sensors

Article
Corrosion Measurement of the Atmospheric
Environment Using Galvanic Cell Sensors
Daiming Yang, Hongwei Mei and Liming Wang *
Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China;
ydm15@mails.tsinghua.edu.cn (D.Y.); mei.hongwei@sz.tsinghua.edu.cn (H.M.)
* Correspondence: wanglm@sz.tsinghua.edu.cn




Received: 16 December 2018; Accepted: 11 January 2019; Published: 15 January 2019


Abstract: An atmospheric corrosion monitor (ACM) is an instrument used to track the corrosion
status of materials. In this paper, a galvanic cell sensor with a simple structure, flexible parameters,
and low cost was proposed for constructing a novel ACM, which consisted of three layers: the upper
layer was gold, used as the cathode; the lower layer was corroded metal, used as the anode; and the
middle layer was epoxy resin, used to separate the cathode and anode. Typically, the anode and epoxy
resin were hollowed out, and the hollow parts were filled with electrolyte when it was wet to form a
corrosive galvanic cell. Specifically, the corrosion rate was obtained by measuring the short circuit
current of the cell. The sensor was made of a printed circuit board (PCB) or flexible printed circuit
(FPC) and a metal coupon, which allowed for early control of the electrical parameters (including
sensitivity and capacity) and could be combined with various metals. Additionally, the sensor
feasibility was studied in water droplet experiments, during which the corrosive current changed
with the electrolyte evaporation. The sensor practicability was also verified in a salt spray test, and
the electric charge was compared using the thickness loss of bare coupons. A contrast test was also
conducted for the corrosivity of different sensors made of aluminum, iron and copper.

Keywords: corrosion evaluation; atmospheric corrosion monitor (ACM); galvanic cell sensor;
salt spray test

1. Introduction
The assessment of the environment in which outdoor equipment with metal shells operate has
attracted great interest in the fields of electronics, petroleum, and transportation [1–3]. However, metal
equipment can easily be corroded in humid air, and the development of corrosion is reported to be
related to the material species and the atmosphere [4,5].
Galvanic corrosion, a typical phenomenon that takes place in alloys or in the joints of different
metals, is driven by the electrode’s potential difference between the corroded metal and the other
conductors, including other metals or carbon [6]. Notably, the corroded metal is more active, with a
low reversible potential and is used as the anode, while the other conductor serves as the cathode. Both
are connected to each other to form a circuit loop, of which one part is the ion current in the electrolyte
and the other part is the electron flow through the metal conductors. To be specific, a primary cell
is constituted of two different metals or alloys covered by the electrolyte. Cast iron is a typical cell,
in which iron and carbon act as the anode and cathode, respectively, when its surface is covered with a
thin liquid film, thereby forming a tiny primary cell. The formed cells lead to iron corrosion, finally
resulting in a rust-covered surface.

Sensors 2019, 19, 331; doi:10.3390/s19020331 www.mdpi.com/journal/sensors

Sensors 2019, 19, 331 2 of 11

There are three typical methods to measure galvanic corrosion in the atmosphere: Coupon testing,
electrochemical methods, and atmospheric corrosion monitors (ACM). Of these, a corrosion coupon is
a simple and cost-effective tool used to quantitatively assess the corrosion rate of a particular metal
in an outdoor environment. However, the exposure time may last for 1–20 years, due to the low rate
of the atmospheric corrosion process [7]. Therefore, this test is time-consuming, and may only yield
an annual corrosion rate [8]. Besides, it is impossible to obtain data during this process, such as the
instantaneous rate in rain or fog. In contrast, other methods, including electrochemical impedance
spectroscopy (EIS) [9–11], optical fiber [12,13], and microwave technology [14,15], are used to detect
the corrosion status of metals. Nonetheless, these methods are not suitable for long-term continuous
testing on site, due to their high requirements in terms of equipment. In comparison, ACM is a simple
device that can monitor the galvanic corrosion rate of metals in the atmosphere in real time [16–18].
An ACM is structured with an open galvanic cell in case of wetting; the current follows through the
cell and the anode metal is corroded. In this way, the corrosion rate can be tracked as a function of
time using a single current sensor. Moreover, corrosivity is largely dependent on the thickness of the
humidity layer and the pollutant deposition rate on the material surface.
In this study, traditional ACMs were first used for the corrosion tests. Using traditional ACMs,
however, it was difficult to make the sensors and to maintain the consistency of the parameters.
Moreover, they only allowed for continuous monitoring for days, rather than months. Therefore, this
paper aimed to describe a new type of ACM sensor that was efficient in production and could easily
regulate the sensitivity and capacity. In addition, the corrosivity was characterized through a water
droplet experiment, and the practicability was also verified with the coupon testing results in the salt
spray experiment.

2. Galvanic Cell Sensor

2.1. Galvanic Corrosion

When a metal (M) comes into contact with aqueous electrolyte solutions, an electrochemical
reaction called corrosion occurs at the interface, which leads to deterioration or degradation of the
metal. The metal is oxidized, which means that the metal loses electrons and becomes a metallic ion
(Mz+ ). Galvanic corrosion occurs between different metals connected through a circuit for current
flow. This is driven by their potential difference [19]. Galvanic corrosion is also referred to as contact
corrosion. The noble metal with more positive potential is not the reason for corrosion of the active
metal with more negative potential, but for corrosion acceleration [20].
A galvanic cell, combining iron and gold foil, is shown in Figure 1. The two metals are connected
by an external wire, and an ideal current meter without resistance is added to track the current.
On the other side, the gold foil is insulated from the iron. If electrolytes cover the metals, a short
circuit corrosion cell appears. The iron loses electrons and becomes a ferrous ion (Fe2+ ). These
electrons pass through the current meter to the gold foil. Oxygen dissolved in the electrolyte obtains
the electrons, combines with water, and becomes hydroxyl ions. According to Faraday’s laws of
electrolysis, the mass of a substance dissolved or deposited during electrolysis is proportional to the
quantity of electricity passed.
Sensors 2019, 19, 331 3 of 11
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Sensors 2019, 19, x FOR PEER REVIEW Cathode: O2 + 2H2O + 4e-  4OH- 3 of 11
Gold foil
Insulator Cathode: O2 + 2H2O + 4e-  4OH-
Electrolyte
Gold foil 4OH-
Insulator
2Fe2+ - Electrolyte A
4OH
I
2+2Fe2+ + 4e-
Anode: 2Fe2Fe -A
4e
I
Anode: 2Fe  2Fe2+ + 4e-
4e-

Iron

Figure1.1.Schematic
Figure Schematic galvanic
galvanic corrosion
corrosionofIron
a Fe-Au
of cell.cell.
a Fe-Au

The The
massmass
lossloss
(m)(m)
in in micro grams(mg)
micro
Figuregrams
(mg) is
is
1. Schematic galvanic corrosion of a Fe-Au cell.
𝑀
𝑚 = M∙ 𝑄 = 𝜔 ∙ 𝑄 (1)
The mass loss (m) in micro grams (mg)
m= is 𝑛𝐹 ·Q = ω ·Q (1)
nF
where M is the molar mass of the metal in mg/mol; 𝑀 n is the valency number of ions of the metal; F is
𝑚= ∙𝑄 =𝜔∙𝑄 (1)
where M is the molar mass of the metal in mg/mol; nisis
the Faraday constant with a value of 96500 𝑛𝐹
C/mol; Q the quantity
the valency of number
electricityoforions
charge in C;metal;
of the and F is
ω is
the Faradaythe electrochemical
where M constant with
is the molar equivalent.
a value
mass of the of Q is
96500
metal accumulated by
C/mol;nQisisthe
in mg/mol; current
the (I)
quantity
valency over time. The
of electricity
number ω of
of ions of or iron (Fe-Fe
thecharge
2+)
metal; FinisC; and
is 0.2893 mg/C. The equation ensures the availability of charge for the evaluation of corrosion.
the Faraday constant with a value of 96500 C/mol; Q is the quantity of electricity or charge in C; and 2+
ω is the electrochemical equivalent. Q is accumulated by current (I) over time. The ω of iron (Fe-Fe )
ω is the
is 0.2893 electrochemical
mg/C. equivalent.
The equation ensures Q the
is accumulated
availabilitybyofcurrent
charge(I)for
over
thetime. The ω ofof
evaluation iron (Fe-Fe2+)
corrosion.
2.2. Sensor Structure
is 0.2893 mg/C. The equation ensures the availability of charge for the evaluation of corrosion.
2.2. Sensor Based on the galvanic corrosion principle above, we designed a corrosion sensor, namely a
Structure
2.2. Sensorcell.
galvanic Structure
The sensor is shown in Figure 2. The gold-plated epoxy resin plate, which was hollowed
Based
with onslots,
five the was
galvanic
adhered corrosion principle
to the surface of the above,
corrodedwemetal
designed
plate. a corrosion
The periphery sensor, namely a
of namely
the epoxy
Based on the galvanic corrosion principle above, we designed a corrosion sensor, a
galvanic
boardcell.
wasThe sensorwith is shown in Figure 2. Thethe
gold-plated epoxy resin plate, whichThe wasentire
hollowed
galvanic cell.filled
The sensorsilicone
is shown rubber to prevent
in Figure external epoxy
2. The gold-plated metal from
resin being
plate, corroded.
which was hollowed
withsensor
five slots,
was was adhered
placed to the surface of thegold-plated
corroded metal plate. The periphery of plate
the epoxy
with five slots, wasin a plastic
adhered tocontainer,
the surface and
of the layerplate.
the corroded metal was connected
The to the
periphery of metal
the epoxy
board bywas
board filled
a wire
was and
filledwith silicone
a current
with meter.
silicone rubber
rubber to preventthe
to prevent theexternal
external metal
metal fromfrom being
being corroded.
corroded. The entire
The entire
sensor waswas
sensor placed in ainplastic
placed container,
a plastic container,and
andthe
thegold-plated layerwas
gold-plated layer wasconnected
connectedto to
thethe metal
metal plate by
plate
a wire and a current meter.
by a wire and a current meter. w = 1.27 mm d = 0.03 mm

Gold plating w = 1.27 mm d = 0.03 mm

Epoxy resin D = 0.05~0.8 mm
Gold plating
Anode metal l = 38.1 mm
Epoxy resin
Silicon rubber D = 0.05~0.8 mm
Anode metal l = 38.1 mm
Container
Silicon rubber

Container
(a) (b)
Figure 2. Component of a galvanic cell sensor (a) and its structure parameters (b).
(a) (b)
To keep the thickness of the epoxy layer uniform and simplify processing, a printed circuit board
Figure
Figure 2. 2. Componentof
Component of aa galvanic
galvanic cell
cellsensor
sensor(a)(a)
and its its
and structure parameters
structure (b). (b).
parameters
(PCB) and flexible printed circuit (FPC) were applied to produce epoxy plates with gold-plated
layers.
To Typically,
keep the thickness theof the epoxy layers ofand
PCBsimplify
is from 0.4 mm to 2.0 mm, and that of FPC
To keep thethe thickness
thickness ofofthe epoxy
epoxy layer
layeruniform
uniform and simplify processing, a printed
processing, circuit
a printed board
circuit board
is smaller,
(PCB) and from about
flexible 0.05
printed mm to
circuit 0.2 mm.
(FPC) The
were literature
applied showed
to produce that the
epoxy insulating
plates medium
with is from
gold-plated
(PCB) and flexible
tens ofTypically,
printed
microns tothe
circuit
hundreds
(FPC) were
of of
microns in size
applied
[16–18].
to produce epoxy
Theisgold-plated
plates
layer was
with
about
gold-plated layers.
layers. thickness the epoxy layers of PCB from 0.4 mm to 2.0 mm, and0.03
thatmm. The
of FPC
Typically, the thickness of the epoxy layers of PCB is from 0.4 mm to 2.0 mm, and that of FPC is smaller,
is smaller, from about 0.05 mm to 0.2 mm. The literature showed that the insulating medium is from
from about 0.05 mm to 0.2 mm. The literature showed that the insulating medium is from tens of
tens of microns to hundreds of microns in size [16–18]. The gold-plated layer was about 0.03 mm. The
microns to hundreds of microns in size [16–18]. The gold-plated layer was about 0.03 mm. The five
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five slots were the same. The width was 1.27 mm and the length was 38.1 mm. They were parallel
five slots were the same. The width was 1.27 mm and the length was 38.1 mm. They were parallel
with an interval
slots were of 2.54
the same. Themm.
width was 1.27 mm and the length was 38.1 mm. They were parallel with an
with an interval of 2.54 mm.
interval of 2.54 mm.
2.3. Key Parameters
2.3. Key Parameters
2.3. Key Parameters
The key parameters of the sensor included sensitivity and capacity. Sensitivity is related to the
The key parameters of the sensor included sensitivity and capacity. Sensitivity is related to the
The key
thickness parameters
of the epoxy boardof the sensor
and included sensitivity
the gold-plated and capacity.
layer, especially Sensitivity
the former. is related
Corrosion will to the
occur
thickness of the epoxy board and the gold-plated layer, especially the former. Corrosion will occur
thickness of the epoxy board and the gold-plated layer, especially the former. Corrosion
and the meter will acquire current only when the liquid film formed on the surface of the sensor links will occur
and the meter will acquire current only when the liquid film formed on the surface of the sensor links
andgold-plated
the the meter will acquire
layer current
and the metalonly when
plate. the liquid
A thicker film
epoxy formed
board on the
needs surface
a thicker of thefilm,
liquid sensor
andlinks
this
the gold-plated layer and the metal plate. A thicker epoxy board needs a thicker liquid film, and this
the gold-plated
results in a lower layer and the of
sensitivity metal
the plate.
sensor.A Four
thicker epoxyformed
sensors board needs
by epoxy a thicker
platesliquid
with film, and
different
results in a lower sensitivity of the sensor. Four sensors formed by epoxy plates with different
this results in a lower
thicknesses—0.05 mmsensitivity
0.14 mm, of themm,
0.23 sensor.
andFour
0.40 sensors
mm—were formedusedbytoepoxy plates
test the with different
sensitivity. They
thicknesses—0.05 mm 0.14 mm, 0.23 mm, and 0.40 mm—were used to test the sensitivity. They
thicknesses—0.05
suffered mm 0.14fog,
from ultrasonic mm,and0.23liquid
mm, and 0.40
films mm—were
formed on theused to testsothe
surface, a sensitivity.
fan was used Theyto suffered
dry the
suffered from ultrasonic fog, and liquid films formed on the surface, so a fan was used to dry the
from ultrasonic
surface. Wet and fog,
dryand liquid films
alternated in aformed
cycle ofon60the
s. surface, so a fancurrent
The changing was used to dry
curves the surface.
shown Wet
in Figure 3
surface. Wet and dry alternated in a cycle of 60 s. The changing current curves shown in Figure 3
and dry alternated
displays the progress in aofcycle of 60 s. Large
corrosion. The changing
values ofcurrent curves
current resultshown in Figure
in a highly 3 displays
sensitive the
sensor.
displays the progress of corrosion. Large values of current result in a highly sensitive sensor.
progress
Therefore,ofthe
corrosion.
thinnerLarge
sensorvalues of current
had higher result in a highly sensitive sensor. Therefore, the thinner
sensitivity.
Therefore, the thinner sensor had higher sensitivity.
sensor had higher sensitivity.

Figure
Figure 3.
3. Sensor
Sensor sensitivity
sensitivity described
described by
by the
the current
current versus
versus the
the thickness
thickness of
of epoxy.
epoxy.
Figure 3. Sensor sensitivity described by the current versus the thickness of epoxy.
The capacity is related to the area of the gold-plated layers and the perimeter of the slots. A large
The capacity is related to the area of the gold-plated layers and the perimeter of the slots. A large
capacity means greater
greater metal
metal loss
loss during
during corrosion,
corrosion, or or that
that the
the electric
electric charge
charge and
and current
currentisislarger.
larger.
capacity means greater metal loss during corrosion, or that the electric charge and current is larger.
Assuming that the sensor is completely wet and that the electrode reaction rate is determined by the
Assuming that the sensor is completely wet and that the electrode reaction rate is determined by the
oxygen diffusion rate, the capacity
capacity is proportional
proportional to to the area of the gold-plated layer, as shown in
oxygen diffusion rate, the capacity is proportional to the area of the gold-plated layer, as shown in
Figure 4a.
4a. In
Inhumid
humidair,
air,where
wherethe theliquid
liquidfilm
film is is
small and
small anddiscrete, thethe
discrete, capacity is proportional
capacity is proportionalto the
to
Figure 4a. In humid air, where the liquid film is small and discrete, the capacity is proportional to the
total circumference
the total of the
circumference slots,
of the as as
slots, shown
shown in in
Figure
Figure4b.4b.ByBythe
theapplication
applicationof ofPCB
PCB andand FPC
FPC design
total circumference of the slots, as shown in Figure 4b. By the application of PCB and FPC design
software, the area of the gold-plated layer and and thethe circumference
circumference of of the
the slots
slots can
can be
be easily
easily achieved.
achieved.
software, the area of the gold-plated layer and the circumference of the slots can be easily achieved.

(a) (b)
(a) (b)
Figure 4. Sensor capacity described by the current versus the area of the gold-plated layer (a) and the
Figure 4. of
Sensor capacity described by the current versus the area of the gold-plated layer (a) and the
number slots (b).
number of slots (b).
Sensors 2019, 19, 331 5 of 11

Figure 4a shows two sensors—one of which has a full-area gold-plated layer and the other with a
half-area silicon rubber layer—immersed in water, with steady-state corrosion currents of about 78 µA
and 34 µA, respectively. The current ratio is 2.3 and close to that of the area. Figure 4b shows two other
sensors—one of which has five slots and the other with three slots—that have been wet by ultrasonic
fog. Tiny water droplets form on the surface, and the temporary steady-state currents are 0.55–0.58 µA
and 0.27–0.35 µA, respectively. The ratio is close to that of the slot.

3. Water Droplet Experiment

3.1. Theoretical Calculation

Conductive water is dropped in the slots of the sensor, and the droplets are connected to the
corroded metal and the gold-plated layer. Oxygen penetrates the droplets into the surface of the
corroded metal or gold-plated layer, and a reduction reaction occurs. Electrons transferred from the
corroded metal to the oxygen are reduced on the gold-plated layer, as determined by the current meter.
Therefore, the galvanic corrosion rate can be obtained from the change of the current.
When the droplet is thick, the diffusion of oxygen in the solution is much slower than the reduction
of oxygen [21], that is, the oxygen is consumed as soon as it reaches the surface of the gold-plated layer.
The corrosion rate is limited by the oxygen diffusion.
Assuming that the diffusion of oxygen in solution satisfies Fick’s first law [22], the diffusion rate
of the oxidant (dmO /dt) is defined as

dmO dc
= − DO · O (2)
dt dx
where the minus sign means that the diffusion direction is opposite to the concentration gradient
(dcO /dx). DO is the diffusion coefficient of the oxidant in the solution. The units of (dmO /dt), (dcO /dx)
and DO are mol/(cm2 ·s), (mol/cm3 )/cm, and cm2 /s, respectively.
It is assumed that the diffusion of oxygen is in a constant state, that is, the diffusion speed at each
point in the diffusion path is equal, and DO is a constant. If the oxygen solubility of the solution in
contact with the air is the oxygen saturation solubility, and the oxygen concentration of the solution
in contact with the gold-plated layer is zero, the oxygen near the gold-plated layer is completely
consumed. The consummation rate of the oxidant can be derived.
dmO c − cOs
= − DO · Oe (3)
dt les

where cOe and cOs are the oxidant concentration at the interface of the electrode and the air, respectively.
les is the thickness of the droplet.
The corrosion current (I) can be described as follows:

dnO
I= · zO · e (4)
dt
dnO dmO
= · A· NA (5)
dt dt
where zO is the electron loss of an oxidant molecule in the reduction reaction. e is electron charge,
1.60 × 10−19 C. (dnO /dt) is the oxidant consummation rate calculated as a molecule number. A is the
area of the gold-plated layer covered by the solution. NA is the Avogadro constant, 6.02 × 1023 C/mol.

3.2. Initial Corrosion

To verify the calculation, a droplet of high-conductivity salt water of 20 µL was added to a
corrosion sensor of D = 0.05 mm. The shape of the water droplet and the corrosion current curve are
shown in Figure 5. Assuming that the water droplet was cuboid initially, the thickness of the solution
Sensors 2019, 19, 331 6 of 11

and the area

Sensors of19,
2019, the gold-plated
x FOR PEER REVIEWlayer covered by the solution can be obtained, and the parameters
6 of 11 in
Table 1 are substituted into (3)–(5) to calculate the theoretical maximum value of the initial corrosion
current.
current. TheThe calculation
calculation valuewas
value was63
63µA,
μA,on
on the
the same
sameorder
orderofofmagnitude
magnitudeas the measurement
as the in in
measurement
Figure 5.
Figure 5.

Figure 5. Salt water droplet on the sensor surface and the initial corrosion current.
Figure 5. Salt water droplet on the sensor surface and the initial corrosion current.
Table 1. Parameters for calculation of the maximum initial current.
Table 1. Parameters for calculation of the maximum initial current.
Parameter
Parameter Value
Value Unit
Unit
DODO 1.9×× 10
1.9 10−−55
cmcm
2 /s2 /s
cOe cOe 0 mol/cm 3
mol/cm 3

cOs cOs 1.38 × 10 − 6 mol/cm 3

1.38 × 10 −6 mol/cm 3

les les 55×× 10 −2

10−2 cmcm
zO zO 44 - -2
A 3.2 × 10−−11
A 3.2 × 10 cmcm2

The experimental
The experimental curve
curve showsthat
shows thatthe
the initial
initial corrosion
corrosioncurrent
currentwas about
was 20 μA,
about which
20 µA, was was
which
significantly lower than the theoretical maximum value. The causes of the difference
significantly lower than the theoretical maximum value. The causes of the difference include include the the
following: the corrosion rate is not only related to the oxygen diffusion rate, but also affected by the
following: the corrosion rate is not only related to the oxygen diffusion rate, but also affected by the
cathode over potential; the discharge process of the charged particles through the electric double
cathode over potential; the discharge process of the charged particles through the electric double layer
layer is not easy; and the reaction is affected by the discharge process.
is not easy; and the reaction is affected by the discharge process.
3.3. Complete Process
3.3. Complete Process
As shown in Figure 5, the corrosion current increases because of the evaporation of the droplet.
As shown in Figure
To investigate 5, the
the whole corrosion
corrosion current
process, increases because
low-conductivity water wasof the evaporation
applied of the droplet.
for the experiment.
To investigate
As time wenttheon,
whole corrosion
the droplet process,
thinned until itlow-conductivity
disappeared. Figurewater was applied
6 illustrates for the
the change of a experiment.
droplet
As time went on, the droplet thinned until it disappeared. Figure 6 illustrates the change of a250
(5 μL) on a sensor of D = 0.4 mm, and the corresponding current curve. Photos were taken every droplet
(5 µL)s, on
andathe pointsofwhen
sensor D = the
0.4photos werethe
mm, and taken were marked on
corresponding the curve.
current When
curve. corrosion
Photos began,
were takentheevery
250 s,current
and theincreased as the thickness
points when the photosof the water
were takenthinned,
werewhen
markedles decreased. WhenWhen
on the curve. A reduced, the film
corrosion began,
on the gold-plated layer disappeared and the current dropped sharply, but not to zero. Finally, the
the current increased as the thickness of the water thinned, when les decreased. When A reduced,
current decreased slowly to zero.
the film on the gold-plated layer disappeared and the current dropped sharply, but not to zero. Finally,
the current decreased slowly to zero.
Sensors 2019, 19, x FOR PEER REVIEW 7 of 11
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Sensors 2019, 19, x FOR PEER REVIEW 7 of 11
(1) (2) (3) (4)

(1) (2) (3) (4)

(5) (6) (7) (8)

(5) (6) (7) (8)

(9) (10) (11) (12)

(9) (10) (11) (12)

(a) (b)
Figure 6.(a) (b)(b).
Change of a droplet on a sensor (a) and its current curve

Figure 6. Change
Figure 6. Change of
of aa droplet
droplet on
on aa sensor
sensor (a)
(a) and
and its
its current
current curve
curve (b).
(b).
Wider droplets were applied for further tests. The current curves are displayed in Figure 7.
Channel Wider1 was filled with a droplet about twice the sizeThe of that in channel
curves2.areThedisplayed
larger droplet led to7.
Wider droplets
droplets werewere applied
applied for for further
further tests. current
tests. The current curves are displayed in in Figure
Figure 7.
aChannel
larger maximum current, and its current lasted for a longer time. Compared with the curve in Figure
Channel11was wasfilled
filledwith
withaadroplet
dropletabout
abouttwice
twicethethesize
sizeofofthat
thatininchannel
channel2.2.The
Thelarger
larger droplet
droplet ledled
toto
a
6,larger
thosemaximum
in Figure current,
7 are more and complicated.
its current Afterfor
lasted thea droplets
longer wetCompared
time. the sensors, thethe
with currents
curve increased
in Figure 6,
a larger maximum current, and its current lasted for a longer time. Compared with the curve in Figure
slowly
those and
in synchronously
Figure 7 are more tocomplicated.
the maximumAfter values. The evaporation of water made the film thin, but
6, those in Figure 7 are more complicated. Afterthe thedroplets
dropletswet wetthethesensors,
sensors,thethecurrents
currents increased
increased
the wetting
slowly area on the gold-plated layer kept constant or changed little. This led to constant contact
slowly andand synchronously
synchronously to to the
the maximum
maximum values.
values. The
The evaporation
evaporation of of water
water made
made the the film
film thin,
thin, but
but
area
the evaporation,
wetting area or the
on “pinning”
gold-plated [23].layer
Then,kept
the constant
dropletsor shrunk,
changed and the This
little. angleledremained
to constant steady or
contact
the wetting area on the gold-plated layer kept constant or changed little. This led to constant contact
even
area increased, that is, constant contact angle evaporation, or “de-pinning”. For a larger water
area evaporation,
evaporation,oror“pinning”
“pinning” [23]. Then,
[23]. Then,thethe
droplets
dropletsshrunk,
shrunk,andandthe angle remained
the angle remainedsteady or even
steady or
droplet,
increased, thethat
“pinning”
is, and contact
constant “de-pinning”
angle steps wouldoralternate
evaporation, until the
“de-pinning”. For droplet
a larger was
water dry. This
droplet,
even increased, that is, constant contact angle evaporation, or “de-pinning”. For a larger water
phenomenon
the “pinning” could be used for the
and “de-pinning” detection
steps would of the wetting
alternate until and corrosion
the droplet status under wetting by
droplet, the “pinning” and “de-pinning” steps would alternate until was
the dry. Thiswas
droplet phenomenon
dry. This
droplets.
could be used could
for thebe detection
phenomenon used forofthe thedetection
wetting andof thecorrosion
wettingstatus under wetting
and corrosion statusbyunderdroplets.
wetting by
droplets.

Figure 7. Comparison of two current curves under wetting by two wider droplets.
Figure 7. Comparison of two current curves under wetting by two wider droplets.
4. Salt Spray Figure
Test 7. Comparison of two current curves under wetting by two wider droplets.
4. Salt Spray Test
4.1. Experiment Platform
4. Salt Spray Test
4.1. Experiment Platform
The test was carried out in accordance with IOS 9227 [24]. The platform is shown in Figure 8.
4.1. Experiment
The
Three slopestest was Platform
were carried
set in out in accordance
the salt at 30◦IOS
spray box with , 45◦9227 60◦ The
, and[24]. fromplatform is shown
the horizontal in Figure
plane, and two8.
Three slopes
corrosion wereofset
sensors D in themm
= 0.4 salt sprayplaced
box at 30°, 45°, and 60°pieces
from theiron
horizontal plane, and
weretwo
The test was carried out inwere
accordanceon each
with IOSslope.
9227Six[24]. Theofplatformcoupons, which
is shown in Figurethe
8.
corrosion
same sensors
material as of D
the = 0.4 mm
sensors, werewere placed on
suspended each slope.
vertically in the Six
box.pieces
The of iron coupons,
coupons were 50 which
mm × 25were
mm
Three slopes were set in the salt spray box at 30°, 45°, and 60° from the horizontal plane, and two
the
× 2same
mm.material
The as thecontained
solution sensors, were suspended vertically in the box. and
The industrial
coupons were 50 mm ×
corrosion sensors of D = 0.4 mm NaClwere and NaHSO
placed 3 , simulating
on each slope. Six ocean
pieces of iron environments.
coupons, which were
25
Themm × 2 mm. inside
temperature The solution contained ◦
35 NaCl and
theNaHSO 3, simulating ocean was ◦ C.
and47industrial
the same material as thethe chamber
sensors, wassuspended
were C, and temperature
vertically of the
in the box. Thesolution
coupons were 50 mm ×
environments. The temperature
Salt ×fog2 was frominside the chamber was air35 °C, and the temperature ofhigh
the solution
25 mm mm.generated
The solution the solution
contained when and
NaCl an compressor
NaHSO was subjected to pressure.
3, simulating ocean and industrial
was
Fog 47 °C. the chamber uniformly via atomizers.
filled
environments. The temperature inside the chamber was 35 °C, and the temperature of the solution
was 47 °C.
Sensors
Sensors 2019,
2019, 19,
19, x
x FOR
FOR PEER
PEER REVIEW
REVIEW 88 of
of 11
11

Salt fog was generated from the solution when an air compressor was subjected to high pressure.
SensorsSalt fog
2019, 19,was
331 generated from the solution when an air compressor was subjected to high pressure.
8 of 11
Fog
Fog filled the chamber uniformly via
filled the chamber uniformly via atomizers.
atomizers.

Coupons
Coupons

Air
Air Compressor
Compressor

Chamber
Chamber Atomizer
Atomizer

Solution
Solution of
of NaCl
NaCl and
and
NaHSO
NaHSO3 3

Sensors DAQ
DAQ
Sensors
Figure
Figure 8.
8. Platform
Platform and
Platform and layout
layout of
of the
the salt
salt spray
spray test.
test.

In
In the
the experiment,
experiment, both
both the
the coupons
coupons andand the
the sensors
sensors were
were corroded.
corroded. The
The coupons
coupons lost
lost iron
iron and
and
rust formed
rust formed
formed onon the
onthe surface.
thesurface. The
surface.The rust
Therust was
rustwas cleaned
wascleaned
cleaned using
using aa rust
a rust
using remover,
remover,
rust which
which
remover, waswas
which aa kind
a kind
was of
of solvent
of solvent
kind that
solvent
that
that dissolved the rust but not the iron. Therefore, the weight loss of the coupons during the
dissolved
dissolved the the
rust rust
but notbut
the not
iron.the iron.
Therefore, Therefore,
the the
weight weight
loss of loss
the of
couponsthe coupons
during the during
experimentthe
experiment
experiment could
could be
could be obtained. be obtained.
The sensors The
obtained. weresensors
The linked to
sensors were linked
a data
were to
to aa data
acquisition
linked acquisition
data(DAQ) system
acquisition (DAQ)
to track
(DAQ) system to
to track
the corrosion
system track
the corrosion
currents
the currents
currents and
and calculate
corrosion calculate
calculate the
the charges.
and the charges.
charges.

4.2. Charge–Thickness Loss

4.2. Charge–Thickness
Charge–Thickness Loss
The
The coupons
coupons werewere taken
taken out for weighing,
out for weighing, and and the
the weight
weight loss
loss was
was calculated.
calculated. The
The experiment
experiment
lasted about 36 h, and two coupons were weighed every 12 h.
lasted about 36 h, and two coupons were weighed every 12 h. The weighed coupons were
The weighed coupons
coupons were not
not put
put
back into the
back into
into thechamber.
the chamber.The
chamber. Thethickness
The thicknessloss
thickness loss
loss ofof
of thethe
the coupons
coupons
coupons was
waswas calculated
calculated
calculated based
based
based on on the
on the
the weight
weight
weight loss,loss,
loss, the
the
the surface
surface area, area,
and and
the the density
density of of
the the
iron. iron.
The The relationship
relationship between
between electric
electric charges
charges of
surface area, and the density of the iron. The relationship between electric charges of the sensors and of
the the sensors
sensors and
andthickness
the
the the thickness
thickness losses
losseslosses
of
of the
theofcoupons
the coupons
coupons is is displayed
is displayed
displayed in in Figure
in Figure
Figure 9. 9.
9.

The relationship between

Figure 9. The
Figure between the electric
electric charges of
of the sensors
sensors and the
the thickness losses
losses of the
the
Figure 9.
9. The relationship
relationship between the
the electric charges
charges of the
the sensors and
and the thickness
thickness losses of
of the
coupons
coupons in salt spray tests.
coupons inin salt
salt spray
spray tests.
tests.
Sensors 2019, 19, 331 9 of 11
Sensors 2019, 19, x FOR PEER REVIEW 9 of 11

In Figure
In Figure 9,9, the
thethickness
thicknessloss
lossand thethe
and charge increased
charge increasedas the testing
as the timetime
testing progressed. The
progressed.
corrosion
The ratesrates
corrosion of theofsensors at different
the sensors anglesangles
at different were basically synchronized.
were basically A largerAangle
synchronized. seemed
larger angle
to cause a slower rate, which might be due to a thicker film covering the sensor. In the
seemed to cause a slower rate, which might be due to a thicker film covering the sensor. In the early early stage of
the corrosion,
stage the change
of the corrosion, the of electric
change of charge
electricon the proposed
charge sensor reflected
on the proposed a good linear
sensor reflected a goodgrowth,
linear
which also
growth, applied
which to the on-site
also applied to thedetection of the atmospheric
on-site detection corrosion
of the atmospheric rate.
corrosion rate.

4.3. Material Types

Types
Different
Different metal
metalmaterials
materialswere
wereused
usedtotomake
make thethe
sensors, including
sensors, aluminum
including aluminum(Al),(Al),
iron iron
(Fe), (Fe),
and
copper (Cu).(Cu).
and copper The corrosivity of the
The corrosivity ofsensors
the sensorsbased on these
based corroded
on these metals
corroded was was
metals compared
comparedby aby salta
spray experiment.
salt spray experiment.
According
According toto the
the standard
standard potential (E00) against the standard hydrogen electrode
potential (E electrode (SHE)
(SHE) for metal
0
reduction, the EE for 2+ −1.622V, −0.440V,
0 for aluminum,
aluminum, iron
iron (Fe /Fe), and
(Fe /Fe),
2+ and copper
copper are
are −1.622 V, −0.440 V, and
and +0.337
+0.337 V, V,
respectively.
respectively. The
The standard
standardpotential
potentialfor
foroxygen
oxygen(O (O2 /OH − is+0.401
2/OH−) )is +0.401V.
V. Mathematically,
Mathematically, the standard
potentials
potentials for
for the
the galvanic
galvanic cell
cell sensors
sensors made
made by by different
differentmetals
metalsare
are
Al − O : 𝐸 0 = 𝐸 0 − 𝐸 0 = 2.023 V (6)
Al − O2 : Ecell = EO2 − EAl = 2.023 V (6)

Fe − O : 𝐸 0 = 𝐸 0 − 𝐸 0 = 0.841 V (7)
Fe − O2 : Ecell = EO2 − EFe = 0.841 V (7)

CuCu−−OO (8)
2 :: 𝐸
0 = 𝐸 0 − 𝐸 0 = 0.064 V
Ecell = EO2 − ECu = 0.064 V (8)

All of the cell potentials are positive, which means that corrosion
corrosion will occur in
in aqueous
aqueous solutions.
solutions.
Therefore, the metals could be corroded in salt spray experiments.
Therefore, the metals could be corroded in salt spray experiments. The corrosion current and charge
are illustrated
are illustrated in
in Figure
Figure 10.
10.

(a) (b)
10. Corrosion currents (a) and electric charges (b) of sensors
Figure 10. sensors made
made of
of aluminum,
aluminum, iron, and
and
copper in salt spray tests.
in salt spray tests.

The
The corrosion
corrosion rates,
rates, expressed
expressed in in current,
current, were
were positively
positively associated
associated withwith the
the cell
cell standard
standard
potentials. Among the
potentials. Among the three
three metals,
metals, aluminum
aluminum was was the
the most
most corrosive
corrosive and and copper
copper waswas the
the least
least
corrosive.
corrosive. The corrosion rate of copper was far behind that of the others. At about 60 h, the fog
The corrosion rate of copper was far behind that of the others. At about 60 h, the fog
stopped
stopped being
being generated,
generated, but but the
the sensors
sensors remained
remained in in the
the chamber
chamber for for corrosion.
corrosion. AsAs soon
soon as
as the
the fog
fog
stopped,
stopped, the
the corrosion
corrosion of of iron
iron and
and copper
copper slowed
slowed down.
down. The aluminum, however,
The aluminum, however, kept
kept the
the same
same rate
rate
for
for about
about 2020 h.
h. It
It is
is well
well known
known thatthat aluminum
aluminum formsforms anan oxide
oxide film
film or or passivation
passivation film
film in
in the
the air
air to
to
cover
cover the
the surface
surface and
and prevent
prevent further
further corrosion.
corrosion. AtAt the
the beginning
beginning of of the
the test,
test, the
the formation
formation of of the
the
oxide
oxide film
film suppressed
suppressed the the corrosion
corrosion rate.
rate. The
The electrochemical
electrochemical reaction
reaction rate
rate was
was mainly
mainly limited
limited by by the
the
anodic reaction. Iron and copper did not form a passivation film, and during the
anodic reaction. Iron and copper did not form a passivation film, and during the fogging they were fogging they were in
sufficient contact
in sufficient withwith
contact the electrolyte. The reaction
the electrolyte. rate was
The reaction ratemainly limitedlimited
was mainly by the diffusion of oxygen
by the diffusion of
in the cathode. When the fogging stopped, the electrolyte on the surface of the
oxygen in the cathode. When the fogging stopped, the electrolyte on the surface of the sensor wassensor was lost, and the
effective
lost, andarea
the of the galvanic
effective area cell wasgalvanic
of the reduced.cell
Meanwhile,
was reduced.the amount
Meanwhile,of oxygen
the participating
amount of oxygen in the
participating in the cathodic reaction was reduced, and the corrosion rate decreased. The reduction
of oxygen just after the fog stopping had little effect on the corrosion rate of aluminum.
Sensors 2019, 19, 331 10 of 11

cathodic reaction was reduced, and the corrosion rate decreased. The reduction of oxygen just after the
fog stopping had little effect on the corrosion rate of aluminum.
The proposed sensor can be used to assess the corrosion rate of wet metal surfaces in the
atmosphere. The rate is related to the form of wetting, including droplet and film, for which the
sensor can measure the corrosivity. The sensor is easy to fabricate by simply attaching a gold-plated
PCB or FPC to the surface of the corroded metal, and tracking the corrosion current through a current
meter to estimate the corrosion rate. This is a generally applicable method. The sensor can be combined
with an embedded DAQ module to create an atmospheric corrosion monitor for long-term, outdoor,
or metal corrosion monitoring.

5. Conclusions
Based on the principle of galvanic corrosion, a new type of galvanic cell sensor was proposed.
The sensors were fabricated using gold-plated PCB or FPC processes. The relationship between the
thickness of the insulation layer and the sensitivity of the sensor was studied. The relationship between
the area of the gold-plated layer, the length of the slots, and the capacity of the sensor was also studied.
Through the water droplet experiment, the corrosion rate was obtained during the evaporation
of the droplet on the sensor surface. The corrosion rate was restricted by the diffusion of oxygen in
the cathode. As the droplet evaporated and thinned, the corrosion current first increased, and then
decreased. A droplet with a larger area led to a larger maximum corrosion current. The curve of the
corrosion current reflected the pinning and de-pinning phenomena of the water evaporation process.
Through the salt spray test, the electric charge of the sensors and the thickness loss of the metal
coupons were compared. In the early stage of corrosion, the sensor showed a good linear development
trend, and was suitable for the on-site monitoring of metal corrosion.
Sensors made of different metals—aluminum, iron and copper—were compared in a salt spray
test. The corrosion rates of the three metals were found to be related to the standard potentials of the
cells. The larger the electrode potential, the faster the corrosion rate. At the same time, the passivation
film suppressed the corrosion by slowing down the anodic reaction. Therefore, the sensors made of
different metals exhibited different corrosion trajectories in the test.

Author Contributions: Conceptualization, H.M. and L.W.; methodology, D.Y.; validation, H.M. and D.Y.; formal
analysis, D.Y.; investigation, H.M.; writing—original draft preparation, D.Y.; writing—review and editing, H.M.
and L.W.; project administration, L.W.; funding acquisition, L.W.
Funding: This research was funded by National Key Research and Development Program of China, grant
number 2017YFB0902702.
Conflicts of Interest: The authors declare no conflict of interest.

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