Journal of Materials Processing Technology 175 (2006) 198205

Corrosive effects of salt hydrate phase change

materials used with aluminium and copper
Anthony J. Farrell , Brian Norton, David M. Kennedy
Dublin Institute of Technology, Dublin, Ireland

Abstract
A disadvantage of phase change materials (PCMs) as thermal energy storage media is corrosion when in direct contact with metal piping,
plates or housings. The corrosion rates of aluminium alloys and copper used in heat exchangers in the air conditioning industry has been
measured along with metallographic examinations following corrosion tests. Ways of preventing corrosion of copper and aluminium by these
PCM materials are discussed.
2005 Elsevier B.V. All rights reserved.
Keywords: Phase change materials; Hydrated salt phase change materials; Corrosion; Galvanic corrosion of copper and aluminium; Latent heat thermal storage
systems; Low energy heat pipe heat exchangers

1. Background
Little previous research has examined the potential corrosive effects of salt hydrates which melt at temperatures
around 18 C [1]. Porisini [2] examined corrosion in metals containing four commercially available salt hydrates of
which two melted within close range of this temperature.
Na2 SO4 1/2NaCl10H2 O and NaOH2.5H2 O which have
melting temperatures of 20 and 15 C, respectively, were used
to determine the corrosion rates on stainless steel, carbon
steel, aluminium alloys and copper [2]. Following thermal
cycling tests, Porisini concluded that stainless steel was the
most corrosion resistant of these metals for use with salt
hydrates, though copper was shown to have a corrosion zone
that did not increase after long periods of time. Cabeza et
al. [36] examined the corrosion resistance of five metals,
including aluminium and copper, which were in contact with
molten salt hydrates with melting temperatures of the order
010, 3236 and 4858 C. Table 1 summarises the corrosion
rates for copper and aluminium found in each case.

12th International Scientific Conference Achievements in Mechanical &

Materials Engineering, Zakopane, Poland.

Corresponding author.
E-mail address: Anthony.Farrell@dit.ie (A.J. Farrell).
0924-0136/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2005.04.058

As shown in Table 1, aluminium is prone to localised

pitting corrosion when in contact with chlorides resulting in the formation of Al(OH)3 . While aluminium has
a low corrosion resistance to chlorides, it is resistant to
sodium acetate. Copper is resistant to calcium chloride
but not to sodium acetate. Sodium sulphate composites
(Na2 SO4 10H2 O + NaCl), despite consisting of a sodium
chloride mixture, is used as a phase change material (PCM)
in commercially available aluminium passive cooling units,
which are quoted to last some 20 years provided the PCM
chamber is airtight [7].
Metal corrosion processes include localised pitting,
erosion, hydrogen embrittlement, oxidation, fretting, fatigue
and dealloying [8,9]. Galvanic corrosion can be quantified by
the potential difference of the metal to a standard reference
hydrogen electrode. The galvanic series shown in Fig. 1 is
based on immersion tests in a seawater electrolyte and provides an indication of the corrosion rate between metals and
alloys in contact in seawater [10]. PCMs in an energy storage
system may behave as a similar electrolyte. Active metals
will behave as an anode and corrode (e.g. magnesium, zinc
and aluminium) and noble metals (e.g. platinum, gold and
silver) will behave as a cathode and be protected [11]. Pitting
is a form of localised corrosion that results in pits in a surface
which can grow to form holes in thin walled component,
such as a tank or pipe. All metals are susceptible to pitting

A.J. Farrell et al. / Journal of Materials Processing Technology 175 (2006) 198205

199

Table 1
Summary of corrosion affects from salt hydrate PCMs
Salt hydrate

Melting
temperature ( C)

Metal

Corrosion

Corrosion rate
(mg/(cm2 h)

Sodium acetate

4858

Aluminium

No corrosion

i
ii

Sodium acetate,
sodium thiosulfate

4858

Copper

Severe corrosion
through CuS

Recommendation

Reference

0
0

Use
Use

[6]

33.2

Do not use

[6]

ii

605

Do not use

Sodium hydrogen
Calcium chloride

(35) 3236
(32)

Aluminium

Severe corrosion
Pitting

Not available
Not available

Do not use

[4]

Sodium hydrogen
Calcium chloride

(35) 3236
(32)

Copper
Copper

Corrosion resistant
Corrosion resistant

Not available

Use
Use

[4]

Sodium phosphate

(35) 3236

Aluminium

Oxidisation with a
black layer

Not available 5.5

Cautionshort
term use

[5]

Calcium chloride

(32)

Sodium carbonate

Aluminium

Severe corrosion

>1000

Not to be used

[3]

Sodium carbonate

Copper

High corrosion

13.9

Short term usage

[3]

corrosion. To avoid or reduce pitting, metals should be isolated from stagnant solutions and where possible protected
from galvanic couples. If protective coatings are used, they
should be non porous or crack free [8] and be good thermal
conductors relative to the materials they are protecting.
Galvanic corrosion is also a form of localised corrosion
that arises when two dissimilar metals are coupled electrically in the same electrolyte allowing extreme segregation
of the alloys within the material to occur [9]. This can arise,
for example when iron and copper are immersed in sodium
chloride. Although oxygen reduction will occur on both metal
surfaces, only the anodic iron metal will corrode. If both metals are of the same surface area, the iron will corrode at twice
the rate than it would if immersed in the solution without a
connection to the copper. In aluminium/magnesium alloys,
for example the magnesium will facilitate intense hydrogen
evolution leading to intense local corrosion and pitting. For
an aluminium alloy/copper combination, the potential of the
copper (cathode) is less than the aluminium alloy (anode).
Therefore, the corrosion rate of the aluminium alloy will
increase in the presence of copper while immersed in an
electrolyte. Fig. 1 sets out the galvanic series and the relative order of galvanic corrosion with respect to aluminium
(Al) and then copper (Cu) [12].

2. Materials specications
Their large thermal storage densities mean PCMs
are a suitable storage medium for heat exchanger heat
sinks/sources. To use PCMs as a thermal storage medium
for conventional air conditioning heat exchangers, the PCM
melting temperature should match approximately the supply
air temperature. This is typically 18 C. Table 2 outlines the
basic chemical composition and melting temperatures for
the two commercially available PCMs used in experiments:

Table 2
PCM characteristics [7,14]
PCM

Melting
temperature ( C)

Salt hydrate

PlusICE E17

17

ClimSel C18

18

Sodium sulphate decahydrate

and sodium chloride
Sodium acetate + additives

PlusICE E17 [7] and ClimSel C18 [13]. Both materials

are white powders, while the ClimSel C18 has a shimmerd
effect caused by a metal infill.
A conventional heat pipe heat exchanger representative
of a low energy alternative to conventional cooling/heating
coils as used in the air conditioning industry [15] was
employed in this investigation. The heat exchanger consisted
of two chambers. One chamber was open to an air circulation system and the other chamber was sealed from the
atmosphere and filled with a hydrated salt mixture PCM. The
PCM acted as the heat sink for cooling and also a heat source
for heating [16]. The size of the heat sink/source chamber
was determined from the cooling/heating duration [17].
Both chambers were interconnected by the heat pipes, which
were constructed from copper tubes onto which aluminium
fins were expanded. The copper pipes were plated with
aluminum. Cracks, gaps, crevices and delaminations can
occur on the surface where galvanic corrosion occurs.
The heat exchanger also incorporated horizontal plates
between the fins at a vertical spacing of 50 mm. These plates
prevented stratification of the PCM sample PlusICE E17,
which became incongruent at depths greater than 50 mm [7].

3. Experiments
Uniform corrosion rates may be expressed generally in
terms of mass loss of the material with respect to the initial

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Fig. 1. Galvanic series for metals and alloys when immersed in salt water.

mass per square metre of surface either on a daily [35] or

hourly basis (ASTM, 1996). An investigation over a 17 h
period was undertaken. The ASTM G1 standard for testing
on an hourly basis was used.
Table 3 provides alloy contents for the aluminium and
copper samples used in the corrosion tests as cited in the
American Society for Testing and Materials (ASTM) G1
UNS classification system [18].
Prior to testing, all samples were cut, measured and polished using grade P400 silicon carbide water proof paper.
Each sample was cleaned of surface particles using a cloth.
The samples were then weighed. A sample of each metal
was then placed into each reference PCM. Two samples of

copper and aluminium were encapsulated separately, and two

samples together, for both PCMs. The reference samples of
PCMs were encapsulated from the air and heated to a fast
melting rate temperature (70 C) for 1 h. The temperature
Table 3
Properties of materials used in experiments
Metal

Aluminium (UNS A92024)

Copper (UNS C38600)

Al (%)
Mg (%)
Mn (%)
Cu (%)
Density (kg/m3 )

93.6
1.5
0.6
4.5
2.78 103

99.9
8.94 103

A.J. Farrell et al. / Journal of Materials Processing Technology 175 (2006) 198205

201

Table 4
Experimental results for test samples
Sample

Copper
mass (g)

Cu
area(cm2 )

After test
mass (g)

Cu mass
loss (mg)

Aluminium
mass

Al area
(cm2 )

After test
mass (g)

Al mass
loss (mg)

Separate copper and aluminium samples in heater at 40 C for 17 h

1: C18
7.9154
5.7000
7.9081
1: E17
8.0956
5.7700
8.0940
2: C18
7.9441
5.7380
7.9376
2: E17
8.0400
5.7570
8.0390

0.0073
0.0016
0.0065
0.0010

4.5754
4.3748
4.6047
4.6164

5.510
5.415
5.686
5.700

4.5750
4.3748
4.6040
4.6164

0.0004
0
0.0007
0

Copper and aluminium samples in heater at 40 C for 17 h

1: C18
3.9755
8.4830
3.9755
1: E17
4.2389
9.0250
4.2389
2: C18
2.5306
5.7760
2.5306
2: E17
2.7801
6.1370
2.7801

0
0
0
0

0.8459
1.0783
0.8960
0.7680

3.74
4.37
3.96
3.08

0.8373
1.0783
0.8860
0.7680

0.0086
0
0.0100
0

was then lowered to 40 C for approximately 17 h. The samples were then removed and cleaned with nitric acid for the
aluminium alloy and hydrochloric acid with a 2:1 reagent
water mix for the copper. The samples were then placed
into separate beakers of water following immersion in the
acids to minimise oxidisation. Each sample was then dried
off in turn. Eight samples of copper and aluminium samples
were weighed using a precision electronic scales. The samples were examined visually with a microscope and images
highlighting areas of corrosion, including pitting and discolouration were recorded. Aluminium samples were also
sectioned using a saw and then polished using silicon carbonate paper on a water polishing disk (grades 2304000).
The corrosion rate on each of the eight samples was determined and recorded.

Table 5
Calculated results for corrosion rates of aluminium and copper
Sample

1: C18
1: E17
2: C18
2: E17

Corrosion rate
Cu and Al separately
(mg/(m2 h))
Cu

Cu + Al together
(mg/(m2 h))
Al

0.838
0.182
0.741
0.114

0.051
0
0.089
0

(g) and D is the density in g/cm3 (8.94 for Cu and 2.78

for Al).

5. Metallographic investigation
4. Results
Results of the mass loss rates for the samples of aluminium
and copper are shown in Table 4. The respective sample area
and mass are also presented for each reference PCM. Table 5
shows the results for the corrosion rates as calculated from
the ASTM G1 standard.
The corrosion rate (R) was determined from the American
Society for Testing and Materials test G1 90 (1994) [18]:
R=

KW
ATD

The corroded samples were examined under a microscope

for signs of corrosion using magnifications of 5, 10, 20 and
50. From photographic images recorded, the average pitt
diameter was measured. From Fig. 2a and b, no pitting was
observed in the copper samples following the corrosion tests.
Fig. 3 shows pitting corrosion was observed in the microscopic analysis for each of the aluminium samples.

6. Discussion of results

where, A is the area (cm2 ), K the constant (1 104 D for

g/(m2 h)), T the duration of exposure (h), W the mass loss

From the tests conducted, pitting was not observed on the

copper samples. There was oxidation in the form of copper

Fig. 2. Microscopic examination of a copper sample tested (a) alone and (b) with aluminium.

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A.J. Farrell et al. / Journal of Materials Processing Technology 175 (2006) 198205

Fig. 3. Microscopic examinations of the aluminium samples. Test 1: aluminium alone, test 2: aluminium with copper, sample 1: C18, magnification factor
10. Pitting across surface between 20 and 30 m, sample 1: C18, magnification factor 20. Pitting observed across the surface between 2.5 and 25.5 m,
sample 1: E17, magnification factor 50. Pitting observed across surface between 2.5 and 7.5 m, sample 1: E17, magnification factor 20. Pitting observed
at points on surface between 2.5 and 17.5 m, sample 2: C1 8, magnification factor 10. Pitting observed across surface between 12 and 20 m, sample 2:
C18, magnification factor 10. Pitting observed across the surface between 10 and 80 m, sample 2: E17, magnification factor 50. Pitting observed across
surface between 2.5 and 8 m, sample 2: E17, magnification factor 20. Pitting observed at points on surface between 2.5 and 10.5 m.

oxide on the surfaces of the copper samples. Oxidation levels

were higher on those samples that were immersed alongside
the aluminium alloy samples in the PCMs. Discolouration
indicated chemical corrosion caused by a chloride ion concentration at the surfaces. Localised pitting corrosion was

observed on all the aluminium alloy samples. Pitting of the

aluminium alloy was most severe on those samples immersed
in the C18 PCM and the highest level of pitting due to galvanic corrosion occurred when the aluminium samples were
coupled with the copper samples. The least amount of pitting

A.J. Farrell et al. / Journal of Materials Processing Technology 175 (2006) 198205

203

Fig. 4. Cross section through sample 2: C18 (from Fig. 3 above).

Fig. 5. Cross section through sample 2: C18 (Fig. 3) highlighting granular pitting corrosion.

was observed on the E17 PCM samples. Localised corrosion

resulting in pitting can cause very rapid failure of thin walled
pipes or plates and lead to leakages or explosions. Fig. 6
shows an aluminium sample with a large 650 m diameter
pit and a series of smaller pits, as illustrated in Figs. 35. This
demonstrates the severity of the corrosion processes associated with using PCMs in direct contact with some metals or
alloys.

Fig. 6. Overall view of large pit (650 m wide) consisting of many small
pits.

7. Corrosion prevention measures

Tin plated copper fins were used for experimental analysis of heat pipe heat exchangers when in contact with sodium
chloride-based salt hydrate PCMs [7]. Tin in that application
was most appropriate because it had the least potential difference between it and copper as shown in Fig. 1. Heat pipe
heat exchangers use aluminium casings and the pipes are copper onto which aluminium fins are expanded, thereby plating
the entire copper surface with aluminium. Minor cracks may
form in the plating and in such cases, the copper will become
cathodic to the aluminium and the PCM will act as the electrolyte resulting in Galvanic corrosion.
The Corrosion and Protection Centre [11] report that
zinc, commercially pure aluminium or cadmium could be
used to protect an enclosure consisting of both copper and
aluminium by behaving as sacrificial anodes. Cadmium is

Fig. 7. Corrosion prevention measures for low energy heat exchanger.

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A.J. Farrell et al. / Journal of Materials Processing Technology 175 (2006) 198205

Fig. 8. Commercially available PCM packets [9].

the most suitable, however, zinc is more readily available

and thus a lower cost metal coating. Where a sacrificial
anode such as zinc is used to reverse the corrosion effects
on the aluminium, then the area of zinc should be larger
than aluminium. In the heat exchanger, the PCM enclosure
should be zinc coated or plated. If there is still insufficient
area available for anodic corrosion of the zinc, then further
sacrificial perforated zinc plates could be used. These can
be immersed in the PCM electrolyte within the top (and base
if necessary) of the chambers. Fig. 7 illustrates this concept.
Other prevention measures include isolating the hydrated
salts from the metals using polymer-based packets. Fig. 8
presents the smallest commercially available packet, which
was custom manufactured for a replacement to the sacrificial
anode used with the heat exchanger discussed presented in
Fig. 7.

8. Conclusions
From the individual corrosion experiments conducted, the
copper samples experienced the greatest mass loss, varying
on average between 0.8 and 0.145 g/(m2 h) for ClimSel C18
and EPS E17, respectively. In comparison with similar surface areas of aluminium, pitting corrosion at a mass loss of, on
average, 7 105 g/(m2 h) while in contact with the ClimSel
C18 occurred. Negligible mass was lost from the aluminium
samples in contact with E17 although localised pitting with
this PCM was observed from the metallographic examination. Pits occurred on all aluminum alloy samples and ranged

in diameter between 2.5 and 8 m for E17 individual samples, increasing up to 30 m for the C18 samples.
For the combined samples of aluminium alloy and copper
in the PCMs, no mass loss occurred with the copper samples
as expected due to cathodic protection. The corrosion rate in
the C18 immersed aluminium alloy samples increased by, on
average, a factor of 8. This was a consequence of the area
imbalance arising from the average copper area of 7.13 cm2
and the average aluminium area 3.85 cm2 . Pitting diameters
increased dramatically for all the aluminium alloy samples
in the galvanic corrosion tests, ranging from 2.5 to 17.58 m
across the surface for E17 samples and up to 25 m for the
C18 samples. Localised deep-pitting of diameters ranging
from 650 to >800 m also occurred on these samples.
It is concluded that a conventional aluminium fin expanded
copper heat pipe heat exchanger will experience galvanic corrosion and localised pitting corrosion when immersed in these
PCMs.
The tests were conducted under airtight conditions, however, a small quantity of air may have been trapped while
pouring the PCM into the containers used. This air would
have accelerated chemical reactions between chloride ions
and iron alloys. This research highlights that pitting corrosion will lead to rapid failure and a reduction in the operating
life of heat exchangers using aluminium in contact with these
PCMs. Pitting processes lead to the development of minute
holes in aluminium parts, leading to leakage of chemicals or
PCM materials. Modifications that may offer resistance to
galvanic and pitting corrosion involve zinc plating the housing chamber and PCM gravity separation plates. If there is

A.J. Farrell et al. / Journal of Materials Processing Technology 175 (2006) 198205

insufficient zinc area (less than the aluminium area) then further perforated plates may be inserted into the PCM chamber
above and below the fin matrix to offer the required sacrificial
alloy corrosive area. To reduce the effects of Galvanic corrosion, the aluminium anode surface area should be as large
as possible and the copper pipe cathode as small as possible.
Different aluminium alloys may also offer greater protection
from this form of corrosion.

[6]

[7]

[8]

Acknowledgements
We wish to acknowledge the assistance from Dr. Tony
Betts, Centre for Research into Engineering Surface Technology at Dublin Institute of Technology, in the development
and completion of this paper, and to Mr. Denis Mc Keown,
Dublin Institute of Technology, for his assistance in preparing
the samples for analysis.

[9]
[10]
[11]

[12]
[13]
[14]

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