Results in Physics 7 (2017) 1760–1777

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Results in Physics
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Electrochemical behavior of tube-fin assembly for an aluminum

automotive condenser with improved corrosion resistance
M.A. Pech-Canul a,⇑, J.C. Guía-Tello b, M.I. Pech-Canul b, J.C. Aguilar c, J.A. Gorocica-Díaz d, R. Arana-Guillén d,
J. Puch-Bleis d
a
Departamento de Física Aplicada, Cinvestav-Mérida, Km. 6 Ant. carr. a Progreso, AP 73 Cordemex, 97310 Mérida, Yuc., Mexico
b
Cinvestav-Saltillo, Av. Industria Metalúrgica No. 1062 Parque Industrial, 25900 Ramos Arizpe, Coahuila, Mexico
c
Departamento de Química Analítica, Facultad de Química UNAM, Ciudad Universitaria, 04510 México D.F., Mexico
d
Airtemp de México, S.A. de C.V., Km 10 carr. Mérida a Umán Tab. Rústico 4193, Umán 97390, Yuc., Mexico

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

Article history: An aluminum automotive condenser was designed to exhibit high corrosion resistance in the seawater
Received 28 December 2016 acetic acid test (SWAAT) combining zinc coated microchannel tubes and fins made with AA4343/
Received in revised form 6 May 2017 AA3003(Zn)/AA4343 brazing sheet. Electrochemical measurements in SWAAT solution were carried
Accepted 7 May 2017
out under laboratory conditions using tube-fin assembly and individual fin and tube samples withdrawn
Available online 10 May 2017
from the condenser core. The aim was to gain information on the protective role of the zinc sacrificial
layer and about changes in corrosion behavior as a function of immersion time. External corrosion of
Keywords:
the tube-fin system was simulated by immersion of mini-core samples under open circuit conditions.
Aluminum
Automotive
The corrosion rate increased rapidly during the first 6 h and slowly afterwards. The short time behavior
Corrosion was related to the dissolution of the oxide film and fast dissolution of the outermost part of the zinc dif-
Galvanic fusion layer. With the aid of cross-sectional depth corrosion potential profiles, it was shown that as the
Zn coating sacrificial layer gets dissolved, the surface concentration of zinc decreases and the potential shifts to less
negative values. The results of galvanic coupling of tube and fins in a mini-cell showed that the tube
became the anode while the fins exhibited cathodic behavior. An evolution in the galvanic interaction
was observed, due to the progressive dissolution of the sacrificial zinc layer. The difference of uncoupled
potentials between tube and fins decreased from 71 mV to 32 mV after 84 h of galvanic coupling. At the
end of such period there was still a part of the zinc sacrificial layer remaining which would serve for pro-
tection of the tube material for even longer periods and there were indications of slight corrosion in the
fins.
Ó 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license ([Link]

Introduction sheet or clad on a core alloy. The core alloy provides structural
integrity while the low melting point Al-Si cladding alloy melts
For environmental reasons, weight reduction is an important and flows during the brazing process, to provide upon cooling a
issue in the development of new automobiles. For this reason, metallic bond between the components. In the case of microchan-
the use of lightweight aluminum alloys has been continuously nel tubes, which are manufactured by extrusion from alloy ingots,
increasing in the automotive industry [1–3]. The condenser of an it is difficult to apply filler metal clad layers. Therefore, the corru-
air-conditioning unit for automotive application is an aluminum gated fins are manufactured from a brazing sheet in which the core
heat exchanger generally manufactured by brazing extruded material is clad on one or both sides with the filler metal.
micro-multiport tubes (in which refrigerant flows) and corrugated The condenser is normally installed in the neighborhood of the
fins (which exchange heat with the air side) [4]. Aluminum brazing front grill of the automobile, so it is subjected to environmental
involves joining the components with a brazing alloy, which is an exposure, and consequently suffers external corrosion. Of main
aluminum-silicon alloy whose melting point is appreciably lower concern is the possibility of tube perforation, leading to coolant
than that of the components; this filler metal is supplied via a thin leaking. In order to avoid this, a careful selection of aluminum
alloys for the different components is of paramount importance.
Conventionally the tube is protected by sacrificing the fins [5–7];
⇑ Corresponding author.
this is achieved by alloying the fin with Zn (to reduce its corrosion
E-mail address: [Link]@[Link] (M.A. Pech-Canul).

[Link]
2211-3797/Ó 2017 The Authors. Published by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license ([Link]
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1761

Fig. 1. Materials structure of the condenser.

Table 1
Compositions (wt%) of the core and filler alloys in the brazing sheet fin. Temper H14.

Si Fe Cu Mn Mg Cr Zn Ti Other Al
Core 0.2–0.6 0.3 0.05 1–1.5 0.05 0.12 2.0–2.4 0.05 0.2 Bal
Clad 7.9–9.5 0.8 0.3–0.4 0.1 0.05 0.05 0.1 0.05 0.2 Bal

Table 2
Composition (wt%) of tube alloy 1197, Temper H112.

Si Fe Cu Mn Mg Cr Zn Ti Other Al
0.2 0.2 0.4 0.1 0.05 0.05 0.05 0.05 0.2 Bal

Amount of Zn coating: 5.5 ± 2.5 g/m2.

potential) and having additions of Mn and Cu to the tube alu- operates, a laboratory study using electrochemical techniques (cor-
minum alloy (to increase its corrosion potential). Another method rosion potential monitoring, electrochemical impedance, potentio-
is by forming a Zn diffusion layer on the surface of the tube mate- dynamic polarization and galvanic corrosion current
rial [7–10]. Zinc has a much lower galvanic potential than alu- measurements) was carried out.
minum, and basically acts as a sacrificial material, so that in the The aim of this paper was to investigate the corrosion behavior
case of an eventual corrosion attack on the microchannel tube it specifically for the tube-fin system, using samples cut out from the
will spread over the surface rather than create a cavity (i.e. deep core of an industrially brazed automotive condenser. External cor-
pitting is prevented). Initially a Zn layer is deposited on the alu- rosion of the assembly was simulated by immersion of small sec-
minum surface (e.g. by Zn thermal spraying) and then the diffusion tions of the condenser core in SWAAT solution. The galvanic
of Zn into the matrix occurs during brazing. Condensers with a tube-fin interaction was examined with a mini-cell containing
combination of sacrificial fin and Zn coated tubing have also been SWAAT solution using tube and fin samples detached from the as
developed in the industry [7,11]; however, an in-depth discussion brazed condenser. The sacrificial effect of the Zn diffusion layer
on the corrosion protection mechanism of such systems is still was investigated with cross-sectional depth corrosion potential
lacking in the literature. profiles. The methodology in this work, using conventional electro-
The present study is part of a research project focused on eval- chemical methods, could be easily implemented in the HVAC
uating the corrosion performance of a condenser which combines a industry to do a quick and reliable characterization of the corrosion
zinc-coated microchannel tube with fins made of AA4343/AA3003 behavior of tube-fin systems.
(Zn)/AA4343 brazing sheet. It was brazed in a controlled atmo-
sphere industrial furnace, using the NocolokÒ flux brazing process
[12,13]. As well known, the standard test for corrosion of automo- Experimental procedure
tive heat exchangers is the saltwater acetic acid test (SWAAT)
which is aimed at reproducing lifetime performance [14–18]. The Materials
condenser in this project is considered to have an excellent corro-
sion resistance since it withstood 40 days of SWAAT without leak- Fig. 1 shows schematically the materials structure of the con-
age. However, in order to understand how the protection method denser. The corrugated fin was manufactured from a brazing sheet
1762 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

Fig. 2. View of condenser core showing the cut sample for electrochemical tests.

(temper: H14) having 16 mm width and 80 lm thickness; modi- the end of the exposure period the cross-section of the tube was
fied AA3003 was used as core material, clad on both surfaces with polished and analyzed by optical microscopy.
AA4343 (using a clad ratio of 10% on both sides). Table 1 shows the
compositions of core and filler alloys. The extruded micro-
multiport tube was manufactured from aluminum alloy 1197 Electrochemical characterization
(see composition in Table 2) with H112 temper. In the as received
condition it had an amount of 5.5 ± 2.5 g/m2 of thermally sprayed The electrochemical measurements were carried at ambient
Zn. During the brazing process (around 600 °C) Zn diffuses temperature in acid seawater solution prepared according to ASTM
inwards, forming a Zn diffusion layer (the sacrificial layer). G85-09 A3 [13], using a Gamry series G300 potentiostat/galvanos-
Microchannel tubes were stacked with corrugated fins and the tat. An Ag/AgCl reference electrode was used to monitor the corro-
ends inserted into the headers to form a regular size automotive sion potential under open circuit conditions (Eoc); for 3-electrode
condenser. The assembly was brazed in a controlled atmosphere cell configuration, the counter electrode was a large area Pt foil.
industrial furnace, using the NocolokÒ flux brazing process. In order to evaluate the overall corrosion behavior of the fins
and external surface of microchannel tubes (mimicking external
Morphology and microstructure characterization corrosion of the condenser under complete wetting conditions), a
mini-core cut from the condenser core (see Fig. 2) was immersed
After brazing, a small section of the condenser core was cut, in SWAAT solution. The cut sample (with dimensions of
embedded in epoxy resin and the face exhibiting the cross- 15
16
12 mm, L
W
H) contained two rows of flat tubes
section of tube-fin joints was ground and polished. The microstruc- and the corrugated fins in between. In order to avoid penetration
ture at a section of tube-fin joint was examined with a field of solution to the microchannels, the ends of the tubes were sealed
emission Scanning Electron Microscope (SEM) Jeol JSM-7600F with epoxy resin, leaving a total exposed area (fins + tube) of
coupled with an energy-dispersive X-ray (EDX) detector. Elemental 18 cm2. Eoc was monitored during 24 h, and during this exposure
mapping using quantitative X-ray mapping was conducted to period electrochemical impedance spectroscopy (EIS) measure-
identify the nature of main constituent particles. Furthermore, ments were carried out (after 1, 4, 8, and 24 h) using a sine wave
the structure in the fin and fillet within the selected joint zone perturbation signal with 10 mV amplitude in the frequency range
was revealed by etching with Keller’s reagent (2 mL HF + 3 mL of 10 kHz–250 mHz with 5 points per decade. Useful information
HNO3 + 5 mL HCl + 190 mL H2O) [19] and analyzed with a Nikon about corrosion kinetics can be obtained with DC polarization
Eclipse LV15N optical microscope. measurements; thus a potentiodynamic polarization curve was
Zn concentration profiles in the sacrificial layer of the obtained for a mini-core sample previously stabilized during one
microchannel tube were obtained by X-ray energy dispersive line hour in the SWAAT solution. It was performed at a scan rate of
scans. 1 mV s1 starting at a potential 200 mV more negative than Eoc.
In order to visualize the corrosion morphology of the sacrificial For comparison, polarization curves were also obtained for individ-
layer, a small tube sample was galvanically coupled to a pair of fins ual components (tube and fin) detached from the post-brazed con-
during 24 h in SWAAT solution (procedure described below) and at denser core.
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1763

Fig. 3. a) Schematic of a single galvanic cell formed in the core under complete wetting condition, and b) schematic of mini-cell used for galvanic corrosion experiment.

The sacrificial ability of the Zn diffusion layer in the was possible to determine (by the difference between initial
microchannel tube was evaluated by cross-sectional depth and final wall thicknesses).
corrosion potential profiles, as follows. A small sample of tube The tube-fin galvanic interaction was investigated with Eoc and
was cut from the as brazed condenser and embedded in epoxy galvanic corrosion current measurements. The conditions for gal-
resin leaving uncovered 0.64 cm2 of external tube surface. The vanic corrosion in a condenser exposed to a corrosive atmosphere
surface at different depths was exposed by performing arise when, under complete wetting conditions, a thin layer of
successive grinding steps with emery paper grade 1200. After electrolyte establishes a corrosion cell between fins and external
each step the sample was rinsed with distilled water and surface of the tube [18]; this is shown schematically in Fig. 3(a).
immersed in SWAAT solution where Eoc was recorded during In order to mimic this situation, the cell for galvanic corrosion
60 min. At the end of the experiment the resin was removed, measurements was constructed as shown in Fig. 3(b). A small piece
the sample was observed in cross-section with an optical of tube and 2 fins were detached from the condenser core. The tube
microscope and the final wall thickness was measured. So, sample was embedded in epoxy resin leaving exposed one of the
with this procedure only the final depth from the surface flat external surfaces (3 mm
16 mm); the fins were glued to
1764 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

Fig. 4. Optical image of tube-fin joint after etching with Keller’s reagent.

the longer inner faces of a rectangular glass cell. Then the cell, with the literature [16–18,25,26] that during brazing Si diffuses from
the flat tube at the bottom, was filled with SWAAT solution to a the melted cladding to the core material and leads to the transfor-
level of 4 mm; thus the area ratio fins/tube was 8:3. The galvanic mation of Al6(Mn, Fe) precipitates to a phase containing Al, Mn, Fe
current (Ig) between tubes and fins was measured during 84 h. In and Si. In the SEM micrograph of Fig. 5 small elongated particles
addition, the open circuit potential of individual (uncoupled) com- were observed in the diffusion zone (labelled as particle type 2).
ponents was measured during 30 min before and 5 min immedi- Fig. 7(a) shows the SEM backscattered electron image of a region
ately after the galvanic experiment. containing this type of particles. The result of EDS mapping of main
alloying elements confirms that these particles correspond to the
Al-Fe-Mn-Si phase.
Results and discussion

Microstructure of the joint Corrosion behavior of mini-core (tube-fin assembly)

Fig. 4 shows an optical image of a section of tube-fin joint after Fig. 8 shows the evolution of Eoc over time for the mini-core
etching with Keller’s reagent. It corresponds to a typical well sample immersed during 24 h in the SWAAT solution. Eoc corre-
brazed fin-to-tube joint where the Al dendritic cells are sur- sponds to a common potential for brazed tube-fins which starts
rounded by the Al-Si eutectic network, with Si present as a needle at approximately 0.88 V vs Ag/AgCl and shifts rapidly to less neg-
like structure [20,21]. Etching was used to visualize more easily the ative values during the first 5 h. After that it slowly reaches a
layered structure of the fin after brazing; the residual cladding pseudo-steady state value around 0.8 V vs Ag/AgCl. In order to
appears bright while the zone affected by Si diffusion appears dark. correlate this potential variation with changes in corrosion rate,
Fig. 5 shows a SEM micrograph of the same joint, before etching electrochemical impedance measurements were carried out after
with Keller’s reagent. In the fillet, apart from the presence of Si 1 h, 4 h, 8 h and 24 h of immersion; the results are presented as
needles, there are block-like precipitates appearing in bright con- Nyquist plots in Fig. 9. Each diagram exhibits the typical impe-
trast (labelled as particle type 1). Fig. 6(a) shows the SEM backscat- dance response for aluminum in acid solutions [27–31], which
tered electron image of a small area with particles type 1. Lacaze consists of a capacitive loop at high frequencies followed by an
et al. [22,23] observed a similar type of particles in the joint zone inductive loop in the low frequency range. It is evident that with
of two brazed multilayer sheets (modified AA3003 core, clad on increasing immersion time the size of the diagrams decreases
both faces with AA4343) and identified them with the Al-Fe-Mn- and the high frequency (HF) loop becomes more depressed.
Si phase. In our case, the result of EDS mapping of alloying ele- According to the literature review for corrosion of aluminum in
ments Fe, Mn and Si (Fig. 6(b)–(e)) suggest that these precipitates acid solutions, the HF loop has often been attributed to multistep
correspond rather to the Al-Mn-Fe phase. These particles were also dissolution and ionic migration through the oxide layer [27] or to
observed by Davoodi et al. [24] for rolled EN AW-3003 alloy after a the dielectric properties of the oxide film itself [28,29,31,32]. For
braze-simulation treatment. It has been extensively discussed in the inductive loop various interpretations have been given: surface
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1765

Fig. 5. SEM micrograph of tube-fin joint before etching.

or bulk relaxation of species in the film [27], coverage relaxation of and fitted data in the Bode plots of Fig. 11). The impedance spectra
the adsorbed intermediate Hads in the reduction of H+ [28,31,33,34] for 8 h and 24 h exhibit a more flattened aspect in the HF range and
or coverage relaxation of other adsorbed intermediates involving this effect has been related to surface inhomogeneity due to rough-
inhibitor molecules as well as reactive products [35], metal disso- ness and the presence of corrosion products. In this case, a better
lution process at the oxide film/electrolyte interphase [32] and fit is obtained if the equivalent circuit in Fig. 10(c) is used instead
localized corrosion (e.g. pitting) [29]. The equivalent circuit most of that in Fig. 10(a). This modified circuit includes a second time
commonly used to fit the experimental impedance data is that constant in the HF range (with parameters R0, Q0 and a0) to
shown in Fig. 10(a) [29,32]. account for impedance response of the surface layer of corrosion
Rs is the solution resistance, Q and a are parameters associated products. A comparison of experimental and fitted data in pre-
with a constant phase element (CPE), Rp is the polarization resis- sented as Bode plots in Fig. 12. The optimum fit parameters for
tance, L and Rind are the elements related to the inductive loop. all the analyzed impedance data are presented in Table 3.
As shown in the schematic diagram in Fig. 10(b), the charge trans- It is interesting to observe that for the impedance data obtained
fer resistance Rct is obtained from the addition of Rp and Rind. The after 1 h in the SWAAT solution, the value of the CPE exponent a1 is
CPE is usually introduced to account for non-ideal capacitive 0.83, but for the other times is between 0.7 and 0.75 (indicating a
behavior of the interfacial charge storage mechanism. The non- strong deviation from ideality). Furthermore, the value of Q1
ideal behavior is related to a frequency dispersion phenomenon increased with immersion time. The effect of decreasing a coupled
which may have different origins, such as: roughness, surface dis- to increasing Q has been related by Córdoba-Torres et al. [37] to a
order, electrode porosity, and non-uniform potential and current double-layer capacitance distribution caused by surface inhomo-
distribution associated to electrode geometry (see Refs. [36,37] geneity. As indicated above, such inhomogeneity was attributed
a
and references therein). Its admittance is given by Y CPE ¼ Q ðjxÞ , here to an increase in roughness and a progressive accumulation
where x is the sine wave modulation angular frequency, Q is the of corrosion products with increasing immersion time.
CPE coefficient (with dimensions X1 sa cm2) and a is an empir- The fit parameters related to the HF loop can be used to deter-
ical exponent (0  a  1) which measures the deviation from the mine the value of the effective interfacial capacitance (Ceff). Two
ideal capacitive behavior. formulas are commonly used in the literature, which according
An attempt was made to fit all the experimental impedance to Hirschorn et al. [38], are associated with either surface or nor-
data in Fig. 9 with the equivalent circuit in Fig. 10(a), however it mal time-constant distributions, depending on the system investi-
was observed that a very good fit was obtained only for the short gated. In the present work the global admittance response of the
immersion times of 1 h and 4 h (see comparison of experimental electrode includes additive contributions from each part of the
1766 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

Fig. 6. a) SEM image and EDS mapping of: b) Al, c) Fe, d) Mn and e) Si for a region with particles labeled as ‘‘type 1” in Fig. 5.

electrode surface (louvered fins and external tube surface). Thus the corresponding value of Ceff for the short immersion time of 1 h
the following relationship [37,38] for a surface time-constant dis- in SWAAT solution is 3.0 lF cm2. This is lower than the typical
tribution was used to estimate Ceff value of the double layer capacitance Cdl (50 lF cm2). So it seems
 ð1a1 Þ=a1 that, as described elsewhere [39,40], this high frequency interfacial
a1 Rs Rp
C eff ¼ Q 1= ð1Þ capacitance represents a series connection between Cdl and the
1
Rs þ Rp oxide film capacitance Cox,
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1767

Fig. 7. a) SEM image and EDS mapping of: b) Al, c) Fe, d) Mn and e) Si for a region with particles labeled as ‘‘type 2” in Fig. 5.

1 1 1 reasonable value (2.3 nm) of the film thickness is obtained [41,42].

¼ þ ð2Þ
C eff C dl C ox So the high frequency arc for short immersion time (1 h) defines a
capacitance which includes contributions from the compact part
where C ox ¼ ee0 =d, e0 is the permittivity of vacuum, e the dielectric of the oxide layer and from the double layer at the oxide/solution
constant of the oxide and d its thickness. The capacitance Cox calcu- interface. For the other immersion periods (4 h, 8 h and 24 h) an
lated from Eq. (1) is 3.2 lF cm2. Assuming a value of 8.4 for e [40] a accurate determination of the interfacial capacitance and its
1768 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

Fig. 8. Variation of open circuit potential with time for the mini-core sample immersed in the SWAAT solution.

Fig. 9. Nyquist diagrams obtained for the mini-core sample after different immersion times in the SWAAT solution.

description in terms of Eq. (2) is difficult because roughness leads to In Table 3, a column for the charge transfer resistance
changes in the real surface area (so that Cdl is not constant) and also (Rct = Rp + Rind) is also included. According to the Stern-Geary
because dissolution of the oxide film takes place. equation the corrosion current density icorr is proportional to the
Results of galvanic corrosion (presented below in reciprocal of Rct ðicorr ¼ B=Rct Þ, with B the proportionality constant;
Section ‘‘Tube-fin galvanic interaction”) showed that the fins exhi- thus, the plot of 1/Rct vs. time in Fig. 13 gives a useful indication of
bit cathodic behavior. Since the area of fins is larger than the exter- the evolution of the corrosion rate during the immersion in the
nal area of tubes in the mini-core the evolution of hydrogen occurs SWAAT solution. It appears that there is a rapid increase of
over a large portion of the area exposed; so, for the system inves- corrosion rate during the first 6 h of immersion, followed by a slow
tigated, the inductive loop can be ascribed to the coverage relax- increase. According to the protection design used during
ation of the adsorbed intermediate in the hydrogen evolution fabrication of the condenser, the Zn diffusion layer in the tubes
reaction. should act sacrificially. So, the initial rise of corrosion rate is
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1769

Fig. 10. a) Equivalent circuit model used to analyze the experimental data in Fig. 9 corresponding to short immersion times (1 h and 4 h), b) schematic Nyquist diagram
corresponding to the circuit in (a), and c) equivalent circuit used to analyze the experimental data corresponding to 8 h and 24 h of immersion in SWAAT solution.

probably due to dissolution of the oxide film and consumption of corrosion current density of the mini-core after 1 h immersion in
the outermost part of the Zn diffusion layer. This is consistent with the SWAAT solution is 27.5 lA/cm2. This can be considered a low
the trend in Eoc. Upon immersion of the mini-core in the SWAAT corrosion rate. However, as suggested by results of impedance
solution the common potential is dominated by the tube. As the measurements it is expected to increase rapidly during the first
Zn diffusion layer starts dissolving the surface concentration of 6 h and slowly afterwards.
Zn decreases and the potential shifts to less negative values.
In Fig. 14 polarization curves for the mini-core sample and
Cross-sectional depth corrosion potential profiles in the tube
uncoupled tube and fins are presented. Ecorr represents the corro-
sion potential determined from the potentiodynamic scan for
Fig. 15(a) shows a SEM image of the cross-section of the tube
uncoupled components. Its values confirm that the tube material
wall after brazing. A Zn concentration profile was obtained with
exhibits anodic behavior (Etube
corr is about 100 mV more negative than EDS line profile analysis, starting from the external surface (as indi-
Efin
corr ). Considering this sequence in potentials only the anodic cated by the red arrow). The result, presented in Fig. 15(b) shows
branch of the polarization curve is shown for the tube and only that the surface concentration is 4 wt% and the diffusion depth is
the cathodic branch is shown for the fins. In contrast, the full polar- about 100 lm.
ization curve for the mini-core is presented. The polarization Based on the specifications of the brazing industry it is very
behavior is consistent with the mixed potential theory: a) the cor- common to measure corrosion potential of brazing sheets as a
rosion potential of the mini-core is a common potential (Emixed) function of time at different depths [43–44] or depth profiling of
intermediate between the Ecorr values of uncoupled electrodes, b) the corrosion potential [45,46]. Although very often the measure-
icorr for the tube material in the mini-core is greater than that for ment is made in salt water/peroxide medium according to ASTM
uncoupled tube, and c) icorr for the fins in the mini-core is less than G69-97 [43], the use of SWAAT solution for such test of corrosion
that for uncoupled fins. Based on the above discussion, the anodic potential has also been reported [44]. In this work the technique
branch of the polarization curve for the mini-core can be ascribed of cross-sectional depth corrosion potential profiling [43–44] was
to dissolution of zinc in the diffusion layer, while the cathodic used. The typical results are shown in Fig. 16. For the initial surface
branch corresponds to the H2 evolution reaction. The Tafel analysis condition, the potential stabilized around 890 mV vs Ag/AgCl.
shows that the Tafel slope of the anodic reaction is 40 mV/decade This corresponds to the free corrosion potential attained by the
and 120 mV/decade for the cathodic reaction. The estimated sacrificial layer. With successive grinding steps the Eoc vs time
1770 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

Fig. 11. Bode plots comparing experimental impedance data (symbols) and fitted values (lines) for the mini-core sample after 1 h and 4 h of immersion in SWAAT solution.
The equivalent circuit in Fig. 10(a) was used. / is the phase angle.

Fig. 12. Bode plots comparing experimental impedance data (symbols) and fitted values (lines) for the mini-core sample after 8 h and 24 h of immersion in SWAAT solution.
The equivalent circuit in Fig. 10(c) was used. / is the phase angle.
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1771

Table 3
Parameters from equivalent circuit analysis of impedance spectra in Fig. 9.

1h 4h 8h 24 h
Rs (X cm )
2
84 79 77 72
Q0
105 (X1 cm2 sa) – – 11.64 9.98
a0 – – 0.72 0.70
R0 (X cm2) – – 87.00 72.21
Q1
105 (X1 cm2 sa) 1.28 4.27 9.69 19.90
a1 0.83 0.72 0.70 0.75
Rp (X cm2) 493.40 448.80 259.04 174.30
Rind (X cm2) 844.80 608.00 625.00 679.40
L (H cm2) 149.31 187.11 148.04 106.92
Rct (X cm2) 1338.20 1056.80 884.04 853.70

Fig. 13. Variation of the inverse of charge transfer resistance with immersion time for the mini-core sample. Values of Rct from Table 3.

curves shift upwards. This means that with successive removal of Tube-fin galvanic interaction
thin layers the zinc content decreases and the potential shifts to
less negative values. The experiment was repeated with several For these experiments the mini-cell shown schematically in
samples and the same behavior was obtained. As indicated above Fig. 3(b) was used. Before coupling the two fins with the small tube
the final depth from the surface (Dx) was calculated as the differ- sample Eoc was recorded for individual elements during 30 min,
ence between the initial and final wall thickness of the tube. For and as shown in Fig. 17 the potential of fins was about 71 mV less
the experiment corresponding to the results of Eoc vs time pre- negative than that of the microchannel tube. Again, this is an indi-
sented in Fig. 16 the determined value of Dx was 90 lm. Consider- cation that when coupled, the zinc diffusion layer in the tube acts
ing that the Zn diffusion depth was 100 lm (according to Fig. 15), it sacrificially and the fins become the cathode in the galvanic cell.
can be concluded that after 4 grinding steps there was still a thin Additional evidence of this behavior is presented in Fig. 18, which
layer of Zn remaining. The potential at this stage was around shows an image captured with a video recorder for a polished
760 mV vs Ag/AgCl and after complete removal of the Zn diffu- tube-fin cross-section after a few minutes of exposure in SWAAT
sion layer (determined in a separate experiment) was 690 mV solution. The bubbles corresponding to the H2 evolution reaction
vs Ag/AgCl. This free corrosion potential of tube alloy material is develop only on the surface of the fin.
in good agreement with that determined elsewhere for aluminum The galvanic current for the tube-fins couple in the SWAAT
alloys with similar composition [47,48]. solution was recorded during 84 h, and typical results are pre-
The results in Fig. 16 support the hypothesis that we put for- sented in Fig. 19. Positive current values indicate that the current
ward in Section ‘‘Corrosion behavior of mini-core (tube-fin assem- flows from the microchannel tube to the fins (i.e. the fins are the
bly)”. The consumption of Zinc in the sacrificial layer due to cathode). A rapid initial rise of Ig is observed, reaching a maximum
corrosion in the SWAAT solution shifts the corrosion potential of value of 29 lA in approximately 15 min. This is related to a quick
the tube (and of the assembly tube-fin) to less negative values. dissolution of zinc in the outermost region of the Zn diffusion layer
1772 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

Fig. 14. Polarization curves for mini-core sample and individual components after 1 h immersion in the SWAAT solution. The corrosion potential determined from the
potentiodynamic scan is represented by Ecorr for the uncoupled components and by Emixed for the mini-core. The Tafel lines are shown for the mini-core sample.

Fig. 15. a) SEM micrograph of cross-section of the tube wall and b) Zinc concentration profile determined with EDS analysis.

driven by a large cathode area (fins/tube area ratio of 8:3) and a reaching a maximum, Ig gradually decreased and tended to stabi-
surface free of corrosion products. Such indication of a quick disso- lize after 24 h at a value around 6 lA. This low value of galvanic
lution of the Zn diffusion layer is consistent with the observed cor- current can be ascribed to a decrease in the difference of uncoupled
rosion behavior of the mini-core immersed under open circuit potentials and to the accumulation of corrosion products.
conditions in SWAAT solution (Section ‘‘Corrosion behavior of The initial and final values of Eoc for uncoupled tube and fins are
mini-core (tube-fin assembly)”). Fig. 19 also shows that after presented as a bar diagram in Fig. 20. It can be observed that the
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1773

Fig. 16. Open circuit potential as a function of time at different depths for the microchannel tube. The first measurement (solid line) was made for the initial surface condition
and the other after successive grinding steps. Dx is the final depth from the surface after 4 grinding steps.

Fig. 17. Measurement of uncoupled potential for the tube and fin during 30 min before the galvanic coupling experiment.

difference in Eoc values between the two components decreased to layer after a certain period of galvanic coupling. Fig. 21 shows
32 mV after 84 h of galvanic coupling (at the beginning it was the appearance of the cross-section of a tube sample after a 24 h
71 mV, as shown in Fig. 17). It is noteworthy that both components galvanic corrosion experiment. No deep pitting is observed; local-
experienced a shift of Eoc to less negative values (84 mV for the ized corrosion starts as small pits growing sideways which then
tube and 45 mV for the fins). In the case of the tube this shift in evolve to form wide shallow pits. It seems that the depth of corro-
open circuit potential can be ascribed to the progressive dissolu- sion penetration shown in this optical image (46 lm) is about half
tion of the zinc sacrificial layer. Optical microscopy was used in the thickness of the zinc diffusion layer. Although the mixed poten-
order to visualize the reduction in thickness of the Zn diffusion tial was not recorded during the galvanic corrosion experiments, it
1774 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

protected by the sacrificial action of the Zn diffusion layer. During

the first 24 h of galvanic coupling the thickness of such layer
decreased to almost half its initial value, but between 24 h and
84 h Ig was very low and therefore the further reduction in
thickness during this period was small. The cross-sectional depth
corrosion potential profiles in Fig. 16 showed that when 90 lm
of the diffusion layer are removed the tube attains an open circuit
potential of around 0.76 V vs Ag/AgCl in the SWAAT solution. The
uncoupled potential of the tube sample after the 84 h galvanic
experiment is 0.803 V vs Ag/AgCl (Fig. 20); so, the overall
reduction in thickness during the 84 h galvanic coupling should
be less than 90 lm. Moreover, this final value of Eoc for the tube
is still about 110 mV more negative (due to the remaining Zn in
the surface) with respect to the corresponding value for bare tube
material (0.69 V vs Ag/AgCl). In other words, the protection
afforded by the Zn diffusion layer is expected to prevail for longer
exposure periods.
Although the uncoupled potential of the tube could eventually
reach the Eoc of bare tube for galvanic coupling periods longer than
84 h (illustrated schematically by the green arrow in Fig. 20), the
Fig. 18. Image of a single fin joint to the tube under immersion conditions in uncoupled potential for the fins is expected to remain approxi-
SWAAT solution, showing bubbles in the fin corresponding to hydrogen evolution. mately constant or slightly shift to less negative values. This means
that the potential difference between components and Ig are
is expected to shift to less negative values as the thickness of the expected to decrease further. The presence of corrosion products
zinc sacrificial layer decreases (following a similar trend as that has also the effect of decreasing the rate of galvanic corrosion. If
observed for Eoc of the mini-core sample immersed in SWAAT solu- the difference of uncoupled potentials tends to zero, the tube
tion, Fig. 8). In other words, with increasing time of galvanic cou- would still be corroding in a nearly uniform manner as the sacrifi-
pling the cathode (fins) becomes less polarized. Nonetheless, the cial zinc layer continues to dissolve. It is conceivable that after a
uncoupled potential of the fins does not remain constant. As shown certain long galvanic coupling period the uncoupled potential of
in Fig. 20 it experiences a shift of 45 mV. This is most likely due dis- the tube could become less negative than that of the fins (resulting
solution of the oxide film and a slight corrosion of the fins. in a polarity reversal) and at that stage the fins will start exhibiting
anodic behavior, protecting the remaining tube material. In this
Corrosion protection method way the perforation of the tube would be prevented at all times.
This suggest that the condenser designed in this project can con-
The results presented in the previous section show that even ceivably have a combined protection mechanism working in two
after 84 h of galvanic coupling the microchannel tubes are still stages (first by the zinc diffusion layer and later by the sacrificial

Fig. 19. Galvanic current as a function of time measured in a mini-cell containing a small tube sample coupled to two fins as shown in Fig. 3(b).
 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777 1775

Fig. 20. Variations of uncoupled potentials for tube and fins as a consequence of galvanic coupling during 84 h in SWAAT solution. The arrow indicates schematically that the
uncoupled potential of the tube could eventually reach the Eoc of bare tube for galvanic coupling periods longer than 84 h.

Fig. 21. Optical image of the cross-section of a microchannel tube after a 24 h galvanic corrosion experiment.
1776 M.A. Pech-Canul et al. / Results in Physics 7 (2017) 1760–1777

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