Engineering Failure Analysis 111 (2020) 104502

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

A metallographic case study of formicary corrosion in heat

T
exchanger copper tubes
Marzena Małgorzata Lachowicz
Wroclaw University of Science and Technology, Faculty of Mechanical Engineering, Department of Metal Forming, Welding Technology and Metrology,
Lukasiewicza 7-9, PL-50371 Wroclaw, Poland

ARTICLE INFO ABSTRACT

Keywords: This paper presents the results of tests for corrosion damage that occurred on the inner surface of
Cu-DHP copper tubes of a shell and tube heat exchanger. A typical image was observed for corrosion
Copper tube caused by the presence of organic decomposition products on the copper surface, leading to the
Analysis of destruction causes formation of carboxylic acids. Light microscopy and SEM was used to describe the nature of the
Formicary corrosion
ant-nest corrosion. It has been observed that the orientation of the formed tunnels can be related
Carboxylic acids
SEM
to their movement along the grain boundaries. The research also focused on the important role of
the surface condition caused by technological processes and non-metallic inclusions on the in-
itiation of corrosive features.

1. Introduction

Copper corrosion caused by carboxylic acids affects copper components used in the HVAC industry. It is estimated that it relates to
10% of all corrosion damage occurring in these systems, and its occurrences are observed after a few months of operation [1,2]. The
name of this unusual form of corrosion (ant-nest corrosion, formicary corrosion) is associated with the morphology of its spread,
which, in the microscopic image, resembles an ant nest. Corrosion damage is initiated on the surface and penetrates deep into the
component. In this way, longitudinal pits are formed, forming microscopic tunnels (Fig. 1). During the corrosion process, copper
oxide (cuprite) deposits in the inner walls of the tunnels, contributing to their blackening. The presence of cuprite provides access to
oxygen, which further stimulates the corrosive processes. The mechanism is dangerous due to the fact that corrosion damage may not
be visible to the naked eye, and this can lead to the destruction of the components without previous obvious symptoms. It can lead to
leakage of the copper tubes, causing a loss of refrigerant. The consequence in this case is not only the failure of the heat exchanger,
but also the risk of environmental pollution. Early recognition of this type of corrosion is very important, as it is possible to limit it
and reduce its development.
Source literature provides data on the occurrence of typical cases of copper pitting corrosion caused by the presence of chloride
ions [3,4]. Numerous instances of stress corrosion have also been documented [5–8]. A synergic association of formicary corrosion
with stress corrosion was observed [9]. Also, Chandra et al. [10] noted that formicary corrosion was more easily initiated, and the
change zone is more extensive when it concerns areas of bends, and therefore locations of significant tensile stresses. No correlation
between this type of corrosion and grain boundaries has been observed, which rejects the intercrystalline character of this corrosion
[2].
Formicary corrosion is a special type of corrosion in which the resulting microanode pitting is small in diameter, and forms a
tunnel deep into the material. From an electrochemical point of view, however, the corrosion mechanism is different from typical

E-mail address: marzena.lachowicz@pwr.edu.pl.

https://doi.org/10.1016/j.engfailanal.2020.104502
Received 7 January 2020; Received in revised form 26 February 2020; Accepted 4 March 2020
Available online 07 March 2020
1350-6307/ © 2020 The Author. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
M.M. Lachowicz Engineering Failure Analysis 111 (2020) 104502

Fig. 1. General schema of changes in the development of carboxylic acid corrosion.

pitting corrosion, in which corrosion changes are usually visible to the naked eye, and the main reason is the presence of chloride ions
in the environment. It is caused by the presence of decomposition products of relatively strong acids belonging to the carboxyl group
on the copper surface, particularly acetic, formic, propionic and butyric acid [1]. Of the mentioned acids, the strongest effect is
attributed to acetic acid. The corrosion rate increases with the vapour concentration (Fig. 2). The severity of the corrosion increases
with the acid dissociation constant that reflects the strength of the acid [2]. In addition to carboxylic acids, two other factors are
necessary to initiate and upkeep the electrochemical processes, and these are: oxygen and moisture. Thus, removing one of them
reduces corrosion.
The appearance of carboxylic acids necessary for the development of corrosion usually involves the use of organic solvents used in
the degreasing, cleaning and etching of tubes, as well as synthetic lubricants used in technological processes. Their decomposition can
lead to the formation of vapours of these acids [1,2]. Therefore, the standard PN-EN 1057:2010 includes restrictions on the content of
residual and potential carbon, which may not exceed 0.20 mg/dm3. The source of organic acids may not always be the production
process, because their presence is also observed in the atmosphere [1]. They can also come from volatile substances of varying
etymology [2].
There is overall agreement regarding the general mechanism of copper corrosion after exposure to carboxylic acids that can be
represented as follows. Copper dissolution initiated by various factors leads to the formation of copper ions. In the presence of
carboxylic acids, they form an unstable complex with them: Cu+ + (ORG)− → Cu(ORG), where ORG: HCOO−, CH3COO−,
CH3CH2COO−, CH3(CH2)2COO− and others. Then, in the presence of oxygen, these unstable compounds are oxidised to form copper
carboxylate and copper oxide Cu2O (cuprite) according to the equation (1):

4Cu(ORG) + 1/2 O2 → Cu2O + 2Cu(ORG)2 (1)

This leads to the formation of surface microcracks in the copper elements. Due to the larger volume of the resulting products of
this reaction, there is a “wedging” effect and the spread of corrosion. The resulting microcracks reveal a “fresh” surface that leads to
an anode reaction taking place inside the crack, with the formation of a copper complex according to the equation (2):

Cu(ORG)2 + Cu → 2Cu(ORG) (2)

Copper (I) oxide can also be formed by direct anode reaction. Cyclic repetition of the above reaction in the presence of water,

Fig. 2. The effect of carboxylic acid concentration on the corrosion rate of copper elements (based on [1]).

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Fig. 3. General view of the examined tube from the shell and tube heat exchanger. The outline indicates the location of the leak in the leak test.

oxygen and acid leads to the formation of tunnels deep into the material. The corrosion rate under such conditions is extremely fast
[11]. The disappearance of one of the factors stops corrosion [10,12]. Corrosion is still a subject of debate, and a significant problem
in this respect is the fact that it is not easy to obtain in laboratory conditions.

2. Research material and methodology

A shell and tube heat exchanger was tested, in which the heat transfer fluid flows through copper tubes, with an external Ø 12 mm
and a wall thickness of 0.8 mm. In the pressure test of the heat exchanger carried out by manufacturer, several leakage points were
found in the copper tubes. The pressure test was realised using a helium leak test. The leak points were located on a straight segment
of the tube. Fig. 3 shows one example of such a leak location. The leak was difficult to observe with the naked eye. Only a microscopic
hole was observed on the surface.
The standard PN-EN 12375:2016-8 specifies the chemical composition of copper used in air conditioning and refrigeration sys-
tems. It assumes the use of copper deoxidised with phosphorus Cu-DHP, which contains more than 99.99% copper, and controller
deoxidiser content. The chemical composition of the tube tested was in accordance with this specification and the phosphorus content
was 0.029 wt%.
Macro and microscopic observations were made using a Leica M205C stereoscopic microscope and a Leica DM6000 metallo-
graphic microscope. The tests were carried out in both a non-etched state and when etched with a chromium anhydride reagent.
Chemical composition microanalysis by EDX/EDS was performed using a Phenom ProX scanning electron microscope.

3. Research on the heat exchanger's copper tube

3.1. Macroscopic tests

The external and internal surfaces of the copper tube were subjected to macroscopic examination at the location of the leak. The
outer surface was free of corrosive damage. Meanwhile, numerous local changes were found on the inner surface of the tube. They
formed banding of small micro pitting that had a dark colour in the macroscopic image. Oval and flat corrosion spots with a
maximum size of 1 mm were also observed locally. Their character is shown in Figs. 4–6. Such an image of damage occurs during
corrosion caused by the presence of products of decomposition of organic substances into carboxylic acids on the copper surface, and
the development of which can lead to intense destruction of copper elements in a short period of use. Initiation of corrosion in the
near-surface area can indicate the significant role of the surface in this respect.
In the stereoscopic image, the optical properties of the examined corrosion products in the areas of corrosion spots were typical
for copper (I) oxide Cu2O (cuprite) that has a ruby red colour fading into black [13]. The presence of cracks penetrating the material
was also observed (Fig. 6b). The oval shape of the early changes can suggest that the initiation of corrosion begins with the formation
of almost flat pitting, and only then local corrosion develops penetrating deeply into the material.

3.2. Metallographic examination

Microscopic tests carried out on the cross-section of the heat exchanger being examined showed the presence of longitudinal
tunnels filled with corrosion products. Such a picture of the damage indicates the occurrence of ant-nest corrosion, in which deep
corrosion changes lead to the formation of channels containing corrosion products (Fig. 7). The tunnels visible in the microscopic
images of cross-sections are probably only a fragment thereof. Microscopic tunnels initiated on the inner surface propagated further
in the tube wall. The corrosion products formed in electrochemical processes were deposited on the inner walls of these tunnels, and
the macroscopic image of these features was characterised by the formation of black areas on the copper surface. As a consequence, it

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Fig. 4. General view of the inner surface of the tube being tested. Visible streaked dark coloured corrosion changes characteristic of formicary
corrosion. Stereoscopic microscopy. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

Fig. 5. (a) View of the inner surface of the examined tube. Visible numerous corrosion features in the form of flat corrosion spots and micro pitting
filled with corrosion products. (b) An enlarged fragment of the area from Figure a. Stereoscopic microscopy.

Fig. 6. (a) View of the inner surface of the examined tube. Visible flat corrosion spots filled with ruby red products and discontinuities occurring as
part of corrosive damage (marked with arrows). (b) An enlarged fragment of the area from Figure a. Visible crack penetrating deep into the material.
Stereoscopic microscopy. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

began its gradual transformation into a hollow tunnel, progressing deeper due to the oxidation of its walls. Finding the exact point of
leakage was difficult due to its small dimensions, but the presence of tunnels was also observed at considerable distances from the
surface of the tube, which proves their large extent (Fig. 7c). Microscopic observations of corrosion also indicate that the tunnels are

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Fig. 7. View of the cross-section made through the tube. Visible tunnels filled with corrosion products initiated on the inner surface (a, b), as well as
crossing the inside of the tube (c). Light microscopy, non-etched.

not formed along a straight line, but form a kind of spiral in the material (Fig. 8). Peltola and Lindgren [2] also observed a similar
microscopic image. Initially, all precipitations were arranged perpendicular to the surface. However, the presence of the fragment of
the tunnel observed on the cross-section indicates that the course of corrosion changes its path. It seems that the two meeting tunnels
probably merge and continue onwards together. However, it cannot be ruled out that the corrosion paths do not cross over (as is the
case with filiform corrosion). The spiral nature of the developing damage will be conducive to changing the course of corrosion.
The surface distribution of oxygen and copper obtained from the cross-section of one of the tunnels is shown in Fig. 9. The EDS
method has a limited capability of quantitative oxygen content analysis, however in this case, a clear qualitative increase of oxygen
content in the areas of corrosion products was observed. It can also be seen that the resulting corrosion products did not fill the tightly
formed tunnels and were also characterised by the presence of cracks, which thus allows further penetration of the electrolyte into the
fracture areas. It also hampers the leaching of reaction products that are inside these tunnels. It is assumed that the main oxide that
forms during corrosion is Cu2O, in which copper occurs in the first oxidation state. Spot microanalysis of the chemical composition
performed using such corrosion products showed that they contained about 12–14 wt% oxygen, which corresponds to 35–40 at% of
this element. This composition is similar to the stoichiometric composition of the Cu2O phase. An example of the spectrum of
characteristic radiation obtained from corrosion products is shown in Fig. 10.
When considering ant-nest corrosion, it is worth noting that from an electrochemical point of view, the formation of pitting on
copper with a cleaned surface is accompanied by a potential difference between the anode centre of the pitting and the surrounding
area, which is about 30 mV [14]. This is not a value that initiates corrosion. However, it has been proved that for copper, there is a
certain critical value of the potential measured outside the pitting, above which its development will occur. For a concave tube
surface, it amounts to +420 mV (NEK) [14]. Pourbaix also points out that the presence of carbon on the copper surface, which has a
high electrode potential in aerated water, can lead to a local increase in the electrode potential of copper up to +650 mV (NEK) [14].
It will ensure a strong development of corrosion under such conditions, and may explain the cause of intensive development due to
the presence of carboxylic acid decomposition products on the copper surface.
Etched microscopic examinations showed the appearance of a single-phase microstructure, characteristic of copper after plastic
deformation. Locally, single inclusions were observed, whose chemical composition obtained by EDS indicated the presence of
phosphorus, iron and oxygen (Figs. 11a, 13, 14). It is important that none of these elements were present in the chemical composition
of the reagent used for etching that could lead to the introduction of these elements from the outside. Metallographic preparation also
did not use any materials that would be based on these elements. Their presence should therefore only be associated with the process
of copper deoxidation and copper contamination with iron, and their interaction has led to the formation of non-metallic inclusions.
Given the EDS spectrum obtained, these are probably iron phosphides, phosphates or oxides of phosphorus and iron (Fig. 14). They

Fig. 8. General view of corrosion at the place of initiation. The spiral character of the tunnel being formed is visible (marked with arrow). Cross-
section. Non-etched. Light microscopy, DIC contrast.

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Fig. 9. Microscopic image (a) along with the distribution of copper (b) and oxygen (c) obtained from this area. Point 1 indicates the place where the
chemical composition microanalysis was performed SEM/EDX.

Fig. 10. The characteristic X-ray spectrum obtained from Point 1 shown in Fig. 9a.

Fig. 11. (a) View of non-metallic inclusions visible on the metallographic specimen. (b) An example of a corrosion tunnel formed at the grain
boundaries. Point 1 indicates the place where the microanalysis of the chemical composition was carried out. SEM.

were found mainly inside the copper grains, but locally also along its borders. Their microscopic image was different from tunnels
filled with copper oxide that were visible in the cross-section on the metallographic specimen (Fig. 11b, 12). The behaviour of these
inclusions under the impact of the reagent used for etching indicates that they are potential corrosion initiation sites. The obtained
spectrum also contained reflections from copper originating from the base material, which resulted from the properties of the EDS
method, in which the electron beam also reaches deeper areas of the material. It can also be due to the presence of this element in
precipitations. From a thermodynamic point of view, in copper, iron can form many types of phosphides, such as: Fe3P, Fe2P, FeP,
FeP2, FeP4 [15,16]. Magnusson [15] determined that the FeP2 phase is the most stable. The creation of this phase would explain the
higher phosphorus content compared to iron in the EDX results (Fig. 14). The reaction between iron and phosphorus in copper has

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Fig. 12. The characteristic X-ray spectrum obtained from Point 1 shown in Fig. 11b.

Fig. 13. (a) Enlarged fragment of the area from Fig. 11a. The microstructure of the tested tube consisting of phase precipitates α with visible twins
and local clusters of minor non-metallic inclusions. Visible corrosion initiation caused by chemical etching of the metallographic specimen. Point 1
indicates the place where the microanalysis of the chemical composition was carried out. (b) A 3D profilometric image of the microstructure
indicating the formation of micro pitting after etching in areas of non-metallic inclusions. SEM.

Fig. 14. The characteristic X-ray spectrum obtained from Point 1 shown in Fig. 13a. SEM/EDX.

been verified in literature, and led to the development of precipitation hardened high conductivity copper alloys by fine-dispersed
Fe2P iron phosphides [15,17]. If they occur with copper, it can have the complex form (Cu,Fe)2P [16]. Other authors indicate the
Fe3P phase as a strengthening phase [18]. On the other hand, copper deoxidation can promote the formation of Cu3P phase

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Fig. 15. (a) Visible microcracks in the area of non-intensified corrosion changes. (b) Enlarged fragment of the area from Figure a. SEM.

Fig. 16. (a) A 3D profilometric image of a corrosion spot covered with oxidation products with visible microcracks in their area of occurrence. (b) A
distribution of carbon obtained from this area. SEM/EDX.

precipitates. In the presence of iron, this phase may have the form (Cu,Fe)3P [16]. The occurrence of Cu and P in the presence of
oxygen promotes the formation of copper phosphates Cu3(PO4)2 or Cu2P2O7 that are characterised by being of higher stability than
copper oxides [19]. It is likely that the simultaneous presence of these three elements can lead to the formation of complex phosphate
phases. This seems most likely, given the presence of oxygen in the obtained spectrum.
It should be noted that data found in source literature clearly show that phosphorus deoxidation of copper and the presence of
copper-related impurities in iron promote formicary corrosion [1,2]. The copper tubes made in accordance with standard PN-EN
12375:2016 did not contain more than 0.04 wt% of phosphorus. Its content was 0.029 wt% in the research material. Kawano [20]
stated that the low phosphorus content in this range increases the susceptibility to ant-nest corrosion. It was considered that the
phosphorus content above 0.2 wt% affects the nature of corrosion from formicary corrosion to pitting corrosion [20,21].
The effect of phosphorus content is associated with the possibility of the formation of phosphoric acid caused by the presence of
phosphorus in copper, consistent with the anode reaction described in (3) [20].

P + H2O → H2PO4− + 6H+ + 5e− (3)

It can therefore be presumed that the presence of phosphorus-rich inclusions will favour the occurrence of a local anode reaction
due to the release of phosphoric acid in their environment.
Microscopic observations of tunnel, which were cutting the surface of the metallographic specimen with an etched surface,
suggest that the formed tunnels may move along the grain boundaries, as illustrated in Fig. 11b. The tunnel mouth was in this case
clearly formed at the boundaries of three grains. Corbett noted similar observations [22]. Tunnel spreading across grain boundaries
rather than inside grains was also observed by other Authors [2]. This indicates that the development of corrosion may be associated
at the later stage with a loss of grain boundary decohesion, and may explain the synergistic relationship between formicary corrosion
and stress corrosion observed at work [9]. This is due to the fact that diffusion is easier along grain boundaries than through grains as
a result of greater surface energy of grain boundaries associated with the presence of more defects in the crystal structure. Conse-
quently, this reduces the value of the energy necessary for diffusion.
Microscopic tests were carried out of a sample from the place of soldering connections of one of the heat exchangers delivered. No
relationship was found between the occurrence of soldered joints and the intensity of the corrosion damage which occurred.

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Fig. 17. (a) Visible microcracks in the area of non-intensified corrosion damage. Point 1 and 2 indicate the places where the microanalysis of the
chemical composition was carried out. (b) Enlarged fragment of the area from Figure a. (c) The characteristic X-ray spectrum obtained from Point 1
shown in Figure a. (d) The characteristic X-ray spectrum obtained from Point 2 shown in Figure a. SEM/EDX.

3.3. Microscopic tests of corrosive features present on the internal surface

The internal surface of the tube was also subjected to microscopic examination in order to characterise the resulting corrosion
changes. Microscopic observations in areas not subject to intensified corrosion damage and in the place of occurrence of spots showed
the presence of microcracks on the surface caused by the formation of copper oxide (Fig. 15). Therefore, the formation of corrosion
spots visible in the macroscopic image (Figs. 4–6) should be associated with the initial stage of corrosion. A characteristic feature of
the created features was their oval shape, which was associated with the deposition of electrochemical reaction products on the

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Fig. 18. (a) Visible microcracks arranged in the direction of machining covered with octahedral crystals of corrosion products. (b) Enlarged
fragment of the area from Figure a. (c) A 3D profilometric image obtained from the area shown in Fig. 18a. SEM.

copper surface, as a result of the reduction reaction.

Microscopic observations carried out in areas with advanced corrosion changes also showed the presence of microcracks that
locally led to the formation of a gap (Figs. 16–18). As a consequence, one of the cracks became dominant. The microcracks are
associated with the formation of stresses that accompany the formation of a large amount of corrosion products with a larger volume
than copper. They are mostly longitudinal to the tube axis and radiate outwards. By opening, they reveal deeper areas of the copper
material. The tops of these cracks will act as microanodes, and as a result, lead to the propagation of corrosion into the material. The
wall of the tunnel and the copper surface surrounding the crack act in this case as a cathode for oxygen reduction. Locally, copper
dissolution leading to the formation of a pumice-like structure was observed locally on the surface surrounded by these cracks. The
formation of corrosion products in the form of octahedral crystals was observed on the outer surface surrounded by cracks. This
indicates that the resulting corrosion products are transported to the external surface, then creating a dark coloured features typical
for this corrosion. This octahedral form of crystals is appropriate for cuprite. The analysed oxygen content in this area was lower than
the stoichiometric ratio, which is due to the fact that the depth of electron beam interaction also includes the area under the oxide
layer (Fig. 18). Bastidas et al. [1] obtained similar shape of crystals as a result of exposure for 21 days of 100 ppm to formic acid and
acetic acid at 30 °C and 100% relative humidity on the copper surface. Segregation and increased carbon content in this areas were
also observed (Fig. 16b). Even carbon microlayers, invisible to the naked eye, on the surfaces of copper tubes, play a special role in
the corrosion progress.
In the tests carried out, it was observed that the cracks arising are affected by roughness occurring on the surface of the tube
resulting from technological processes related to the shaping of the tube (Fig. 18). In particular, such unevenness that promotes
moisture retention, which in the presence of breakdown products of organic substances to carboxylic acids, begins the self-accel-
erating corrosion process. As a result of the tests, it was found that the emerging corrosion centres follow along this unevenness
(Fig. 19). The cracks and surface roughness promote corrosion because the attack is probably intensified by differences in oxygen
concentration in the cavity and on the camber, which can be a driving force for corrosion through the formation of differential
aeration. Inside the gap, oxygen access is difficult and replenishment is only possible by diffusion. The metal dissolves as a result of
anode processes that leads to the formation at the gap outlet of corrosion products. They limit the outflow of solution from the inside
of the gap and the access of oxygen. The cathode reaction in the gap finishes due to depletion of oxygen. The main site of cathodic
oxygen reduction is on the surface.

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Fig. 19. (a) Visible corrosion products arranged according to surface unevenness due to machining. (b) Visible corrosion centres initiated on the
unevenness of the copper tube surface. (c) A 3D profilometric image obtained from the area shown in Figure b. SEM.

For the reasons given above, care must be taken to ensure the proper surface condition, in particular the cleaning process of HVAC
system components. Corrosion reduction will also be supported by keeping these elements dry by strictly controlling the humidity of
the outer surface of the tubes. However, even maintaining proper procedures for cleaning the surface of copper heat exchanger tubes
at the stage of their manufacture may not protect them against the possibility of contamination in the operating environment.
Therefore, this type of corrosion can still be a significant problem for many heat exchangers.

4. Summary

In the research presented, the corrosion occurring on the inner surface of the tubes made of Cu-DHP taken from a shell and tube
heat exchanger has been described. The use of light microscopy and SEM techniques allowed the visualisation of the nature of ant-
nest corrosion. The main conclusions can be drawn as follows:

(1) Corrosion moved from the inner to the outer surface of copper tubes. The beginning of corrosion is associated with the formation
of microscopic surface cracks caused by the formation of copper oxide. As corrosion progressed, an opening was observed and one
of the cracks formed became dominant. The corrosion products were transported to the outer surface in the form of octahedral
crystals, creating a dark coloured changes typical for this corrosion. Locally increased carbon content was observed in the area of
corrosive features.
(2) Microscopic observations of tunnels, which were cutting the surface of the etched metallographic specimen, suggest that the
orientation of the tunnels may be related to their movement along the grain boundaries. It was also observed that in the initial
stage of their development, they form a kind of spiral penetrating the material.
(3) A corrosion attack can be initiated in the area of non-metallic inclusions rich in phosphorus in the tube material. They were found
mainly inside the copper grains, but locally also along its borders. This may explain why corrosion develops in the copper
deoxidised with phosphorus.
(4) The presence of various types of structural gaps will facilitate the formation of corrosion. An important role in this area is played
by surface unevenness associated with the technological processes used in shaping tubes, such as drawing and machining, be-
cause the attack is intensified by differences in oxygen concentration. A factor that reduces the risk of formicary corrosion in
tubes will be their smooth internal surface. This minimises the possibility of contamination deposits on the unevenness of the

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internal walls.
(5) The location of the damage in a straight segment of the tube suggests that stress does not play a major role in the initiation of
formicary corrosion. However, it can be assumed that local internal stresses will facilitate the formation of surface cracks and
promote the propagation of corrosion. The more so because observations of the cases of its synergistic interaction with stress
corrosion have been described in source literature. Such stresses may be conditioned by technological processes, e.g. tube
bending.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

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