Engineering Failure Analysis 37 (2014) 1–11

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Engineering Failure Analysis

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Failure analysis of copper tube used in a refrigerating plant

K. Chandra a,⇑, Vivekanand Kain a, P.S. Shetty b, Ram Kishan b
a
Materials Science Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India
b
Technical Services Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India

a r t i c l e i n f o a b s t r a c t

Article history: This paper reports the failure analysis of a leaked copper tube used in a refrigerating plant
Received 11 November 2013 for carrying polyol ester oil for lubrication and cooling of compressor bearings. Failure had
Accepted 26 November 2013 occurred at the bent region of the tube in the form of a wide diametric crack. The crack was
Available online 3 December 2013
intergranular and filled with corrosion products. The failed region on the inner diameter
side of the tube had red–brown and dull-black surface films which were identified as
Keywords: cuprous oxide. No degradation or decomposition of the lubricant oil was detected. The
Copper
microscopic examination of the cross-section of the tube showed corrosion degradation
Failure analysis
Formicary corrosion
on both the outer and inner diameter surfaces with similar morphology. The corrosion
Ant-nest corrosion morphology consisted of pit tunnels with fine longitudinal cracks bridging individual pit-
Cracking ted regions typical of ant-nest corrosion. A few cracks, at the bent region of the tube, had
originated through the pits and propagated along the wall thickness. The failure was con-
cluded to be due to ant-nest corrosion of copper in the presence of carboxylic acid. Organic
compounds used during the fabrication and joining of the copper tubes, if not properly
cleaned, may decompose to carboxylic acid in presence of air and moisture.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Pure copper tubes are frequently used in various heat-transfer units, such as air-conditioners, refrigerators, evaporators,
solar systems, radiators and condensers [1]. In the present case, pure copper tubes were used to carry oil for lubrication and
cooling of compressor bearings in a refrigerating plant. The lubricant was polyol ester (POE) oil which flowed inside the cop-
per tubes at a temperature and pressure of 30 °C and 1.4 MPa respectively. The dimension of the tubes was 22 mm outer
diameter (OD) and 1.5 mm wall thickness. Brazing was done for joining of copper tubes in the plant. After less than one year
of commissioning, leakage of lubricant oil was noticed at the bent portion in one of the copper tube. This paper describes the
failure analysis that was carried out to investigate the root cause of failure of the copper tube.

2. Experimental

The inner diameter (ID) surface of the failed tube was examined for corrosion appearance using both a stereo microscope
and a scanning electron microscope (SEM). To examine the microstructure of the copper tube, the cross-sectional surface
was mounted and grounded on successively finer grits of emery papers followed by mirror-polishing to a finish of 1 lm
using a diamond paste. Swab etching of the polished samples was done in a chemical solution (5 g FeCl3 + 50 ml HCl + 100 ml
water). The as-polished and etched samples were examined using both optical microscope and SEM.

⇑ Corresponding author. Tel.: +91 22 25595402; fax: +91 22 25505151.

E-mail address: kchandra@barc.gov.in (K. Chandra).

1350-6307/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.engfailanal.2013.11.014
2 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11

Fig. 1. The failed copper tube as observed from the ID side showing through-thickness crack (indicated by arrow) along the diameter of the tube. The ID
surface around the crack is dull-black in appearance with an oily-film present.

The acidity of the used and fresh POE oil was determined using alcoholic KOH titration according to ASTM standard D 974
[2]. Fourier-transform infrared (FTIR) analysis in the infrared range of 4000–550 cm1 was also performed on the used and
fresh POE oil to determine the degradation of oil, if any. The copper tube ID surface was analyzed using a micro laser Raman
spectrometer to identify the surface film. The excitation source used was Argon ion air cooled laser of 514 nm wave length
with a power of 18 mW. The sample was placed on the microscopic stage and an objective lens of 50 magnification was
used. The spectral range was 100–1000 cm1 and the acquisition time was set at 60 s.

3. Failure analysis

3.1. Visual examination

The photograph (Fig. 1) shows the cut portion of the failed copper tube in which leakage was noticed. The failed tube was
further cut longitudinally into half to examine the ID surface. The failure was observed in the form of a wide and through
wall thickness crack (evident with naked eye) at a location where the tube was bent at 90°, as seen in Fig. 1. The crack
was aligned along the diameter of the tube (Fig. 1). In addition, ID surface around the crack was red1–brown and dull-black
in appearance with an oily-film present. The black surface film was also present at several other locations away from the failed
region on the ID side of the tube.

3.2. Stereomicroscopic examination

Fig. 2(a and b) show the ID surface near the failed region of the tube as examined by the stereo microscope. A single (with-
out branching) wide crack (Fig. 2(a)) filled with corrosion products was present at the bent region of the tube. In addition,
red–brown and black corrosion films on the surface were present around the crack. Intergranular attack and very fine pits
were also noticed near the failed region (Fig. 2(b)) of the tube. Intergranular attack was more clearly distinguished during
SEM examination of the surface which is described later. Pitting attack at several locations and well defined lines of pits
(probably along the machined lines) were also present on the ID surface away from the failed region (Fig. 2(c)).

3.3. SEM examination of the ID surface

SEM micrographs in Fig. 3 show the ID surface at the failed region. Fig. 3(a) reveals a very wide crack filled with the cor-
rosion products. At several locations around the main crack, intergranular corrosion was noticed on the ID surface. Fig. 3(b)
shows one of such location where clear corrosion attack is observed along the grain boundaries. Since, the crack was too

1
For interpretation of color in Fig. 1, the reader is referred to the web version of this article.
 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11 3

Fig. 2. Stereo micrographs of the ID surface of the failed tube. At the failed region, showing: (a) a single wide crack filled with corrosion products together
with red–brown and black corrosion films on the surface, (b) intergranular attack and very fine pits. (c) Away from the failed region, showing pitting attack
and well defined line of pits. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

wide (Fig. 3(a)) to be able to clearly distinguish the cracking mode, the crack tip was examined to find out the crack prop-
agation path. It is clear from SEM micrograph in Fig. 3(c) that the crack in the failed copper tube had propagated along the
grain boundaries. A sample was also cut away from the failed region for SEM examination of the ID surface. SEM micrographs
in Fig. 4 show the surface appearance of the ID side of the copper tube away from the failed region. There were number of
locations at which intergranular corrosion (Fig. 4(a)) and fine pits (Fig. 4(b)) were observed on the tube ID surface. In addi-
tion, thick corrosion deposits were also noticed on the ID surface (Fig. 4(b)).

3.4. Microstructural examination

The failed sample shown in Fig. 1 was cut longitudinally so that the cut piece contained the through-thickness crack.
The cut sample was mounted such that the cross-section of the tube containing the through thickness crack could be
mirror-polished. The optical micrograph in Fig. 5(a) shows the main crack covering the full thickness of the tube. A number
of pits were also observed near the failed region at the ID side of the copper tube. Few smaller cracks were also observed
4 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11

Fig. 3. SEM micrographs of the ID surface at the failed region of the copper tube showing: (a) very wide crack filled with corrosion products, (b)
intergranular corrosion and (c) the region of crack tip. The crack propagation path is along the grain boundaries.

emanating from these pits on the ID side and propagating along the thickness of the tube. The optical micrograph
(Fig. 5(b)) shows one of the cracks originating from a deep pit on the ID surface. These smaller cracks propagating through
the thickness of the tube were present very close to the main crack and only at the bent region of the tube. This is due to
the high residual stresses present in the bent region that caused even higher stress concentration at the pit leading to crack
initiation and propagation towards the OD side. Shallow pits and cracks were also observed at the ID side of the copper
tube away from the bent region; however, the features of cracks were different. These cracks were longitudinal in nature
as opposed to transverse cracks observed at the bent region. The optical micrograph in Fig. 5(c) was taken on the straight
portion of the tube near the ID side sufficiently away from the bent portion showing presence of a number of shallow pits
and fine cracks (indicated by arrows) bridging the individual pitted regions. The corrosion degradation was limited to about
40–50 lm thickness from the ID side of the tube. Similar corrosion morphology i.e. cracks bridging individual pitted
regions were also observed along the main crack (Fig. 5(d)) indicating this to be the primary mechanism for failure of
the copper tube.
The microstructure of the copper tube in the etched condition is shown in Fig. 6. The microstructure in the unaffected
region of the tube showed well annealed single phase of a (face centered cubic) grains (Fig. 6(a)). The crack originating from
 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11 5

Fig. 4. SEM micrographs of the ID surface away from the failed region of the copper tube showing: (a) intergranular corrosion and (b) fine pits together with
surface deposits.

a pit as shown in Fig. 5(b) in as-polished condition was also examined after etching and the corresponding optical micro-
graph is shown in Fig. 6(b). Crack propagation path appears to be along the grain boundaries, however, it is not conclusive.
Initially, it was suspected that the corrosion degradations of the copper tube i.e. pitting, intergranular corrosion and
cracking were limited to the ID surface which was exposed to the flowing POE oil. Therefore, the optical and SEM examin-
ations were mainly concentrated near the ID side of the polished cross-section of the failed tube. Later, examinations were
also done near the OD side of the failed tube. Surprisingly, corrosion degradations that were observed near the ID side were
also observed at the OD side. SEM micrograph, shown in Fig. 7, was taken at the OD side of the failed tube near the bent
region. A number of shallow pits or corrosion attacks were observed on the OD side and these were restricted to only around
40 lm of tube thickness from the OD side. A number of fine cracks emanating from these pits were also observed. One of
these cracks starting from a pit on the OD side had propagated along the tube thickness (Fig. 7). Most of the other cracks
were aligned along the longitudinal direction of the tube interconnecting the individual pits present on the tube OD surface.
The longitudinal cracks might be associated to stresses that were generated by the formation of voluminous corrosion
products.

3.5. Analysis of POE oil

The organic lubricant oil has been reported to decompose into carboxylic acid with usage or in contact with moisture and
air [3,4], which may increase the corrosion susceptibility of copper. Since, initially the corrosion degradation of copper tube
ID surfaces was suspected to be due to its contact with the POE oil, the acidity of the POE oil in which failure was observed
was determined and compared with fresh POE oil. Table 1 shows acidity number of fresh POE oil and the used POE oil in
which failure of copper tube was observed. For comparison, the acidity number of POE oil used in another unit of the refrig-
erating plant was also measured (Table 1) in which no failure of tube occurred. In all the cases, the measured acidity numbers
of the oils were negligible and showed no significant change in the acidity with usage. This indicated that the used POE oil (in
which failure had occurred) was not degraded or decomposed to carboxylic acid to have caused corrosion of copper tubes.
Fig. 8 shows the comparison of FTIR spectra of three different samples of POE oil: fresh oil, the used oil in which tube
failure had occurred and the used oil in which no tube failure was noticed. The FTIR responses of all the three samples of
POE oil are similar to that reported for POE oil lubricant [5]. The FTIR peaks positions for all the three oil samples were same
with no extra peak observed apart from the regular ester peak (C@O stretch) for polyol esters and CAH stretch. The results of
6 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11

Fig. 5. Optical micrographs of the cross-section of the failed copper tube in as-polished condition showing: (a) through-thickness crack, (b) a crack
originating from a deep pit on the ID surface and propagating through the thickness of the tube at the bent region, (c) straight portion of the tube near the ID
side sufficiently away from the bent region showing presence of a number of shallow pits and fine cracks (indicated by arrows) bridging the individual
pitted regions and (d) similar corrosion morphology, i.e., cracks bridging individual pitted regions along the main crack.
 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11 7

Fig. 6. The microstructure of the failed copper tube as observed under an optical microscope in the etched condition showing: (a) annealed structure
consisting of a grains and (b) the same crack as in Fig. 5(b) which appears to be intergranular.

Fig. 7. SEM micrograph showing the cross-section at the OD side of the failed tube near the bent region. A number of shallow pits interlinked by
longitudinal cracks (indicated by arrows) typical of ant-nest corrosion are evident at the OD side. A crack is also shown to be originated from a pit on the OD
surface and propagating towards the tube thickness.

Table 1
Acidity number (mg KOH/g) of different samples of POE oil, determined according to ASTM D974.

Sample description Acidity No. (mg KOH/g)

Fresh oil 0.0241
Used oil, in which no tube failure occurred 0.0265
Used oil, in which failure of copper tube occurred 0.0222
8 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11

Fig. 8. FTIR spectra of three different samples of POE oil: fresh oil, the used oil in which tube failure had occurred and the used oil in which no tube failure
occurred.

Fig. 9. Comparison of micro laser Raman spectra of two different regions of the copper tube: the one region where black surface film was present near the
failed location and the other region of bright surface film away from the failed location.

FTIR spectroscopy was also compared with the ASTM standard E 2412 [3] that reports the standard practice for condition
monitoring of in-service lubricants by FTIR spectrometry. Based on the comparison, it was concluded that there was no deg-
radation or contamination of the POE oil used in the refrigeration plant in which failure of copper tube had occurred.

3.6. Micro laser Raman spectroscopy of copper tube surface

The surface film on the ID side of the failed copper tube was analyzed using micro laser Raman spectrometer. Since, the
copper tube was painted from the OD side; the OD surface could not be analyzed. Raman spectroscopy was performed on
two different regions of the tubes: the one region where red–brown and black surface film was present near the failed loca-
tion and the other region of bright surface film sufficiently away from the failed location. Fig. 9 shows the comparison of
Raman spectra of these two regions. The Raman spectrum of the surface film at the failed region consisted of peaks corre-
sponding to cuprous oxide (Cu2O) indicating the red–brown and black film to consist of Cu2O. The Raman spectrum of the
other bright surface of copper tube did not show any peak indicating it to be pure copper without any significant surface
compound.

4. Discussion

The leakage in the copper tube was the result of pitting and cracking through the full thickness of the tube. Two obser-
vations from the failure analysis point out that there was no role of tube ID environment (POE oil inside the tube) on the
failure or corrosion degradation of the copper tube. One observation was that there was no degradation or decomposition
 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11 9

of POE oil to carboxylic acid as indicated by the acidity number measurement and FTIR analysis of the oils. The other impor-
tant observation was that corrosion attacks in the form of pitting and cracking were observed on both the ID and OD sides of
the tubes. Therefore, the source of corrosion and subsequent failure of the copper tube had to be something else.
At the bent region of the tube, apart from the main crack, there were other smaller cracks originating from the surface pits
on both the ID and OD sides (Figs. 5(b) and 7) and propagating along the tube wall thickness. It is natural to assume that the
crack initiation at these locations were the result of high stress concentration at the pit surface together with the high resid-
ual stress at the bent region. However, the environment responsible for pitting corrosion on both the ID and OD sides of the
copper tube has to be identified. Moving away from the bent region, i.e. on the straight portion of the tube, the examination
of the cross-section of the failed tube showed similar features of corrosion degradation on both the ID and OD sides, i.e. indi-
vidual pits interlinked by fine cracks. These cracks were longitudinal in nature. The morphology of this corrosion degradation
resembles to a unique type of corrosion experienced in thin-walled copper tubes in air-conditioning units and refrigerators
and described in various literatures [1,6–9] as ant-nest corrosion or formicary corrosion due to its unique morphology. The
morphology of this corrosion is similar to an ant-nest when viewed in cross-section and hence its name.
Copper tubes that have suffered ant-nest corrosion were mainly used in heat-transfer units such as evaporators, air-con-
ditioners, refrigerators, condensers, radiators, and solar systems [1,9,10]. This type of corrosion was first reported in the early
1970s by Edwards et al. [11] in copper pipes used for cooling water in an air-conditioning system. Later, a number of cases of
similar morphology were reported all over the world. Attack generally starts at some local discontinuity on the metal sur-
face, such as a defect or small scratch in the surface oxide or metal and the process continues as self-propagating minute pit
tunnels formed by interconnecting random microcavern channels containing porous copper oxide. Pits created by this type
of corrosion are so fine that they are not visible to the un-aided eye [6]. Microscopic pits usually start on the surface of the
copper tubes and progress into the tube wall, similar to the corrosion attack shown to be extending across the tube thickness
(Fig. 5(d)) in the present case. Tube perforation is reported [1,12] to occur quite early i.e. within weeks or months and not
years. The failure in this case was also observed in less than one year after the commissioning of the refrigeration plant.
In many cases, pits have been shown to run parallel to the surface of the tube [9], similar to that observed in the present
case, where pits are shown to be running along the longitudinal direction (Figs. 5(c) and 7). The micro-tunnels associated
with ant-nest corrosion are generally filled with corrosion products (mainly porous Cu2O), which are generated during
the corrosion process [1,7,12]. This cuprous oxide may transport to the tube surface forming a black tarnish film or scale.
Therefore, depending on specific environment ant-nest or formicary corrosion are typically identified by the color of the tube
surface around the corroded regions which are generally reddish brown or reddish purple to black, typical of oxidized copper
[7,9]. Stereomicroscopic examination of the copper tube in the present case showed similar reddish brown and black surface
films around the failed region (Fig. 2(a and b)). In addition, the main crack was filled with porous corrosion products as
examined by SEM (Fig. 3(a)). The black or reddish-brown surface films present around the failed region on the ID surface
were identified to be Cu2O using micro laser Raman spectroscopy (Fig. 9). The bright surface in other regions of the copper
tube did not show presence of such an oxide. These evidences further consolidate the argument that the failure of copper
tube was due to ant-nest corrosion.
Generally, ant-nest corrosion develops in air-conditioners and chiller units stored after assembly, during leakage tests
after installation, or in the initial stages of operation [6,9,11]. This is associated to residual organic compounds that remain
on copper tubes during production and fabrication, that may advance to ant-nest corrosion with the simultaneous presence
of moisture, air and the decomposition of the organics to acids. A wide variety of corrosive media are responsible for ant-nest
corrosion which include chlorinated organic compounds (trichloroethane, trichloroethylene, etc.) used for degreasing, clean-
ing and pickling of the copper tubes or by certain types of synthetic lubricant oils used in forming or joining copper tubes
[1,6–9,12]. The hydrolysis of these organic chemicals, for example, esters or aldehydes could lead to formation of carboxylic
acids in humid air or on the copper surface. In some cases, carboxylic acid such as formic acid and acetic acid were detected
in the system [9]. Borofluoride fluxes used for brazing or soldering of copper tubes and its decomposition products, HF, have
also been suspected as the corrosive media [6–9,12].
The general consensus regarding the mechanism of ant-nest corrosion is penetration of carboxylic acid at the discontinu-
ities in the air-formed copper oxide films leading to dissolution of Cu via anodic reaction [6–9,12]:
Cu ! Cuþ þ e ð1Þ
In the presence of carboxylic acid ions, the copper ions react to form an unstable cuprous complex:
Cuþ þ ðORGÞ ! CuðORGÞ ð2Þ
   
where (ORG) is HCOO , CH3COO , C2H5COO etc.
This complex is oxidized by oxygen to form cupric carboxylate and cuprous oxide:
4CuðORGÞ þ 1=2O2 ! Cu2 O þ 2CuðORGÞ2 ð3Þ
Due to the volume expansion associated with the formation of Cu2O, microcracks may initiate and radiate outward within
the corrosion pit wall under a wedging effect [9,12]. These microcracks are similar to that observed in the failed copper tube
on the cross-sectional surface in the present case (Figs. 5(c) and 7). The microcracks expose more surfaces of copper to the
corrosive media and the process proceeds within the microcrack to give the cuprous complex according to:
10 K. Chandra et al. / Engineering Failure Analysis 37 (2014) 1–11

CuðORGÞ2 þ Cu ! 2CuðORGÞ ð4Þ

Cuprous oxide may also form directly by anodic reaction:
2Cu þ 2OH ! Cu2 O þ H2 O þ 2e ð5Þ
The cathodic reactions are:
O2 þ 2H2 O þ 4e ! 4OH ð6Þ
and

O2 þ 4Hþ þ 4e ! 2H2 O ð7Þ

These cyclic reactions such as (3) and (4) repeat over and over to promote the corrosion [6–9,12].
As stated earlier, the various organic chemicals used during manufacturing, fabrication and joining of copper tubes, if not
properly cleaned, could lead to ant-nest corrosion even during the storage of component subsequent to manufacture [6,9,11].
The use of self-evaporating or synthetic-based, water soluble lubricating oils have been greatly implicated in causing ant-
nest corrosion in several studies [6,7]. The FTIR analysis showed significant amount of these lubricants retained on the ID
surface of the copper tube even after hot water rinsing [7]. The fact that the failed copper tube showed corrosion attack (pit-
ting and longitudinal cracks interlinking individual pits) both on the ID and OD surface and along the entire length of the
tube strongly support the tube degradation to be due to ant-nest corrosion. This corrosion attack was limited to only about
40–50 lm of tube thickness on both the ID and OD sides along the straight portion of the tube and hence was not much of
concern. However, the real concern is at the bent region of the tube where the residual stress is tensile in nature and much
higher in magnitude. This led to a number of cracks initiated at the surface pits on both OD and ID tube surfaces and prop-
agating along the tube thickness. As crack propagated, fresh surface of copper was exposed to the corrosive media leading to
ant-nest corrosion across the wall thickness (Fig. 5(c)), finally resulting in tube leakage or failure.
In the present study, Figs. 3 and 4(a) clearly showed intergranular corrosion and cracking on the tube ID surface. No in-
service failures due to ant-nest corrosion of copper tubes have so far reported intergranular attack [6–13]. This is completely
a new observation that intergranular corrosion was associated with the ant-nest corrosion on an in-service failed copper
tube. However, in a laboratory experiment intergranular corrosion was observed in copper tubes in an atmosphere with a
mixture of either trichloroethylene or dichloro-difluoromethane and water [13]. Intergranular corrosion or intergranular
stress corrosion cracking have been reported [14–16] in in-service failures of copper tubes in air conditioning and refriger-
ation plants but these were not associated with ant-nest corrosion.

5. Conclusions and recommendations

Failure analysis was carried out in a leaked copper tube used for carrying POE oil for lubrication and cooling of compressor
bearings in a refrigerating plant. Failure of the tube was at a location where it was bent at 90° in the form of a wide through-
thickness crack. ID surface in and around the crack was red–brown or dull-black in appearance and crack path was intergran-
ular. The red–brown and black surface films were identified as cuprous oxide. No decomposition or degradation of lubricant
could be measured using FTIR analysis. The failure of the copper tube was associated to ant-nest corrosion that occurs in the
presence of carboxylic acid. Organic compounds used during the fabrication and joining of the copper tubes, if not properly
cleaned, may decompose to carboxylic acid in presence of air and moisture. The examination of polished cross-section of the
failed copper tube showed pitting and fine cracks interlinking the individual pitted regions on both ID and OD sides which
are typical of ant-nest corrosion. Cracks were also observed originating from the pits and propagating along the thickness of
the tube on both ID and OD sides at the bent region, which led to the leakage in the tube. Crack propagation was aided by
intergranular corrosion of copper after exposure of underlying fresh metal to the carboxylic acid.
Since, ant-nest corrosion requires the presence of an organic compound, as-well-as air and moisture, removing any of
these should eliminate the problem. Control measures against ant-nest corrosion include the use of lubricating oils with low-
er carboxylic content, drying the copper surface prior to storage with inert gas and surface treatment with organic inhibitors
that makes the copper surface hydrophobic.

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