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Abhat1983 PDF
Abhat1983 PDF
t983 110384192X/83/04031~-2050300/0
PrintedinGreatBrilain ~ 1983PergamonPres~lhl
A. ABHAT
Institut for Kernenergetik und Energiesysteme (IKE), University of Stuttgart, Stuttgart, FRO
Abstract--Heat-of-fusion storage materials for low temperature latent heat storage in the temperature range
0-120°C are reviewed. Organic and inorganic heat storage materials classified as paraffins, fatty acids, inorganic
salt hydrates and eutectic compounds are considered. The melting and freezing behaviour of the various substances
is investigated using the techniques of Thermal Analysis and DifferentialScanning Calorimetry. The importance of
thermal cycling tests for establishingthe long-term stability of the storage materials is discussed. Finally, some data
pertaining to the corrosion compatibilityof heat-of-fusion substances with conventional materials of construction is
presented.
3. HEAT-OF-FUSION STORAGEMATERIALS
Desired material properties
fThe following abbreviations are used in the text:
LTES = latent heat thermal energy storage. A large number of organic and inorganic substances
PCM = phase change (heat-of-fusion) storage material. are known to melt with a high heat of fusion in any
SEVok30,No.4--8 3 13
314 A. ABHAT
f I _
HEATEXCHANGERDEVELOPMENT ]
I MATERIALINVESTIGATION q
1
1
HEAT STORAGE I THERMAL EXPERIMENTAL 7
MATERIALS - - MATERIALS? ANALYSIS, INVESTIGATION]
PARAMETRIC
INVESTIGATION
F- I I LABORATORY
MODELS J
PROPERTY FREEZING
CHA-
DATA RACTERISTICS
1 INTEGRATION
WITH HEATING/
COOLING
SYSTEMS
PILOT UNITS FIELDTESTS
~Z~ [CO~;~I~I~ITYI I SIMULATION I L
n~,~S~
vKtu~,
i FORMANCEOFJ
yr.-l/
LJCOMPARISONS
Fig. 1. Flowchart providingan overviewof the various steps in the developmentof a latent heat storage system.
required temperature range, e.g. 0-120°C. However, for able properties they possess in comparison with in-
their employment as heat storage materials in LTES organic compounds. Some of these advantages include
systems, these phase change materials must exhibit cer- their ability to melt congruently, their self-nucleating
tain desirable thermodynamic, kinetic and chemical pro- properties, and their compatibility with conventional
perties. Moreover, economic considerations of cost and materials of construction[3]. We shall now examine
large-scale availability of the materials must be con- some of the important heat storage material groups in
sidered. The various criteria that govern the selection of some detail.
phase change heat storage materials are summarized in Para~ns. Paraffins, as we normally understand them,
Table I. are substances having a waxy consistency at room tem-
perature. Chemically speaking, paraffin waxes consist
Candidate heat storage materials primarily of straight-chain hydrocarbons with only a
It is quite apparent that no single material can fully small amount of branching, such as 2-methyl groups,
satisfy the long list of criteria listed in Table 1. Trade- near the end of the chain. Paraffins contain in them one
offs are hence made in the selection of candidate heat major component called alkanes, characterized by
storage materials. Within the operating temperature C,H2,+z; the n-alkane content in paraffin waxes
range of 0-120°C, candidate PCMs are grouped into the usually exceeds 75 per cent and may reach lOOper
families of organic and inorganic compounds and their cent[13]. Depending on the chain length of the alkane in
eutectica, as seen in Fig. 2. Sub-families of organic the paraffin, paraffins may be even-chained (n-paraffin)
compounds include paraffin and non-paraffin organics. or odd-chained (iso-paraffin).
Figures 3(a, b), respectively show the latent heat of Pure paraffins contain only alkanes in them, for
fusion per unit mass and per unit volume of some heat example the well-known paraffin octadecane, C~,H38.
storage materials of interest in the temperature range The melting point of the alkanes increases with the
0-120°C[1, 19, 23, 29]. Of particular interest is Fig. 3(b), increasing number of carbon atoms; alkanes containing
which provides information on the compactness of an 14--40 C-atoms possess melting points between 6 and
LTES system for a given amount of energy storage. 80°C and are generally termed as paraffins. Commercial
Figure 3(b) shows that the organic compounds have a waxes, on the other hand, may have a range of about 8-15
volumetric latent heat storage capacity in the range 125- carbon-numbers [13].
200 kJ/dm ', whereas that of the salt hydrates is almost In their solid phase, paraffins are generally found in
twice as much, between 250-400 kJ/dm 3. two allotropic modifications that differ in their physical
Notwithstanding the disadvantages concerning properties and the crystal structure. The primary
volume requirements, the organic substances serve as modification existing at higher temperature, i.e. slightly
important heat storage materials due to the several desir- above the melting point of the substance, is soft and
Low temperature latent heat thermal energy storage: heat storage materials 315
B, KINETIC CRITERIA
C. CHEMICAL CRITERIA
D. ECONOMIC CRITERIA
THE PHASE CHANGE MATERIAL SHOULD BE
I INEXPENSIVE
Paraffins 1
Compounds
Non-parafhn 1
Orgamcs ~]
OrgonlCS
Eutectic~" )
I,~orgo~n,cs compounds I
Eutectlc~: }
Fig. 2. Families of phase change heat storage materials[3].
316 A. ABHAT
450 l i
A, PARAFFINS
1, PARAFFIN 5913
2, PARAFFIN 6106
400 3. PARAFFIN 5838
Paraffins
4, PARAFFIN 6035
Non-Paraffin Organics
-~ 350 5. PARAFFIN6403
• Inorganic Compounds 6. PARAFFIN6499
L21
[] Eutectic Compounds 7, OCTADECANE
o
~E
300 25 •
29
37 B. ORGANICCOMPOUNDS
~ 250 22 19 27 28 36 A
• 7 20 8, CAPRILIC ACID
24
33A ,&013 35 5 ~6 9. POLYGLYCOLE 600
c
.o
u'l
200 23• 19
26
•
r, N A18 39•
1U.
11,
CAPRICACID
LAURICACID
u_ 150 A A • 4 12. MYRISTIC ACID
8 10 30 E Ig
A
41 13. POLYGLYCOLE 6000
"6 9
A ~2 •
31• •32 17 38 14. LOXIOL G 32
~ 100 15. PAI241TICACID
T 16. STEARICACID
17. BIPHENYL
18. PROPIONAMIDE
19. NAPTHALENE
I I I I I
20. ACETAMIDE
0 10 20 30 40 50 60 70 80 90 100 110 120
(a) Melting Point [°C] C. IHQRGAN1CCOMPOUNDS
®
100
"1- p, EUTEGTIC COMPOUNDS
Fig. 3. Latent heat of fusion per unit mass and per unit volume of selected phase change heat storage materials
undergoing a phase transition within the temperature range 0-120°C.
plastic, the individual crystals are needle-shaped. The paraffin mixtures and are not completely refined of oil.
secondary modification existing at lower temperature, i.e. Manufacturers' data on their physical properties as well
below the melting point, is hard and brittle, the crystals as cost data are also included in Table 2.
are disc-shaped. The transition from one crystal form to Non-para#in organics. Although a number of non-
another is reversible [28]. paraffin organics have been included in Figs. 3(a)--(b), we
Paraffins qualify as heat-of-fusion storage materials shall restrict our discussion to the group of materials
due to their availability in a large temperature range and called "Fatty acids". Other non-paraffin organics may,
their reasonably high heat of fusion. Furthermore, they however, be assumed to have properties similar to those
are known to freeze without supercooling [4]. Due to cost of the fatty acids.
considerations, however, only technical grade paraffins Fatty acids. Fatty acids are organic compounds
may be used as PCMs in latent heat stores. Table 2 lists characterized by CH3(CH2h,COOH with heat of fusion
some technical grade materials, which are essentially values comparable to that of paraffins. Some fatty acids
Low temperature latent heat thermal energy storage: heat storage materials 317
1,20 2)
_ 1)
C14 4.5 165 20
CL5 - C16 8 153 0,50 2) 20
5913 3) C]_3 - C24 20 22 - 24 189 144 0.900 0.760 2.1 0.21 0.50 4
0CTADECANE C18 0 28 244 189 0.814 0.774 2.16 0,15 150,0 4
6106 3) C16 - C28 5 42 - 44 189 145 0,910 0.765 2.1 0.21 0.70 4
P].16 4) 45 - 48 210 165 0.817 0,786 2.5 0,44 2) 20
5838 3) C20 - C33 < 0.5 48 - 50 189 145 i0.91P 0.769 2.1 0.21 1,00 4
6035 3) C22 - C45 4 58 - 60 189 150 0.gL~O 0,795 2.1 0.21 0,60 4
6403 C23 - CLE5 < 0,5 62 - 6 4 189 150 0.915 0,790 2.1 0,21 1,00 4
6499 3) C2_].- C50 3 66 - 68 189 157 0.930 0.830 2.1 0.21 0,80 4
2) COSTESTIMATESARE FOR 1974 (REF. 2(]) 4) MANUFACTURERS OF PARAFFINP116: SUN OIL COMPANY,USA
of interest to low temperature LTES applications are called decomposition. Unless special measures are taken,
listed in Table 3. Ihis phenomenon is irreversible, i.e. during freezing, the
Fatty acids are known to possess a reproducible mel- solid phase does not combine with the saturated solution
ting and freezing behaviour and freeze with little or no to form the original salt hydrate. Another important
supercooling[4, 19]. They hence qualify as good PCMs. problem with salt hydrates is their poor nucleating pro-
Their major drawback, however, is their cost which is perties resulting in supercooling of the liquid salt hydrate
2-2.5 times greater than that of paraffins. prior to freezing. Suitable measures must be adopted to
Salt-hydrates. Salt hydrates, characterized by eliminate supercooling or reducing it to a minimum.
M.nH20, where M is an inorganic compound, form an Typical methods suggested in the literature for this pur-
important classs of heat storage substances due to their pose are: (1) addition of nucleating agents that have a
high volumetric latent storage density (see Fig. crystal structure similar to that of the parent
3(b)). In fact, their use as PCMs has been propagated as substance [25]: (2) using a "cold finger" in the PCM[20];
early as 1947124]. Table 4 provides a list of some salt (3) promoting heterogeneous nucleation by using (rough)
hydrates melting in the temperature range 0-120°C along metallic heat exchanging surfaces in contact with the salt
with their thermophysical properties and cost data. hydrate[4]. We shall examine the influence of these
The major problem in using salt hydrates as PCMs is techniques on the melting and freezing characteristics of
that most of them melt incongruently, i.e. they melt to a salt hydrates in greater detail at a later stage.
saturated aqueous phase and a solid phase which is The selection of a salt hydrate as a PCM can be eased
generally a lower hydrate of the same salt. Due to by an understanding of the binary phase diagrams, M-
density differences, the solid phase settles out and H20, for which the reader is referred to Ref. [30]. To
collects at the bottom of the container, a phenomenon illustrate the use of the phase diagrams, two examples
318 A. ABHAT
NA2HP04,12H20 35,0 281 405 1.520 (s) 1,70 (s) 0,514 (32%) 0,95 16
1.442 (L) 1,95 (L) 0,476 (49"C)
80
L ~,m
c_)
o
e~ 2O
D
- - "1-
%
-20 z z
-40
0 20 t,0 60 80
Weight % Zn(NO3)2
Table 5. Physical properties and cost data of some organic and inorganiceutectic compounds
MATERIAL MELTING HEAT-OF-FUSION SPECIFIC COST REFERENCE
(WEIGHT ~ OF COMPOUND POINT HEAT
IN BRACKETS)
°C KJ/KG KG/DM
3 KJ/KG K DM/KG
NA2S04 (31%)
NACL (13 %) 4 234 1) _ 16
KCL (16 %)
H20 (40 %)
CACL2 (48 %)
NACL (4.3 %) 26.8 _1)
20
KCL (0.4 %)
H20 (47.3 %)
Table 6. Details of measurement techniques employedfor the determination of melting and freezing behaviour of
phase change heat storage materials[6]
MEASURB'~ .~P/~qATI~ DESIGN+ QUANTITYOF ~F.ASLIRB~TS MADE DATA EVALL~TED
IECI-INIQUE HEAT STORAGE
SUIBST/~CE
IN THE TESTS
(ORDER OF
MAGNITUDE)
ELEMENT
/5/
structure. There are also other structures in which the Measurement techniques
guest molecules participate in the water lattice directly, Primarily two measurement techniques are employed
these substances are known as semi-clathrates and in- for the determination of the melting and freezing
clude hydrates of amines and tetra alkylammonium characteristics: (1) Differential Scanning Calorimetry
salts [20]. (DSC), and (2) Thermal Analysis (TA). Table 6 provides
Examples of clathrate hydrates are[20]: SO2.6H20 details of the two measurement techniques and a listing
(mpt), 7°C; AHF+ =247kJ/kg), C2H40" (6.9)H20 (rap, of data that may be evaluated.
ll.l°C). The two techniques distinguish themselves in terms
Examples of semi-clathrate hydrate are [20]: of the type of measurements made, the quantity of the
(CH3)3N.(10~/4H20) (mp, 5.9°C, AHF=239kJ/kg), sample used in the tests and the speed with which results
Bu4NOH.32H20 (mp, 30.2°C). can be obtained. For example, the DSC provides quick
Like salt hydrates, clathrate hydrates may melt con- and reliable results in the form of Energy-Time diagrams
gruently or incongruently. They also tend to supercool (Thermograms) using very small quantities of the sample
and hence suitable nucleating techniques must be found (ca. 1-10mg)). Evaluation of the thermograms yields
to promote crystallization. rather precise values of the phase transition tem-
peratures during melting and freezing of the sample, the
4. MELTING AND FREEZING CHARACTERISTICS heats of fusion and solidification and the specific heat
By melting and freezing characteristics of phase variation as a function of temperature. The DSC is,
change heat storage materials, we understand the however, a severe test for substances that supercool,
behaviour exhibited by these materials during heating since the supercooling tendencies are maximized due to
and cooling, viz. melting and freezing ranges, congruency the small quantity of the samples and the poor nucleation
of melting, nucleation characteristics, supercooling of the conditions in the DSC testing pans. Consequently, for
melt and stability to thermal cycling. A comprehensive materials like salt hydrates, the DSC fails to provide
knowledge of the melting and freezing behaviour of meaningful information on the degree of supercooling
heat-of-fusion storage substances, and particularly its and on the freezing point of the substance[7, 19].
reproducibility as a consequence of repeated melting and The Thermal Analysis technique, on the other hand,
freezing of the substances, is hence essential for the involves the determination of Temperature-Time (T-t)
assurance of the long-term performance of a latent heat diagrams, or the Heating and Cooling curves, recorded
store. during the melting and freezing of the sample. The
TA-technique uses about 10 g to a few kilograms of the
fmp = melting point. sample, depending on the apparatus used, and is hence
AH~- = heat-of-fusion. slower. With proper care, the rate of heating and cooling
Low temperature latent heat thermal energy storage: heat storage materials 321
_J.--g/ Louric _ 5o
Acid ~_
~ 4°rT, It
30 I I
2Oo "i'o' 11min]
't4o 20
0
I ,
20
, i
40
i i
60
i
~
J ~ i
100
J i
120
i~
140
rim=hi
60 , i- , , i , r ~
(c) ,-s o ~ ~
~ ]o Na2HPO4. V 4o
12 H20 30
10 2O
i
O t.O 80 120 160 2(10 240 280 0 2 t. 6 10 12
tlm~l ~lh]
Fig. 6. Typical heating and cooling curves for representative heat storage materials belonging to the material
families of (a) commercial paraffins, (b) fatty acids,and (c) inorganic salt hydrates [3].
can be well controlled and relatively accurate results can seen in Fig. 6(a), the paraffin exhibits two freezing
be gained. If the tests are undertaken in glass containers, ranges: a narrow freezing range characterized by QN
they suffer from the disadvantage that metallic surfaces (Region II) and a larger freezing range characterized by
that generally form the heat exchanging surface within a NP (Region III). The two freezing ranges respectively
latent heat store, or other means that are employed to signify a liquid-to-solid transition and a solid-to-solid
improve heat transfer in a latent heat store, are transition[3]. A part of the total latent heat of fusion
absent. Nucleating conditions different to those is stored in the substance during each of these trans-
in actual LTES systems hence exist. Experiments itions.
done in scaled-sown test models are the most accurate as Not all commercial waxes (all of these are essentially
conditions similar to those in large-scale LTES systems paraffin mixtures) display a freezing behaviour as shown
are simulated within them. These tests are also the in Fig. 6(a). For the sake of comparisons, the cooling
slowest in comparison to those in glass apparatuses due curves obtained during slow cooling of three different
to the large quantities of phase change materials they paraffins are presented in Fig. 7 [17]. The paraffins in-
require (1-10 kg). cluded in the diagram are seen to vary extensively in their
Thermal cycling of the sample to obtain data on the freezing interval. While the n-paraffin 6106 exhibits a
reproducibility of the melting and freezing behaviour of rather fiat freezing plateau during the time period of the
the substance may be undertaken using both measure- experiments, the iso-paraffins 6403 and 6035 undergo
ment techniques. Any variations observed in the form of freezing in a temperature range. In fact, the freezing
the endothermic or exothermic peaks on the DSC-ther- interval of paraffin 6035 is extremely large, rendering it
mograms, or alterations in the values of the ther- completely unfit for use in an LTES system.
mophysical properties of the thermally cycled heat
90 , , , , ,
storage materials, serve as a measure of the change in 1--
their melting and freezing characteristics. In the TA- 80~ -- Paraffin 61.03
measurements, on the other hand, changes in the form It \ - - - Paraffin 6035
~ 70I', ~.._ ~ - - - - P a r a f f i n 6106
of the temperature-time diagrams or in the heat transfer
rate into or out of the sample provide information on the ® 60 = \
influence of thermal cycling.
50 \ ~
We shall now discuss some results for the melting and
freezing characteristics of PCMs belonging to three ~o " ~ "" "" ~--~~ ~
materials groups: paraffins, fatty acids and salt hydrates.
Paraffins
13°
2o 4 2i ; ,i ~i
(a) TA-measurements. Figure 6(a) shows typical heat- Time [h]
ing and cooling curves obtained during TA-measure- Fig. 7. Comparison of cooling curves for three different com-
ments with a technical grade n-paraffin, paraffin 6106. As mercial paraffins[17].
322 A. ABHAT
]MANUFACTURER'S RECOMMENDED
FREEZING RANGE
38 - 43 *C
36 - 43 "C
10
PARAFFIN 6&O3
HEATING 2 CYCLE
RUN NO 1L2
HEATING RATE 5KtMIN
/
G2~
Another important observation with paraffin is the
large difference between the experimentally measured
b
freezing range and the manufacturer's data, as seen
L L I
through th6 example of Paraffin 6106 in Table 7. This 8 1'0 I~N]12 "~141
I iTIWE j
result is of particular importance to the design and 280 290 300 310 320 330 3~0 350
TEMPERATURE [K} ]
operation of a LTES system, which calls for an exact
knowledge of the phase transition temperature range of
the heat storage material. Further quantification of these
results can be carried out using the DSC-technique.
(b) DSC-measurements. Typical thermograms for n-
025
and iso-paraffins are presented through the example of
X
Paraffin 5838 and Paraffin 6403 in Figs. 8 and 9, PARAFFIN 6~03
respectively[7]. The n-paraffin exhibits a sharp peak COOLING 2 CYCLE
RUN NO 1~3
around 46°C and secondary peaks at temperatures be- I N G RATE 5K/MIN
tween 12 and 46°C, whereas the iso-paraffin exhibits one ua
il I/
I/
amount of supercooling during the freezing of fatty acids
does not hamper their potential use as heat storage
substances.
Although fatty acids are good heat storage sub-
stances, they are somewhat too expensive for large-scale
IO 15 20 2S TIME [MINI
heat storage applications. They are, however, far cheaper
) 317 31~ 31--15 31"J& I. T E M P E R ~ K"'~
|
than research grade paraffins and are recommended for
Fig. 10. DSC-thermograms of lauric acid, representative of fatty the function tests of new "passively-operating" heat-of-
acids [6]. fusion storage system designs. Recent discussions with
manufacturers indicate that the cost of some fatty acids
Fatty acids can be brought down by about 50 per cent as a result of
(a) TA-measurements. The melting and freezing large scale production. For LTES systems operating
characteristics of fatty acids are presented through the within a narrow temperature range, the cost of heat
example of lauric acid in Fig. 6(b), which contains storage material per kilojoule of stored energy may then
the heating and cooling curves for this material [3]. The compare fairly well for fatty acids and commercial
freezing plateaus are long and flat and no supercooling is paraffins.
PALIMITIC ACID 5 61,2 +- 0.07 59.9 _+ 0.13 196.1 + 2.0 197.0 -'! 3 . 0
324 A. ABHAT
0 ~
2,5
uq
2,0
RUN NO : 183 RUN NO. : 184.
I COOLING : /,,.CYCLE COOLING : t,.CYCLE
RATE : 2.5 KIMIN RATE " 2.5 K/NIN
.!
1,5
tr
o 0
=: 1.0
/_
ud
<[ 0.5
B
0 I I 2
290 3O0 3~0 250 2/*0 230
TEMPERATURE [K] TEMPERATURE [K]
I i !
20
o3
u RUN NO.: 197 RUN NO. : 198
H E A T I N G : 11 CYCLE COOLING : 11. CYCLE
RATE : 2.5 K / M I N RATE 2.5 K / M I N
z 1.5
o
I..-
&.
r,,"
0
1.0
w
z
w
0.5
0 t I I 1
290 300 310 260 250 2t,0
TEMPERATURE [K] TEMPERATURE [ K ]
r 1 1 T r q i
I•
|
I.,I(~
AT I ~ I.CYCLE
RUN NO. 106
HEATINO RATE 1.2~" KIMIN COOLING I.CYCLE
RUN NO 10g
CI8 I COOLING RATE 1.25 KI HIN
0.t.
i i
I 2 3 t, 5 8 i • - TIME IMIN]
2~78 TEMPERATt.h~.IK] 258
f.__----
"0.6 ~1.21 HEATING 5 CYCLE
RUN NO. 116
COOLING 3 CYCLE HEATING RATE 5.0K/MIN
RUN NO 113
COOLING RATE 2.5K! MIN m~08
-2.2
Fig. 13. DSC-thermogramsfor calcium chloride 6-hydrate, tested in non-hermetically sealed (or "open") pans [6].
hand, results from measurements in open pans show a hydrates to obtain a reproducible melting and freezing
large scatter as a consequence of the decomposition of behaviour. Although only limited success has been
the salt hydrates. reported with the methods employed, we shall discuss
In practical systems, the use of salt hydrates is hence them here briefly for the sake of completeness.
recommended only in hermetically sealed or encap- (a) Suspension media. Addition of suspension media or
sulated heat-of-fusion storage system designs. It is fur- thickening agents to the salt hydrate to prevent separa-
thermore recommended to use the salt hydrates in an tion of the solid and liquid phases has been recom-
atmosphere free of air[6, 7]. mended [l l, 27]. The use of a thickener also assists
Modified salt hydrates. The discussion in the preceding in suspending the nucleating agents within the heat stor-
section has been restricted to the investigation of the age medium bulk, which otherwise tend to collect at the
behavioural characteristics of "pure" salt hydrates i.e. in container bottom due to density differences. Thickening
which no foreign substances are intentionally added to agents, however, displace a part of the salt hydrate in the
prevent segregation and/or to eliminate supercooling of heat store, thus reducing the volumetric heat storage
the substance prior to crystallization. There have been capacity of the heat store. Furthermore, they work
several attempts in the literature to "modify" salt towards a lowering of the melting point of the heat
Low temperature latent heat thermal energy storage: heat storage materials 327
Table 12. Some suspension media for use with inorganic salt hydrates
HEAT OF FUSION MATERIALS ~USPENSlON MEDIA REFERENCE
CACL2,GH20 HYDROXY ETHYL CELLULOSE 11
CA(NO3)2,4H20 POLYACRYLIC ACID 11
NACO3.1OH20 POLYETHYLENE OXIDE 11
NA2HPOh.12H20 STARCH 11
NA2S203.SH20 wOOD PULP 11
NA2SO4.10H20 CLAY (BENTONITE, ATTAPULGITE) 11, 26
Table 13. Some nucleatingagents for use with inorganic salt hydrates
HEAT STORAGE NUCLEATINGAGENT DEGREE OF SUPERCOOLING REFERENCE
SUBSTANCE (PCM) (SEEDCRYSTAL)
WITHOUT SEED WITH SEED
CRYSTAL CRYSTAL
K K
LICLO3.3H20 KCLOq, NA2SIF6, K2SIF6, BASIF6 2 - 8 1) 0.5 23
KF.4H20 PUMICE STONE 15 - 24 9.5 23
CACL2.6H20 BACO3, SRCO3, BAF2, SRF2 10 - lq 3 - 5 1) Ii, 23
NA2SO4.10H20 BORAX 14 2 - 5 8, 23, 26
ZN(NO3)2.BH20 ZNO, ZN(OH)2 2 - 7 i - 6 4, 19
KF.2H20 AL203 25 - 35 5 - 8 23
storage substance. Table 12 lists some suspension media Using a mixture of 68.2 wt per cent Na2SO4 • 10H20 and
recommended for different salt hydrates. 31.8wt per cent H20, Biswas[9] reports good results in
(b) Nucleating agents. A nucleating agent is a material comparison to pure Glauber salt. Nucleation of the deca-
having a crystal structure similar in lattice spacing to that hydrate occurred readily, even without the addition of
of the heat storage substance. They serve as nuclei for borax. Furbo[14] reports some preliminary results with
the PCM crystals to grow on them during freezing of the several different salt hydrates and finds them attractive in
PCM and are also termed as "seed-crystals". For good use in comparison to sensible heat storage in water.
results, measures should be taken whereby the nucleat- The major disadvantage of the extra water principle is,
ing agents are homogeneously dispersed within the bulk however, the loss in volumetric heat storage capacity in
PCM and/or they are in contact with the heat transfer relation to that of the pure salt hydrate. For example, with
surface. Table 13 provides a list of some of the com- Biswas' composition of Na2SO4.10H20 and n20, a
monly recommended nucleating agents for use with salt mass about 50 per cent larger and a volume 70 per cent
hydrates and the reduction in the degree of supercooling larger than for an ideally efficient system based on pure
attained with their use. Na2SO4.10H20 would be required to store the same
(c) Extra water principle. Extra water may be added to amount of heat [9].
a salt hydrate to allow dissolution of the anhydrous salt in (d) Other techniques. Another technique to avoid phase
the water at the melting point of the salt hydrate, so that separation in incongruent melting salt hydrates is that
the heat storage medium becomes a saturated salt solu- suggested by Carlsson et al.[lO], who propose chemical
tion at the melting point. During cooling, the solubility modification of an incongruent heat-of-fusion system to
of the salt in water for temperatures below the melting make it behave as a congruent system. Through the
point decreases with decreasing temperatures resulting in addition of 2 wt. per cent SrCI2 • 6H20, the melting point
crystallization of the salt hydrate. Thus at temperatures of the resultant salt hydrate was altered so that the
below the melting point, the storage medium consists of melting point maximum for CaCI2.6H20 coincided with
a salt hydrate solid phase and solution. Upon repeated the point where equilibrium between CaCI2.6H20
heating and cooling, the solid phases of the salt hydrate CaCIE.4H20 and the solution exists. Upon melting of the
then completely go into solution or crystallization out of modified salt hydrate, the peritectic point was thus by-
solution takes place. Soft stirring of the medium may, passed and the formation of the lower salt hydrate
however, be necessary to overcome the density differences (CaCI2.4H20 in this case) avoided.
between the salt solution and the solid phases/23/. The
stirring effect has been achieved in some practical systems 5. THERMALCYCLING
by employing the direct contact heat exchange principle, One of the most severe tests that phase change heat
wherein cold oil sprayed through fine pores directly in the storage materials must undergo is thermal cycling in-
molten phase of the heat storage substances simultaneously volving repeated melting and freezing of the heat storage
cools down the liquid and creates a mixing effect/12/. materials. For example, for a 20-yr life of a one-day heat
328 A. ABHAT
50 , ,
To ~ 2 0 0 Sample A. Not Thickened
--~-rJo I Sample B, Thickened
S
f- -- ~ Ambient Air Temperature
o I,
T ~ ~ I:'
o Cycle No
,s ,._..-
~ ~200
201 200
1000
I 1 i I
100 Hours 1 2 3 Time [ h] /.
~ Heating ._L.
- ~- Cooling
Fig. 14. Temperatureprofilesmeasured during thermal cyclingtests with two samples of Glauber salt plus 3 wt. per
cent Borax. Sample B uses in addition 8 per cent thickener as suspensionmedia for the salt hydrate and nucleating
agent[27].
store, the phase change material experiences one melting- profile following cycling. However, the material without
freezing cycle dailp or a total of 7365 cycles during the the thickener contained approximately 30-35 per cent
system life. liquid at the end of the cooling cycle. A sediment layer
The influence of thermal cycling on the phase change formed which remained throughout the testing period. As
material characteristics must be measured experiment- a consequence, the non-thickened material attained a
ally. Laboratory measurements comprising at least 1000- higher temperature during its heating cycle, as seen in
2000 cycles are recommended, particularly with the in- Fig. 14.
organic salt hydrates, to establish the long-term thermal The heat stored in Glauber salt as a function of ther-
stability of the PCM. The measurements should include mal cycling was measured using standard calorimetric
the temporal variation of temperature within the PCM and techniques[22]. Two different samples consisting of
the temporal variation of the heat transfer rate during the Na2SO4" 10H20 with 3 per cent Borax and thickened
charging and discharging of the storage substance. The material comprising 88wt. per cent Glauber salt+
thermal energy stored in the PCM during each cycle 2.64wt per cent Borax+9.36 wt per cent attapulgite
should be computed and the variation of the stored energy clay were included in the tests. The samples weighed
with the number of thermal cycles should be studied. 150 g each and were cycled within a temperature range
A large gap exists today in the area of thermal cycling 27-38°C. Figure 15 shows the measured thermal energy
tests. Limited thermal cycling (120 cycles) carried out per gram of mixture (AH) as a function of thermal
with paraffins and lauric acid exhibited no degradation of
the materials[4]. Short-term thermal cycling (up to 90
cycles of Na2HPO4 • 12H20 showed that the material melts Glaubers SaLI+ 3 % Borax
congruently when it is not contaminated with the hepta- 6O •¢/•TheoreticaJ-Pure 251 0
J
hydrate, i.e. when the formation of the heptahydrate has 5O
been prevented by appropriate nucleation[27]. AH
A. 4O t kJ/kg
Test results describing the temperature variation in
Na2SO4' 10H20 over 1000 heating-cooling cycles are 30 1255
nucleating agent, and the second sample comprising the o 2b 6b ,6o ,,o ,8o 21o 2~o 36o 3~o ~ ,.&o
same constituents as above plus 8 per cent thickener that No. of Cycles
Table 14. Corrosion investigations with selected phase change heat storage materials
HEAT STORAGE PHASE TEMPERATURE R£F.
MATERIAL OF CONSTRUCTION
MATERIAL TRANSITION LEVEL OF MELT
TEMPERATURE DORING TESTS STAINLESS MILD TIN PLATED COPPER AL.qg,5 ALMG3
OF P(24 (APPROX.) STEEL STEEL MILDSTEEL
(°C) (°C) 1.4301 1.0330
2. WAX ESTER, 80 + 0 o + 0 + 17
58
LDXIQL G 32
3. LICLD3.3H20 8.1 20 0 0 + O 0 0 23
4. CACL2,~%0 29.7 50 + + O + - 18
5. NA2S04.10H20 32.4 50 + 0 0 + O + 8
7. Z~(N%)2,e~20 36.4 55 + O + 18
60 0 0 + O O 0 23
59.1 70 + A) _ B) O 0 O 20
- ~t~CL2.~ 2 0 (4?MOL%)
Fig. 16. Surface of Cu99.9 sample after 50 days contact with the Fig. 18. Scanning electron microscope photograph of AIMg3
melt of sodium thiosulphate 5-hydrate[17].
sample surface showing pitting corrosion after 80 days contact
with the melt of sodium hydrogenphosphate 12-hydrate[17].
Table 14 reveals that aluminum (A199.5) and aluminum
alloy AIMg3 are incompatible with the salt hydrates 7. S U M M A R Y
investigated, with the exception of Na2S203.5H20. With
Na2HPO4.12H20, samples of both metals experienced Latent heat storage in the temperature range 0-120°C
is of interest for a variety of low temperature ap-
surface thickness reduction as well as surface attack, with
plications, such as space heating, domestic hot water
a white layer of aluminum hydroxide AI(OH)3covering the
metal surface after a short period of contact[17]. Figure 17 production, heat-pump assisted space heating, green
shows results for the variation of the surface thickness house heating, solar cooling, etc. The development of
reduction and the mass loss (corrosion) rate with time for dependable heat storage systems for these and other
A199.5 and A1Mg~ samples immersed in molten applications requires an understanding of two essentially
Na2HPO4.12H20. Initially the rate of corrosion is fairly diverse subjects: heat-of-fusion storage materials and
high, but drops with time and attains an asymptotic value heat exchangers. The present paper reviews the state-of-
after about 100 days of contact. Scanning electron micro- the-art of heat storage materials.
scopy investigations indicated pitting corrosion with trans Inexpensive commercial paraffins, fatty acids, in-
organic salt hydrates, and eutectica of organic and in-
and intercrystalline cracks on the A199.5 surface after 80
days of contact, as seen in the photograph in Fig. 18. The organic compounds are the important materials families,
aluminum alloy AIMg3,on the other hand, exhibited fewer to which candidate heat-of-fusion storage materials with
cracks and tended more towards shallow pit formation[17]. phase transition temperatures within the temperature
From these and other results, it may be concluded that range 0-120°C belong. While the inorganic salt hydrates
mild steel and stainless steel are essentially compatible are generally preferred due to their higher volumetric
with most heat storage materials, whereas aluminum and heat-of-fusion in comparison to the organics, they usu-
copper or their alloys are only preferentially compatible. ally suffer from the disadvantages of supercooling and
decomposition upon melting.
Furthermore, common plastics are stated to be generally
corrosion resistant to most inorganic salt hydrates and The knowledge of the melting and freezing charac-
their eutectic compounds[23]. teristics of the heat storage materials, their ability to
undergo thermal cycling and their compatiblity with
4 construction materials is essential for assessing the short
AS v and long-term performance of a latent heat store. Using
-o
AI 9 9 . 5 ---O---- --'-t~-.-
two different measurement techniques--differential
c AI M g 3 ~ -.4~-.-- n E
o
30
scanning calorimetry and thermal analysis--the melting
w
-o and freezing behaviour of the heat storage materials is
determined. Results from measurements undertaken with
representative organic and inorganic substances are dis-
~ 20 2
...i cussed. Commercial paraffins are characterized by two
phase transitions--a solid-liquid and a solid-solid phase
transition--which may be spread over a large tem-
perature range depending on the paraffin concerned, n-
l "~--- •~ . ~. Paraffins are preferred in comparison to their iso-coun-
• ~ 'E-- "-'-t
i i terparts, as the desired solid4o-liquid phase transition is
i oi L i
2o ~ ' ,~o ,6o
' 0
200 generally restricted to a narrow temperature range. Fatty
Time [ d ] acids are organic materials with excellent melting and
Fig. 17. Temporal variation of the surface thickness reduction freezing characteristics and may have a good future
and corrosionrate of A199.5and AIMg3samples in contact with scope, if their cost can be brought down. Inorganic salt
sodium hydrogenphosphate 12-hydrate[17]. hydrates on the other hand, must be carefully screened
Low temperature latent heat thermal energy storage: heat storage materials 331
for congruent, "semi-congruent", or incongruent melting 10. B. Carlsson, H. Stymne and G. Wettermark, An incongruent
substances with the aid of phase diagrams. Incongruent heat-of-fusion system--CaCI2.6H20--made congruent
melting salt hydrate may be "modified" to overcome through the modification of the chemical composition of the
system. Solar Energy 23, 343-350 (1979).
decomposition by adding suspension media, or extra 11. D. Chahroudi, Suspension media for heat storage materials.
water, or other substances that shift the peritectic point. Proc. Workshop on Solar Energy Subsystems for the Heat-
The use of salt hydrates in hermetically sealed containers ing and Cooling of Buildings. Charlottensville, Virginia,
is recommended. Moreover, the employment of metallic U.S.A., 56--59 (1975).
12. D. D. Edie et al., Latent heat storage using direct contact
surfaces to promote heterogeneous nucleation in a salt heat transfer. In Sun H (Edited by K. W. Boer and B. H.
hydrate is seen to reduce the supercooling of most salt Glenn), pp. 640-644. Pergamon Press, New York (1979).
hydrates to a considerable extent. 13. Encyclopedia of Polymer Science and Technoh~gy, Vol. 14,
Finally, some results from thermal cycling tests and pp. 768-769. Wiley, New York (1971).
corrosion investigations are presented to illustrate their 14. S. Furbo, Heat storage with an incongruently melting salt
hydrate as storage medium. In Thermal Storage of Solar
importance in the appropriate choice of materials from Energy (Edited by C. den Ouden), pp. 135-146. Nijhoff, The
the standpoint of the life of a latent heat store. Hague (1981).
15. Gmelin's Handbuch der anorganischen Chemie, Verlag
Acknowledgements--The article forms part of a lecture given by Chemie GmbH, Berlin, FRG, Various Editions (1927-1966t.
the author at the Ispra course "Thermal Energy Storage" 16. D. V. Hale, M. J. Hoover and M. J. O'Neill, Phase Change
organized by the Commission of European Communities (CEC) Materials Handbook. NASA Contractor Report NASA CR-
in June 1981. The full lecture is included in the course proceed- 61363, NASA Marshall Space Flight Centre, Alabama I1971).
ings published by D. Reidel Publishing Co., Holland on behalf of 17. D. Heine and A. Abhat, Investigation of physical and chem-
CEC. ical properties of phase change materials for space heat-
ing/cooling applications. In SUN: Mankind's Future Source
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332 A. ABHAT
APPENDIX
CONiROL I
TEMPERATURE
RECORDER I
TEST TUBE
THERMOSTAT / THERHOCOUPLE
HEAT STORAGE MATERIAL
I~r moco~q~e
II II II /r Seal
910
THERMOCOUPLES
TEl TE2 TE3 TEe TE5
STORAGE CHAMBER
, }
" ~ C H A N G E R
ALUMINIUM ~ P I P E
CALORIMETER
THERMOCOUPLE
WIRING
C2. Laboratory model of the finned annulus heat exchanger element [5]