images of the porous material SZ.

Table 1 shows the chemical property of the porous most insoluble in water and has nearly neutral chemical
materials. The chemical composition of the inner part characteristics.
of the porous materials was determined by means of The mean granular diameter of FL, SZ, SL, and PE
X-ray fluorescence spectrometry. It can be seen that is 10 mm, 3 mm, 10 mm, and 2 mm, respectively.
the porous materials are mainly composed of SiO2,
Al2O3 and Fe2O3. The last column gives pH value of 2.1.3. Coating materials
the filtered liquid of the mixture of water and ground Latex and polymer modified cement (PMC) paste
fine powder of the porous materials. Details of the were used as the coating materials for porous granules
grinding, mixing and filtering can be found in next sec- loaded with organic PCM. The latex provided by Sika
tion. The pH value was determined by means of pH test Ltd., (Hong Kong) was a modified styrene emulsion.
paper. It was found that the porous materials were al- Its technical data are listed in Table 2. Mix formulas
D. Zhang et al. / Solar Energy 78 (2005) 471–480 475

Table 1
Chemical property and density of the porous materials
Porous materials XRF results of the inner part of porous materials (ms. %) pH Bulk density (g/ml)
SiO2 Al2O3 Fe2O3 K2O Na2O CaO MgO MnO TiO2 SO3 SrO
FL 48.95 29.39 11.34 1.72 n 4.52 1.29 n 1.68 0.86 0.26 7 0.97
PE 74.85 12.45 1.22 6.75 3.51 1.23 n n n n n 8 0.13
SL 55.73 17.01 16.13 3.81 1.75 2.02 1.90 0.31 1.35 n n 7 0.57
SZ 38.82 21.47 25.73 3.15 n 4.73 2.89 0.35 1.41 1.45 n 7 0.63

Table 2 uum grease. The vacuum pump was used to evacuate air
Technical data of Sika latex from the porous material. The vacuum meter was used to
Density (g/ml) Solids content (%) pH value Color monitor the vacuum pressure inside the system. The
1.02 50 ± 1 7.5 ± 0.5 White
evacuation process continued for about 30 min at the
vacuum pressure of 88.1 kPa. Then, the valve between
the flask and the container of PCM liquid was turned
open to allow the PCM liquid to flow into the flask to
Table 3
cover all the porous material granules. Finally, the vac-
Mix formulas of the polymer modified cement paste and normal
cement paste
uum pump was turned off. Air was allowed to enter the
flask again to force the PCM liquid to penetrate into
Formula Cement Latex Water Polymer/ the pore space of the porous material granules. After pre-
codes (g) (g) (g) Cement (%)
scribed immersion time, the porous material granules
PMC1 200 40 35 10 were taken out of the flask and cleaned with dry cotton
PMC2 200 80 0 20 towel. If needed, the PCM and porous material granules
PMC3 200 20 50 5 were heated to the desired temperature in the process.
NC 300 0 110 0
After the vacuum impregnation process, the porous
material granules loaded with PCM were treated with
coating materials. In the coating process the porous
of the polymer modified cement paste are shown in
material granules were immersed in the coating materi-
Table 3. The raw materials of the polymer modified ce-
als slurry for 5 min. Then they were taken out of the slur-
ment paste are silicate cement, latex and distilled water.
ry and put onto stainless steel mesh. The mesh was
shaken manually to separate the coated granules and
2.2. Vacuum impregnation method
form uniform coating layer on their surface. Cement
based coatings need 28 days of curing.
Fig. 5 shows a schematic drawing of the vacuum
impregnation setup. The porous material granules were
placed inside a flask, which was connected to a vacuum 2.3. Characterization techniques
pump, a vacuum meter and a container of PCM liquid.
The connecting joints of the system were sealed with vac- 2.3.1. Pore structure
Mercury intrusion porosimetry (MIP) and image
analysis (IA) were used to characterize the pore struc-
Phase changing material
ture of the porous materials. MIP test was conducted
on AutoPore IV 9500 (Micromeritics Instrument Corpo-
ration). The intrusion accuracy of AutoPore IV 9500
Valve was ±1% of full scale intrusion volume. IA was con-
ducted on Olympus BH2-UMA and Leica Q500MC.
Vacuum meter

Porous 2.3.2. Phase changing behavior


granules Differential scanning calorimetry (DSC) analysis was
Vacuum pump used to evaluate the phase changing behavior. The gran-
ular composites were crushed to coarse powders, which
Heater
were used to conduct the DSC test on SERARAM DSC
92. Its heat measurement accuracy was ±1%. Its temper-
ature measurement accuracy was ±0.1 °C. The DSC
sample weight was around 70 mg. The temperature-ris-
Fig. 5. Schematic drawing of the vacuum impregnation setup. ing rate was 5 °C/min. The atmosphere was N2.
476 D. Zhang et al. / Solar Energy 78 (2005) 471–480

2.3.3. Chemical properties 100


The chemical composition of the porous materials Porosity

Absorption and porosity (Vol.%)


90
Natural immersion
and their lixiviumÕs pH value were determined by means 80 Vacuum impregnation
of X-ray fluorescence spectrometry (XRF) on JEOL
70
JSX-3201Z and pH test paper. In the determination of Relative error limit of absorption measurement: ±5%

the chemical composition, the porous material granules 60

were firstly splitted, their splitted surface was used in 50


the test. In determination of pH value, the porous mate- 40
rials were ground into fine power by means of a swing 30
grinder. Then the powder was mixed with distilled water
20
in ratio of 1:20 and stirred for 8 h at a speed of 600 RPM.
The mixture was then filtered through four layers of 10

Fisher medium-fine filter paper with particle retention 0


PE SL SZ FL
of 2–5 lm. Then the pH value of the filtered liquid was
Porous materials
tested.
Fourier transformation infrared spectrum analysis Fig. 6. Comparison between vacuum impregnation and natural
(FTIR) was used to study the possible chemical reac- immersion.
tions between the PCMs and the porous materials. For
the pure PCMs, they were melted and formed into thin immersion time were 30 min. In the natural immersion
film on the surface of KBr slice, which was used to con- process, the porous materials were immersed in liquid
duct FTIR analysis. For the PCMs inside composites, directly for 1 h without vacuum evacuation. The absorp-
the composites granule was placed on the surface of tion value was average of at least three samples, and its
KBr slice and heated by a heating lamp, making the relative error limit was about 5%.
PCMs inside the granule melting and flowing out onto The difference between the absorption results of the
the surface of KBr slice; then the KBr slice with thin film vacuum impregnation and natural immersion is quite
of the PCMs was used to conduct the FTIR analysis. clear. Especially for expanded clay (SL and SZ), there
The FTIR analysis was conducted on EQUINOX 55 is a more than three times increment in the absorption
of Bruker Optik GmbH. of vacuum impregnation method comparing to that of
natural immersion. For the other two kinds of porous
2.3.4. Sealing performance of coatings materials the increment is about 40%. Possible reason
Anti-osmosis test was used to evaluate the sealing of the different increments for different porous materials
performance of coatings. In this test, the same setup may be found in their pore structures (Fig. 3). There are
and similar steps for the vacuum impregnation process more fine pores in expanded clay (SL and SZ) than in
were used to evaluate the anti-osmosis performance of the other two kinds of materials. It is more difficult for
coatings against liquid under vacuum pressure. Coated liquid to permeate into pore space with smaller diameter
porous material granules without PCM were placed into than that with larger diameter. So the vacuum impreg-
the flask. Then the vacuum evacuation process was nation method is more effective and necessary for the
started and continued for 1 h. Then liquid was allowed porous materials with finer pores.
to enter the flask and cover all granules before the valve
between the inner air and outside was turned open. The 3.1.2. Effect of immersion time and processing
immersion continued for 1 h. Then the granules were ta- temperature
ken out of the liquid and cleaned with dry cotton towel. The viscosity of all PCMs in our studies is in the same
The weight-increasing ratio of the granules in the test range, from about 3 to 10 mPa s (Fig. 2). This resulted in
was used to evaluate the anti-osmosis performance of similar absorption results for all PCMs in the porous
the coatings. materials.
Fig. 7 shows the effect of immersion time on the PCM
absorption in porous material (SL). The absorption in-
3. Results and discussion creases with the immersion time at a gradually smaller
rate.
3.1. Vacuum impregnation results Fig. 8 shows the effect of processing temperature on
the absorption results. The absorption increases with
3.1.1. Comparison with natural immersion the temperature at a gradually smaller rate, for the vis-
Fig. 6 shows the results of PCM absorption in porous cosity of PCMs decreases with temperature at a gradu-
materials by means of the vacuum impregnation and ally smaller rate too.
natural immersion methods. In the vacuum impregna- Although a lower viscosity and longer immersion
tion process, the vacuum evacuation time and the time would lead to a larger absorption in general, they
D. Zhang et al. / Solar Energy 78 (2005) 471–480 477

60
105 °C 90 °C 51 °C 22 °C

50
Absorption (Vol.%)

40

30

20
Phase changing material: Butyl stearate
Porous material: Expanded clay (SL)
10 Relative error limit of absorption measurement: ±5%

0
0 10 20 30 40 50 60
Immersion time (min)
Fig. 9. Determination of phase changing parameters on DSC
Fig. 7. The effect of immersion time on the vacuum impreg- curve.
nation results.

of the composite, which can be calculated according to


60 the following equation:
60mins 30mins 20mins 10mins 5mins

50
HV ¼ q  Hm ½J=ml
where, q is density of the composite; Hm is the thermal
Absorption (Vol.%)

40 energy stored in unit weight of the composite. Hm can


be determined based on the DSC curve. As shown in
30 Fig. 9, the integrated area between the base line and
the DSC curve, HDSCcurve, has the following form:
20 Phase changing material: Butyl stearate Z
Porous material: Expanded clay (SL)
H DSCcurve ¼ ðY BaseLine  Y DSCcurve Þ  dT ½J  C=ðg sÞ
Relative error limit of absorption measurement: ±5%
10

Hm can be calculated from HDSCcurve:


0 Z
20 40 60 80 100 120
H m ¼ ðY BaseLine  Y DSCcurve Þ  dt
Temperature ( °C )
Z  
Fig. 8. The effect of processing temperature on the vacuum dt
¼ ðY BaseLine  Y DSCcurve Þ  dT 
impregnation results. dT
dt
¼ H DSCcurve  ¼ H DSCcurve =h ½J=g
dT
also result in higher processing cost. So it is not effective where YDSCcurve is the specific heat flow, YBaseLine is the
and economic to elevate the processing temperature and base line of the DSC curve, h is the temperature-rising
to prolong the immersion time unlimitedly. In Figs. 7 rate in the DSC test. Hm is calculated by the testing sys-
and 8, it can be seen that 30 min and 30 °C above the tem automatically at the end of the DSC test. The rela-
phase changing temperature are proper choices for the tive error limit of Hm is ±1%. And the relative error limit
immersion time and the processing temperature, of HV is about ±2%.
respectively. The phase changing temperature is divided into start-
ing temperature (TS), peak temperature (TP) and ending
3.2. Phase changing behavior of the composites temperature (TE). The peak temperature (TP) is the tem-
perature at the peak point of the DSC curve. The start-
Phase changing behavior is described with two ing temperature (TS) and the ending temperature (TE) of
parameters, thermal energy storage density and phase phase changing are the temperatures at the intersection
changing temperature, which can be determined by of the extrapolated base line and the tangents to the
means of DSC analysis. Fig. 9 shows an example of DSC curve drawn at the inflection points of the left
DSC curves of the composite. Thermal energy storage and right sides of the peak (Fig. 9). The error limit of
density (HV) is the thermal energy stored in unit volume temperature determination in DSC test is ±0.1 °C.
478 D. Zhang et al. / Solar Energy 78 (2005) 471–480

0.5 PCM: Lauric acid


Exo 60
Ending temperature

Phase changing temperature (˚C)


0.0 Peak temperature
Starting temperature
Error limit of temperature: 0.1˚C
Specific heat flow (W/g)

-0.5 55

Lauric acid
-1.0 FL with PCM
SZ with PCM 50
-1.5 SL with PCM
PE with PCM
-2.0
45

-2.5

Endo
-3.0 40
10 20 30 40 50 60 70 Pure PCM FL with PCM SZ with PCM SL with PCM PE with PCM

Temperature ( °C )
Fig. 12. Phase changing temperatures of composites.
Fig. 10. DSC curves of the composites loaded with PCM.

slightly with the increase of the volume fraction. The


Fig. 10 shows the DSC curves of composites made of phase changing temperature span (TE–TS) is different
porous materials and one kind of fatty acid (lauric acid), for different porous materials or different volume frac-
and lauric acid by itself. Fig. 11 shows the thermal en- tion of PCM.
ergy storage density as function of the volume fraction Thermal conductivity (physical factor) and pore
of PCM in composites. The linear relationship between structure (geometrical factor) of the porous materials
the thermal energy storage density and volume fraction may affect the phase changing temperatures of the
of PCM is quite clear and understandable. composites. It is quite easy to understand that the ther-
Compared to the thermal energy storage density, the mal conductivity of the pore skeleton of the porous
phase changing temperatures are affected by the porous materials influences the heat transfer rate from outside
materials in a more complicated way, as shown in Fig. to the PCM inside the pore space, which in turn influ-
10. The phase changing temperatures of the composites ences the length of the phase changing temperature
made of different porous materials and different volume span and phase changing temperatures. Next, the por-
fraction of PCM are shown in Fig. 12. The peak temper- ous geometry has significant influence on the phase
ature (TP) and ending temperature (TE) of phase chang- changing behavior (Findenegg and Schreiber, 2002;
ing shift toward high temperature direction with the Zhang et al., 2004). Inside limited porous space, vol-
increase of volume fraction of PCM. In contrary, the ume increment of melting PCM leads to pressure incre-
starting temperature (TS) of phase changing decreases ment. According to Clapeyron equation, volume and
pressure increments lead to elevation of melting tem-
perature. And the elevation is larger for higher volume
PCM: Lauric acid fraction of PCM. Additionally, the limitation of pore
150
on the volume increment is strengthened for smaller
Relative error limit of H V : ±2% Pure PCM
pore diameter. So the pore diameter has direct influ-
ence on the phase changing temperature, as described
by Gibbs–Thomson equation (Findenegg and Schrei-
100
PE with PCM
ber, 2002):
H v (J/ml)

1
DT /
rt
SZ with PCM
50 where DT, r and t are phase changing temperature shift,
SL with PCM pore radius and thickness of PCM film in pores, respec-
FL with PCM tively. This suggests that the phase changing tempera-
tures change with the pore diameter. Because the pore
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
diameter in porous materials scatters in range from
Vf nanometer to millimeter, the shifts of phase changing
temperatures of PCM in the composites are different,
Fig. 11. Thermal energy storage density of composites versus which in turn results in a widened phase changing tem-
volume fraction of PCM. perature span.
D. Zhang et al. / Solar Energy 78 (2005) 471–480 479

3.3. Chemical compatibility between PCMs and porous 50


Relative error limit of absorption measurement: ±5% 46.9%
materials

PCM absorption(Wt.%)
40
The porous materials used in our research are chem-
ically stable and neutral, as shown in Table 1. The alka-
line (K2O and Na2O) content is quite low for the 30

expanded clay and fly ash. For the expanded perlite 22.8% 23.6%
the mass fractions of K2O and Na2O are 6.75% and 20
3.51%, which are slightly high compared to those of
the other two kinds of porous materials. The pH value
10 8.22%
of lixivium of the ground powder of the porous materi-
als is shown in the same table, which is consistent with
1.18%
the XRF result. All these suggest that the expanded clay 0
and fly ash are chemically stable and neutral; while the Latex PMC 2 PMC 1 PMC 3 NC

expanded perlite has a very weak alkalinity. Coating materials


In order to examine the chemical compatibility of Fig. 14. Result of anti-osmosis test.
PCM and porous materials, composites made of PCMs
(including fatty acid, paraffin, and butyl stearate) and
material by itself. Solid content was about 75% in the
porous materials (including expanded clay, fly ash, and
thickened latex. Expanded clay (SL) and butyl stearate
perlite) were stored in normal testing room for 1 year.
were used in the anti-osmosis test.
Then they were used to conduct chemical compatibility
As shown in Fig. 14, the sealing performance was en-
test by means of FTIR. In Fig. 13, the upper part shows
hanced remarkably by the addition of latex in cement
the FTIR spectrum of fatty acid (lauric acid) without
paste, increasing more than four times as polymer/
contact with the porous materials; the lower part shows
cement ratio increased from 0% to 20% in term of the
the FTIR spectrum of the same fatty acid after stored in-
reciprocal of PCM absorption. And the latex was an
side the porous space of the expanded perlite for 1 year.
even more effective coating material by itself. Its sealing
No obvious difference can be found between these two
performance was about 40-fold higher than that of nor-
spectra, which suggests that the effect on the fatty acid
mal cement paste (NC) and about 7-fold higher than
caused by the weak alkalinity of the expanded perlite
that of the best polymer modified cement paste
is negligible. Fatty acid is very stable in the expanded
(PMC2). So latex by itself is the best choice as the coat-
perlite for long time. FTIR results for other PCMs
ing material for the composites.
and porous materials were similar.

3.4. Sealing performance of coating materials 4. Concluding remarks

Fig. 14 shows results of anti-osmosis test of different Fabrication method and performance of granular
coating materials, including latex, polymer modified ce- phase changing composites made of organic PCMs
ment paste (PMC) and normal cement paste (NC). The and granular porous materials are presented in this
formulas of the PMC and normal cement paste are listed paper, the following conclusions can be drawn.
in Table 3. Latex was thickened before used as coating (1) Organic PCMs (including fatty acids and their
derivatives, and paraffin) and inorganic porous materi-
als (including expanded clay, fly ash and perlite) are suit-
100
able raw materials for the phase changing composites
80 with respect to high load of PCM, chemical compatibil-
ity, large thermal energy storage density, feasibility of
Transmittance (%)

60
large scale processing, non-toxic and low cost.
40 Lauric acid (2) Vacuum impregnation method is effective in load-
100 3500 3000 2500 2000 1500 1000 ing porous materials with organic PCMs. Up to 65% of
PCMs by volume can be loaded in porous materials by
80
this method. In addition, its setup is quite simple, cheap
60 and easy of scale-up. The key parameters in the vacuum
impregnation method are immersion time and process-
40
Lauric acid after storing in PE for 1 year
ing temperature, which should be optimized.
3500 3000 2500 2000 1500 1000
-1
(3) The thermal energy storage density increases al-
Wavenumber cm
most linearly with the volume fraction of PCMs in
Fig. 13. FTIR results of fatty acid. the composites. As the volume fraction increases, the
480 D. Zhang et al. / Solar Energy 78 (2005) 471–480

temperature span of phase changing becomes widened, International RILEM Workshop on Frost Resistance of
which suggests that the porous materialÕs physical prop- Concrete, Cachan Cedex, France, pp. 105–116.
erty (thermal conductivity) and geometrical property Hadjieva, M., Stoykov, R., Filipova, T., 2000. Composites salt-
(pore structure) have remarkable influences on the phase hydrate concrete system for building energy storage.
Renewable Energy 19, 111–115.
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The research in this paper was financially supported by Volume I: Background and Scientific Principles. CRC,
the National Natural Science Foundation of China Florida, pp. 1–30.
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