Solar Energy. VoI. 41. No. 2, pp. 183-191, 1988 0038-092X/88 $3.00 + .

00
Printed in the U.S.A. Copyright ~ 1988 Pergamon Press pie

ON THE STABILITY OF CALCIUM CHLORIDE

HEXAHYDRATE IN T H E R M A L STORAGE SYSTEMS

A. BRANDSTE'ITER
Department of Engineering Physics, Research School of Physical Sciences, Institute of Advanced
Studies, The Australian National University, Canberra, A.C.T., Australia

Abstract~The long-term stability of calcium chloride hexahydrate phase change material, as a heat
storage medium for solar and similar applications, was assessed in a 400-g nonstirred sample of for-
mulated material. Accurate monitoring of enthalpy and temperature profiles over extended periods of
daily melt/freeze cycling was achieved by a unique method of continuous thermal analysis. Results lead
to the conclusion that in the presence of supercooling suppressants, such as strontium or barium salts
and possibly sodium chloride, the formation of calcium chloride tetrahydrate can be inhibited totally by
means of extra water above the hexahydrate composition. Heats of fusion and crystallization in excess
of 200 kJ/kg have been routinely registered.

1. INTRODUCTION of subcooling in relation to the concentration of het-

erogeneous nucleation centers and their initial size.
Calcium chloride forms stable hydrates with two, four,
Whereas reference 5, mostly quoting D. Turnbull,
and six molecules of water, as illustrated by the CaCI,
essentially addresses the shape of nucleation surface
solubility curve, Fig. 1. Figure 2 is a rotated mirror
and its affinity for the crystalline material, reference
image of Fig. I, more akin to the conventional phase
6 seeks to establish self-consistent heat balances be-
diagram, with added 13-tetrahydrate curve. It can be
tween each growth center and the rest of the system,
seen that for CaCI2 concentrations below the peritec-
ignoring the forces governing the growth and the dy-
tic, point P, the lower hydrates can never become the
namics of the nucleation process. It thereby is ca-
thermodynamically stable species since in this region
pable of predicting ultimate subcooling temperatures
their melting points are below that of the hexahy-
but not their development in time.
drate. This is the essence of the "extra water prin-
Although it is beyond the direct scope of this ar-
ciple'[2-4], which consists of moving the stoichio-
ticle, the further question as to the heat-of-fusion val-
metric CaCIz'6HzO composition to the left beyond
ues attainable with the CaCi2"6HzO system is ad-
the peritectic by addition of water. It does not imply,
dressed. One reason for this is that the extra water
however, that tetrahydrate formation is now uncon-
dosage affects directly the quantity of material ame-
ditionally excluded, since kinetic factors can modify
nable to reversible melt/freeze transitions and there-
the phase equilibrium. First, in its metastable re-
fore the "available" heat of fusion. A second reason
gions, below its solubility curve (Fig. 2), the tetra-
is that we have measured exceptionally high heat of
hydrate can solidify if the hexahydrate has super-
fusion values, over 10% in excess of the 191 kJ/kg
cooled that far. Second, concentration gradients can
value for pure CaCIz'6H20 quoted by Lane[7], or the
create regions in the solution where the tetrahydrate
even much lower values for technical varieties quoted
does become the stable species. These problems of
by Carlsson et al.[8]. Enthalpy curves exhibiting such
supercooling and coricentration gradients call for spe-
high heat of fusion values are presented, along with
cial means, such as additives promoting nucleation
details on the experimental procedures used in ob-
of the hexahydrate and dissolution of transiently
taining these curves. A more comprehensive account
formed tetrahydrate, to inhibit incongruent phase
on experimental procedures is given elsewhere[9]. The
transitions and ensuing segregation.
acronyms PCM, for phase change material, and CCH,
Regarding the extra water principle, a foremost
for calcium chloride hexahydrate, not necessarily of
question relates to its optimal dosage and to the ef-
the exact CaCI2-6H20 composition, will be used in
fects of the extra water at and off this optimal dosage
the following.
and at different temperatures. This article treats these
matters in some detail. Similar questions arise in re-
lation to the other additives mentioned, but will not 2. TEMPERATURE-COMPOSITIONRELATIONSFOR
be discussed here. An analysis modeling the PCM's THE CCH SYSTEM
nucleation and supercooling behavior, based on our The basic data for the relevant calculations are (1)
data and differing in important respects from anal- the molar weight of CaCiz: 110.990 g, and of water:
yses by other authors[5], will be published else- 18.016 g, and (2) the solubility vs. temperature re-
where[6]. This analysis views in particular the degree lations such as expressed by Fig. 1
We shall use in particular the values given in
* With the 49.62 wt% peritectic composition quoted by Lange's Handbook of Chemistry[10]. Table 1 shows
Lane[7], this value would be 9.4%. (1) these CaCIz/HzO weight ratios for 0, 10, 20 and
183
184 A. BRANDSTETTER
Table 1. Saturation values for CaCI., in aqueous solution
c~160
-r

I~0 / Temperature T
°C
weightration
(a)
weight %
(b)
degree of
hydration
(c)
o120 : L, '

~I00
J,
0 0.595 37.3 10.35
5 0.62 38.3 9.94
.80 10
15
20
0.650
0.69
0.745
39.4
40.8
42.7
9.48
8.93
8.27
60 25 0.83 45.4 7.42
28 0.93 48.2 6.62
30 1.02 50.5 6.04
20
I I I
10 20 30 /+0 50 60 rium state will as a rule feature a phase of "super-
TEMPERATURE ('C) natant" liquid. This supernatant--and also intersti-
Fig. 1. Calcium chloride solubility curve, after Pauling[l]. tiM--liquid actually is saturated solution in equilibrium
with the solidified hexahydrate and as such its com-
position, at temperatures below 30°C, is as given in
30°C, and our interpolations for 5, 15, 25, and 28°C Table 1, independent of the relative amounts of solid
based on Fig. 1. Added in Table 1 for convenient and liquid present. This was verified by examining a
reference are (2) weight-percent values in grams CaCl., number of samples of varying water content--both
per 100 gram solution, and (3) the hydration values in excess and deficient relative to the hexahydrate
in mols of water per mol CaCI2 corresponding to the composition--which all were found to have very
weight ratios. nearly identical liquid phase compositions.
The point at 30°C, for concentration 50.5 wt%, is In a system of solidified CCH and supernatant liq-
just beyond the peritectic point, P (Fig. 2), which uid, weight fractions (s) and (1), with CaC12 weight
according to M e l l o r [ l l ] , citing Roozeboom[12], is fraction X, in the solid and Xt in the liquid phase, the
located at 29.8°C and has the weight-percent con- overall CaCI2 weight fraction X is given by
centration 50.25, as compared with 50.66 for the pre-
cise 6-hydrate composition. (Lane[7] now quotes x = (s).X, + (1)% (1)
29.45°C, at 49.62 wt%, for this peritectic point and
29.6°(] for the CCH melting point). It should be em- The weight fraction of supernatant liquid is thus
phasized that all the values in Table 1 specifically given by
refer to CaC12"6HeO as the solid in equilibrium with
(l) = (X - X,)/(X, - X,), (2a)
CaCI2 solution at the given concentration-tempera-
ture points. the ubiquitous "lever rule," as for example quoted
When calcium chloride solution at or near the by Abhat[3] and Kimura and Kai[4].
hexahydrate composition is cooled below freezing Xt is as obtained from Table 1, (b), and Xs is the
temperature, for example to 20°C, the final equilib- weight fraction of CaC12 in CaCI_,-6H20 (i.e., 0.5066).
In terms of the degree of hydration H ((c) in Table
1) eqn. (2a) becomes

6.1606
0.5066
H+6.1606
, ~ 6C 2H/ (l) = (2b)
Xt- 0.5066
,., .=-t~H
Figure 3 is a graph of eqn. (2b) for a number of

='~-="~,./,020 ~ ...~-t,H temperatures, using the Xt values given in Table 1,

(b), and some additional values taken from the inset
in Fig. 3 (and the solubility-to-weight fraction con-
version X -~ = S -I + l). These (1) vs. H curves ob-
viously are not exactly straight lines, although they
are close enough to be mistaken for such.
I I I I The experimental points in Fig. 3 were obtained
0 20 t,O 60 BO 100 120 %0 160 from a series of samples of known composition, in
(3RAM CaEt= PER 100gmsHzO various containers ranging in size up to 2 liters, by
Fig. 2. Ninety-degree rotated mirror image of Fig. 1, with weighing them and their supernatant liquid parts. This
added tetrahydrate curve (curve not added because of simplistic procedure obviously ignores the interstitial
irrelevancy). part of the liquid and therefore as a rule undervalues
 Thermal storage systems 185

I 30 29.5 29 ~CLI00 /

100 30"C

8o
g 50 , , ,
6.02 6.06 6~o 6.~c. ~o zo . 30
~9 ~'C " * " ~7"C TEMPERATURE
(C)
"7 /29C /28C

~0 /
20

6.10 620 620 6/,0 6.50 6.60 6.70 6.80 6.90

HYDRATION NUMBER.(mol ~ 0 per mo{ Co Ct2)

Fig. 3. Weight percent supernatant CaCI2 solution vs. "hydration number" (tools H20 per mol CaCI:).
For temperatures in the 0 to 300C range. Plot shows calculated curves (not straight lines) and experi-
mental points. Inset: CaCIz-6H20 solubility curve used for these calculations.

(1), Moreover, even though the weighing may be at ture of 330C at which the points determining this
room temperature, 20 to 25°C, the amount of super- density relation were obtained was selected for prac-
natant liquid found in a sample largely reflects its tical reasons: since our samples of CCH usually were
amount at the time of its formation following freez- stored in a "hot box" at approximately this temper-
ing, at which time the temperature may have been ature, this curve provided for fast determination of
much lower. Our data points close to the 0°C and concentration by simple weighing (to 0.01 g) of a
10°C curves suggest this is a likely explanation, since given volume (approx. 250 ml) of any sample from
some of the samples were, in fact, allowed to freeze this hot box. Actual states of hydration, for example,
outdoors. to establish the density vs. H relation of Fig. 4 were
A quantity of interest directly related to the frac- determined by a dehydration method, in which the
tion of supernatant liquid is the excess of water caus- residual solid was subjected to 350 to 400°C for 15
ing it. Up to the peritectic concentration this quantity min following the initial boiling off. The curve in
is simply given by Fig. 4 represents a best linear fit to the experimental
points shown.
Weight percent excess water Note that the material used, although essentially
( H - 6) x 18.016 x 100 "technical grade," containing in particular close to
(3) 0.5 wt% NaCI, is relatively pure CaCI2 aqueous so-
219.086 + (H - 6) x 18.016
lution, as evidenced by the transition temperature in
Figure 4 presents this weight-percent excess water excess of 29°C of its CCH form. The presented den-
function for convenient reference. Figure 4 also of- sity vs. H relation should, therefore, represent fairly
fers an empirical relation of the density of CaCI2 so- closely pure CaCI2 solution.
lution as a function of concentration. The tempera-
3. TETRAHYDRATEFORMATIONAND HOW TO
P R E V E N T IT
% 1. ~ O expt't points (33 C) ' For correct evaluations in the region about the ct-
{,0F "w j tetrahydrate peritectic point it is clearly helpful to re-
draw this region, Fig. 2, on a magnified scale such
as in Fig. 5. In this drawing points P and Q are placed
in accordance with Fig. 1 in G. A. Lane's =Technical
Note" [ 13], purportedly after Roozeboom[ 12], except
Y I I
that point P here has been located at exactly 29.8°C
6.0 6.5 7.0 7.5 to comply with Mellor[11], citing Roozeboom, as al-
tool Hz0/tool CaCI2 ready mentioned.
Note that very accurate location of melting points,
Fig. 4. Calcium chloride solution specific gravity vs. "hy- etc., is here of little interest since we refer to tech-
dration number" (tools H20 per tool CaCl2), empirically
determined for "technical" material near the CaCI2"6H20 nical CCH; and second, that the 13 (and T) tetrahy-
composition. drate species (see Fig. 2) can safely be ignored as
186 A. B RANDSTETTER

centration just, but safely, below the peritectic, such

32 as H = 6.14. This, according to Fig. 3, would amount
to a loss of I 1% storage capacity at 25°C, 6% at 20°C,
.~31~ etc. Note that in practical situations the lowest tem-
perature reached by this PCM could normally be ex-
pected to assume values such as 20°C. It follows that
~30 __
ca.
heat of fusion values measured over repeated cycles
with a sample containing excess water should be in-
~-29 creased by an appropriate factor, depending on the
t
I amount of extra water and the low-temperature level,
to yield the true heat of fusion value, in distinction
t+9.5 50 50.5 51
Weighl" % CaC[2 from the achievable heat storage capacity. An ac-
count of this is taken in the results presented in the
Fig. 5. Phase diagram of calcium chloride-water system following section.
in narrow concentration range around the hexahydrate. The In the metastable region, the "hatched area" in
hatched area indicates the metastable region where tetra-
hydrate can form due to supercooling of the hexahydrate. Fig. 5, tetrahydrate can form due to subcooling of
the hexahydrate or to concentration gradients creating
regions where the tetrahydrate is stable. The preven-
long as compositions above the hexahydrate (i.e.,
tion of these conditions is possible by (1) minimizing
above 50.66 wt%, do not occur; therefore "tetrahy-
the time span of hexahydrate subcooling--not nec-
drate" in the following refers to the ct-tetrahydrate
essarily the subcooling temperature differential, as
only.
shown in the following section; and (2) retarding any
A CaCI2 solution super-saturated with tetrahydrate
formed tetrahydrate in its descent to the container
at any point between P and Q, Fig. 5, will form a
bottom. Having been formed ~legitimately" in a dense
solid phase of weight fraction (s) given by
region, such tetrahydrate is then bound to traverse
(s) = ( X - X t ) / ( X s - Xt) (3a) lower-density regions where it no longer is thermo-
dynamically stable and only requires the necessary
with CaCI2 weight fraction X, = 0.6063 in the solid time to return into solution.
and Xt in the liquid phase. In terms of the hydration Subcooling can be inhibited by additives called
degree H, nucleators, such as, in the case of CCH, certain
strontium and barium salts[7], possibly also by the
6.1606
Xl presence of sodium chloride[4]. GravitT-induced seg-
H + 6.1606 regation can largely be suppressed by thickening, or
(s) = (3b)
0.6063 - Xt "thixotropic," additives as pioneered by Mafia
Telkes[14], for example, certain silica-based clays[7].
Of special interest here is H = 6, the stoichio- Nucleating and thixotropic additives, which need not
metric composition of the hexahydrate, which was be further specified here, were found to be totally
the basic, explicit object of the work by Carlsson et effective in preventing phase separation in our sam-
al.[8] and criticism thereof by Lane[13]. ple, as well as in a prototype space heating system
At temperature corresponding to the point Q employing 200 kg of our PCM.
(31.8°C, but Lane's book quotes 32.78°C[7]), the
weight fraction for saturation is 0.5066. At this com-
position, the amount of solid tetrahydrate in equilib- CONTINUOUSTHERMAL
4. E X P E R I M E N T A L :
rium with the solution can be calculated through eqn. ANALYSIS
(3b). With H = 6 and X t = 0.5025 (the weight frac- Our methodology, involving continuous evaluation
tion for saturation of the tetrahydrate at the peritectic of the PCM's enthalpy under melt/freeze cycling
according to Fig. 5), (s) = 0.040 is the weight frac- conditions, has been generally described earlier[15]
tion of precipitated CaCI2"4H20.* and first results were published recently[16].
The weight fraction of liquid is thus 0.960 and its The PCM enthalpy change, referred to unit mass,
composition is that of tetrahydrate-saturated solution is computed every 30 s in terms of the energy balance
at the peritectic (i.e., 0.5025) weight fraction CaCI2, in a surrounding water bath, on the basis of a pre-
corresponding to hydration degree H = 6.10. At 25°C, cisely calibrated heat conductance out of this bath and
this composition leaves 7% supernatant liquid, ac- precisely measured electrical energy supplied to this
cording to Fig. 3, but at 28°C this becomes 18%, etc. bath by a heater and a stirrer.
Disregarding for the present the possible forma- The results presented refer to a 400-(more pre-
tion of tetrahydrate in its metastable region at con- cisely 382) g sample of CCH formulated with excess
centrations below peritectic, we may then conclude water and nucleating and thixotropic additives, now
that the optimal excess quantity of water is for con- completing over 18 months of temperature cycling at
the rate of one or two melt/freeze cycles a day. Four
* With the 49.62 wt% peritectic composition quoted by cycles a day were attempted but was not found pos-
Lane[7], this value would be 9.4%. sible within the existing constraints due to the ~re-
 Thermal storage systems 187

alistic" geometry of the sample: an upright cylinder respectively, as given by Lane[7]. Figure 6 to 9 in-
72 mm in diameter filled with the P C M to about 70% dicate how these beat-of-fusion values were calcu-
o f its 90ram height. Some of the cycles had partic- lated. A lower limit on the "true" heat of fusion of
ularly fast or particularly slow heating or cooling CaCI2-6H20 is estimated in each case as the observed
phases within a range of about 15 to 43 °. value scaled upward according to the amount of su-
Large amounts of data of enthalpy and tempera- pematant liquid corresponding to the sample's degree
ture profiles have been collected over these 18 months of hydration and that plot's base temperature.
on magnetic disk and partly retrieved in the form of It should be borne in mind that the heat of fusion
printouts and graphic displays. A selection of plots exhibited by a cycled sample is limited by the heat
showing temperature profiles and associated enthalpy evolved during solidification, since only up to this
curves vs. time, for 24 and 12 h melt/freeze cycles amount can subsequently be absorbed upon melting.
for different ambient regimes is shown in Figs. 6 to Therefore, if (congruent-) melting proceeds to com-
9. A very slow traverse through the crystallization pletion, as normally expected, this heat of fusion must
zone is shown in Fig. 10; and Fig. 11 is a graph of equal the heat evolved during the previous solidifi-
enthalpy vs. temperature obtained from the same data cation. The variations in heats of fusion exhibited in
as Fig. 6 and is used to derive heats of fusion by the Figs. 6 to 9 probably have their origin in the varying
method described by Feilcbenfeld et al.[17]. As seen CaCI2 concentration in the trapped interstitial liquid
in Fig. 11 a correct value of the heat of fusion could as explained in the previous section. A lower limit
be obtained by this method only by way of imposing for the heat of fusion is, consequently, given by the
specific heat slopes adjusted to their assumed values upper limit of this variable found in a large number
of 1.4 and 2.2 J/g°C for the solid and liquid states, of cycles.
respectively. Cycle No. 106, Fig. 6, which ran on 7 January,
The plots shown in Figs. 6 to 9 exhibit existing 1986, is a candidate for exhibiting this upper limit,
variations in a number of characteristics, including both generally and in comparison with its close
enthalpy of fusion and crystallization, degree of sub- neighbors. The sample was inspected visually at times
cooling and subcooling time intervals. As to the en- before and after this cycle and appeared totally liquid
thalpy characteristics, their analysis has led to values when molten and near solid when frozen. A value of
for the heat of fusion which are 10% higher than re- 220 J/g is indicated in Fig. 6 as a lower limit for the
cently quoted by Lane[7]. Similar values were ob- heat of fusion of CaCI2"6H20 obtained in that cycle,
tained also by Feilchenfeld and co-workers[17], and in good agreement with the value obtained by Feil-
we feel confident that our measurements are accurate chenfeld and co-workers[17]. Many similar values
within about 2%. The values obtained depend to some were obtained in other cycles, both before and after
minor degree on the specific heats of the liquid and cycle No. 106, and cycle No. 542, shown in Fig. 9,
the solid CCH, assumed to be 2.1 and 1.4 J/g°C, presents one such example.

CYCLE No. 106

k8 From7 Jan.1986.05:39 i'" " ' ~ "~'r-l:l
kk,
Cz, o

.~3z,
r~
~28,
N 2~,
20'
16
0 2b I00 120 I/:0I(~0180 200 2~ 2~0
TIME POINTS
2500(30

~ i n p u t : 1+.6x2.1÷10.1x1-¢,
/ -~1 Latenfheat° N usi°n : 231.-221'=k210/kkgJ/kg
..._1
I,--
,.z,
-50000
Fig. 6. Daily cycle No. 106 (7 Feb. 1986). Temperatures measured at point locations as approximately
indicated in the inset. Each "time point" represents 6 min. Cycle 106 was found to have the highest
measured heat of fusion: 220 J/g, corrected for excess water.
188 A. B RANDSTETrER

% .+~+#o. ~o+ or,++r,Oed,cate,.:,+

32
~3O
~. 2B
26
/Y/o+++ •++t\
22
20
18 I I "-'~- t I I' I I I I I I I I } •
0 5 10 25 3O 35 I~I ~+5 50 55 60 0 ½ 10 15 20 25
TIME POINTS' ' TIME POINTS
125000 2500O0
Specific heat estimates: :~
Solid: 7"0 + 5.0:1"~
--3 Liquid : 103 + S0: 2'IkJ/kg'C
)-
O-
.J
,(C
T I c:, T
k,-
i,J

-25000 100000
Fig. 7. Expanded-scale portions of the temperature and enthalpy curves of cycle 106, showing the sen-
sible-heat gain and loss patterns and derived specific heat values in the solid and liquid state.

CYCLENo. ~.I CYCLE No.~2

~0 From 3 Nov 1985.03:15 ~ 14
to /,Nov.1965, 03:13 ~ AIR ---~
38
,-, 36 -~ +l I
............... I® ®®®1%
<~ 32
(:~cC
~30
~28
26
2~
0 20 m 0o +o ,oo ,2o ,+o ,+o ,0o 2oo 220
TIME POINTS

250000

-S0000
P i g . 8. C y c l e nos. 41 and 42, o f the f+~st r e c o r d e d s u i t a b l e f o r p r e s e n t a t i o n . N o t e the l o n g f r e e z i n g t i m e
due to the smaller downward temperature excursion, which also is in part responsible for the relatively
lower heat o f fusion.
 Thermal storage systems 189

CYCLE No. 5k2 i ~ 'R P ~

/+8 T -~'~-0"H'~rch]'~'%,02:z.1 t--~-~qH
I ( 2 melt/freeze cycles } I(~) ¢®®1~
~o . . . . . . . . . . . . ®

~:28

TIME POINTS
250000 =,z-,,,- - - T . . . .

Sensible heat
/
.1 • 10.5 x 14,
\ = 37kJ/kg /
/
'~ Latent heat o~fusion: ZU,-37~=207kJ/kg /

-50000
Fig. 9. Two consecutive cycles on day 542 (March 20, 1987). Note (a) the variation in the degree and
time of subcooling (compared with cycle 41, Fig. 8); and (b) the heat of fusion values comparable to
those obtained a year earlier.

3 0- m" NOTE: Limitof data resolution is 0'01"C for track"B"

| 01"C for all others

.~28 . . . . ~"~ - -

I I,~ ,,~,,,,P.,,~l ~ Starting on day NO. 578 Terminated on day NO. 581

0 20 &O 60 80 100 120 I~,0 160 180 200 220 2&O 260 280 300 320 3/+0 360
TIME POINTS
2SC)C)O0 {5 time points = 1 hour}
A

)- Enthalpy of Crysta((izafion: 170 kJ/kg ( fitted )

n
<
"I-

Z
W

-5(~X)0
Fig. 10. Enthalpy variation during very slow traverses through the crystallization region, after which
the PCM was visually inspected and no tetrahydrat¢ deposit was found.
190 A. B RANDSTETTER

2~0
this slope . . . . . _ _ ~ , ~ t - - ~ ' ~ F e d line
200 odjusted to F" ~" R2=0"53
2.2 ~ °c
A
t, .,/a_E :3.z
~160 /'~ ," AT

120 rain femp ~ o: ° , t

<
po nts.-'--~,l~° ~ ~ - - . . mQx temp
i . points.
80 CYCLE 106 ~ lr~
i,l
%1:
• 1
o,

40
• slope adjusted tol.4~°C
- ....----, ~ "~ , . J , ,
20 22 2/+ 26 28 30 32 3t, 36
TEMPERATURE {°C)
Fig. 11. Enthalpy vs. temperature "scatter plot" for cycle 106 during heat-up--only minimum and
maximum temperature points are shown for each plotted enthalpy value.

5. DISCUSSION hydration method to determine degrees of hydration,

only at a much higher temperature. Our tests have
The continuous calorimetric evaluation of PCM un-
indicated that tetrahydrate does not form at the com-
dertaken in this study, over many hundreds of melt/
position H = 6.14, whereas tetrahydrate started
freeze cycles, has provided unusual insight into the
forming following the first melt cycle at slightly lower
long-term behavior of PCM under near-practical heat
water content. We too have NaCI in our sample, about
storage conditions. Essentially unmodified "techni-
0.45 wt% according to Atomic Absorption Spectro-
cal-grade" calcium chloride hexahydrate was inves-
photometer analysis (Perkin Elmer Model 303), but
tigated in this experiment, but the method lends itself
our results as stated do not confirm Kimura's that this
to similar investigations on other materials as well,
NaCI could replace excess water in the prevention of
including in particular chemically modified CCH such
tetrahydrate formation.
as studied by Kimura, Lane, Carlsson, Feilchen-
Finally, from recent experience with a near-prac-
feld[4,7,8,18], and others.
tical system for space heating employing some 200
In regard to the ultimate stability against forma-
kg of CCH phase change material, we find that this
tion of tetrahydrate, what can be said is that up to
PCM, with its 29.3°C transition temperature (see Figs.
now, after more than 600 daily melt/freeze cycles,
6-10) and over 300 MJ of latent heat per net cubic
no tetrahydrate formation has been observed with
meter, is indeed proving to be a useful heat storage
samples that have slightly beyond the minimum ex-
medium. The stability of this system has been tested
cess water. Moreover, tests have shown that tetra-
so far over a nonstop period of 9 months of daily
hydrate does form rapidly at slight deficiencies of
melt/freeze cycles, powered by off-peak electricity,
water, below about H = 6.10. (This tetrahydrate can
without showing any noticeable effect of deteriora-
be remelted at temperatures just above 46 °, and on
tion.
addition of the missing water the material then re-
verts back to normal "defacto" congruent behavior.)
Kimura reported measurements on CaC12 at hy-
6. CONCLUSION
dration degree H = 6.11. This, if accurate, would be
below the peritectic composition H = 6.10 according Using a new method of "continuous thermal analy-
to Mellor[11] and therefore the reported absence of sis," together with results obtained over the past year
tetrahydrate could have been expected. It is not clear, with a near-practical space heating system, it has been
on the other hand, on what basis Kimura assumed a found that calcium chloride-based PCM can be sta-
value of H = 6.14 for the peritectic (cf. the value of bilized against incongruent melting. From the de-
H = 6.255 given by Lane[7]). It is, moreover, likely tailed results reported in this article, it can be con-
that all the hydration values measured by Kimura's cluded that this stabilization is achieved without
group "by heating in an oven at 150°C for 3 to 6 h" significant change from the normal CCH transition
were low due to incomplete dehydration, which could temperature nor from its normal heat of fusion value,
explain why at H = 6.11, purportedly above the peri- with the latter actually somewhat higher than re-
tectic, no tetrahydrate formation was observed by this ported in the literature.
group. Their explanation, however, was that dis-
solved NaCI (0.4 wt %) prevented it[4]. Acknowledgments--The author gratefully acknowledges
As already mentioned, we have used a similar de- support provided under the National Research, Develop-
 Thermal storage systems 191

ment and Demonstration Program which is administered by Change Material from Industrial Waste for Thermal
the Commonwealth Department of Resources and Energy. Storage, final report to National Energy Research, De-
Substantial contribution by Prof. S. Kaneff and helpful dis- velopment and Demonstration Council (NERDDC),
cussion with P. O. Carden and B. K. Selinger also are Grant No. 84/4203, May (1987).
gratefully acknowledged. 10. J. A. Dean (ed.), Lange's Handbook of Chemistry, llth
ed. p. 10. McGraw-Hill, New York (1973).
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