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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
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
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
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)
-2.0
-2.5
Endo
-3.0
0 20 40 60 80
temperature (°C)
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)
0.10 1.0
FL 0.9 FL
SZ SZ
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)
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
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.
50
HV ¼ q Hm ½J=ml
where, q is density of the composite; Hm is the thermal
Absorption (Vol.%)
-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.
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
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
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.
changing behavior.
Ismail, K.A.R., Castro, J.N.C., 1997. PCM thermal insulation
(4) No change in chemical structure of PCMs after in buildings. International Journal of Energy Research 21,
1 year storage in the porous materials has been found 1281–1296.
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(5) Thickened latex was the best choice as coating Performance comparison of high-temperature packed bed
materials in our research, whose sealing performance operation with PCM and sensible-heat pellets. International
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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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