materials

Article
Effect of Zinc Phosphate on the Corrosion Behavior of
Waterborne Acrylic Coating/Metal Interface
Hongxia Wan 1 , Dongdong Song 1,2, *, Xiaogang Li 1,3, *, Dawei Zhang 1 , Jin Gao 1 and Cuiwei Du 1
1 Institute for Advanced Materials and Technology, University of Science and Technology Beijing,
Beijing 100083, China; wanhongxia88@163.com (H.W.); dawzhang@126.com (D.Z.); g.jin@163.com (J.G.);
dcw@ustb.edu.cn (C.D.)
2 Aerospace Research Institute of Materials and Processing Technology, Beijing 100076, China
3 Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences,
Ningbo 315201, China
* Correspondence: sddtheone@126.com (D.S.); lixiaogang99@263.net (X.L.);
Tel.: +86-010-68383576 (D.S.); +86-010-62333931 (X.L.)

Academic Editor: Yong-Cheng Lin

Received: 22 April 2017; Accepted: 30 May 2017; Published: 14 June 2017

Abstract: Waterborne coating has recently been paid much attention. However, it cannot be used
widely due to its performance limitations. Under the specified conditions of the selected resin,
selecting the function pigment is key to improving the anticorrosive properties of the coating.
Zinc phosphate is an environmentally protective and efficient anticorrosion pigment. In this work,
zinc phosphate was used in modifying waterborne acrylic coatings. Moreover, the disbonding
resistance of the coating was studied. Results showed that adding zinc phosphate can effectively
inhibit the anode process of metal corrosion and enhance the wet adhesion of the coating, and
consequently prevent the horizontal diffusion of the corrosive medium into the coating/metal
interface and slow down the disbonding of the coating.

Keywords: waterborne acrylic coating; zinc phosphate; LEIS

1. Introduction
Serious environment problems have directed attention toward water-based coatings because of
their low volatile organic compounds VOC advantages [1–3]. However, waterborne coatings have
performance limitations; moreover, they have been extensively used indoors, where the corrosion
environment is below the C3 level [4]. Thus, waterborne coatings need to have improved performance
for long-term applications [5–8]. Acrylic coatings have good barrier properties and ageing resistance,
which has attracted much attention [9,10]. Disbonding is the first sign of coating/metal interface
corrosion [11–14], which is the most common form of failure that limits coatings, especially for
long-term applications of waterborne coatings [15]. Hence, the ability to resist disbonding characterizes
the coating service life, which is the main purpose for developing long-lasting water-based coatings
suited for harsh environments [16]. Traditional coatings would exhibit significant cathodic disbonding
under different environments that would affect the coating service life. Adding an electrochemically
active antirust pigment is a common method for improving the antirust capacity of the coating [17,18].
Therefore, the effect of an electrochemically active antirust pigment on the cathodic disbonding process
when added into a waterborne acrylic coating is significant.
Much attention has been given to phosphate antirust pigments for their relative environmental
protection [19–23]. Phosphate pigments mainly contain aluminum tripolyphosphate [24] and zinc
phosphate [25]. The antirust function and mechanism of zinc phosphate have been previously studied.
Bethencourt et al. [26] studied the failure process of a waterborne acrylic zinc phosphate coating using

Materials 2017, 10, 654; doi:10.3390/ma10060654 www.mdpi.com/journal/materials

Materials 2017, 10, 654 2 of 13

electrochemical impedance spectroscopy (EIS). The corrosive failure of composite coatings in 3.5%
NaClMaterials
solution were divided into three stages: the first stage is the water diffusion stage,2 of
2017, 10, 654
wherein
13
the coating impedance decreases; the second stage involves the zinc phosphate coming in contact
with coatings
water, wherein
in 3.5% NaCl a passivation
solution were rustdivided
resistance effectstages:
into three reaches theafirst
certain
stageconcentration
is the water diffusionafter water
stage, wherein
absorption; and the the thirdcoating
stage isimpedance
the start ofdecreases;
the shieldingthe second
declinestage afterinvolves
the zinc the zinc phosphate
phosphate is exhausted.
Yaweicoming
Shao in al.
et
Materials contact
10, 654with
[27,28]
2017, water,the
studied wherein
corrosiona passivation
inhibitionrust of zincresistance
phosphateeffect inreaches 2a
an oil-based certainepoxy
of 13
concentration
coating using after water absorption;
EIS and electrochemical and the
noise, third
and threestage
showed is the
thatstart of the
zincstage shielding
phosphate decline
provides after the
a recovery
coatings in 3.5%
zinc phosphate NaCl solution
is exhausted. were Shao
Yawei divided etinto
al. [27,28] stages: the first
studied is the water
the corrosion diffusion
inhibition of zinc
effect for coating defects.
stage, wherein theCurrently, researchers
coating impedance [29] found
decreases; the secondthatstage
when the corrosive
involves the zinc medium
phosphate permeates
phosphate in an oil-based epoxy coating using EIS and electrochemical noise, and showed that zinc
the oil-based
comingepoxy in coating/metal
contact with water, interface,
whereinzinc phosphate
a passivation partly
rust dissolves
resistance effect and forms
reaches metal substrate
a certain
phosphate provides a recovery effect for coating defects. Currently, researchers [29] found that when
phosphate concentration
and after the
stabilizes water absorption;film,
protective and the third stage
which is the start
contains γ-Fe ofOthe, shielding
α-FeOOH, decline after the and iron
γ-FeOOH,
the corrosive medium 2 3
zinc phosphate is permeates the oil-based
exhausted. Yawei Shao et epoxy coating/metal
al. [27,28] studied the interface,
corrosion zinc phosphate
inhibition of zincpartly
phosphate.
dissolves Moreover,
and forms the protective
metal substrate film contains
phosphate and carboxyl
stabilizes andthe hydroxyl
protective
phosphate in an oil-based epoxy coating using EIS and electrochemical noise, and showed that zinc
groups
film, that
which enhance the
contains
combination
γ-Fe2O , of coating
α-FeOOH, and
γ-FeOOH, metal.
and Some
iron researchers
phosphate. [30]
Moreover, have
the proposed
protective
phosphate provides a recovery effect for coating defects. Currently, researchers [29] found that when
3 that
film zinc
contains phosphate
carboxyl can
formand
stabletheiron
hydroxyl phosphates
corrosive medium
groups and block
that permeates
enhance themedium
the oil-based diffusion
combination epoxy intoand
ofcoating/metal
coating theinterface,
channels
metal. zinc
Some and slow down
phosphate
researchers [30] corrosion.
partly have
However, dissolves
proposedthe that and
zincof
effects forms
zincmetal
phosphate substrate phosphate
can formactive
phosphate and
stable fillers
iron stabilizes
phosphates
on the
andprotective
the waterborne block mediumfilm, which
acrylic contains
diffusion
cathodic into the
disbonding
γ-Fe2and
channels O3, α-FeOOH,
slow down γ-FeOOH, and iron
corrosion. phosphate.
However, the Moreover,
effects ofthe protective
zinc film contains
phosphate active carboxyl
fillers on the have
process, especially involving the interface corrosion mechanism of cathodic and anodic processes,
and hydroxyl groups that enhance the combination of coating and metal. Some researchers [30] have
waterborne
not been acrylic cathodic
comprehensively studied.disbonding process, especially involving the interface corrosion
proposed that zinc phosphate can form stable iron phosphates and block medium diffusion into the
mechanism of cathodic and anodic processes, have not been comprehensively studied.
In this paper,and
channels weslowstudied
down the coating/metal
corrosion. However, the interface
effects ofcorrosion
zinc phosphate process
activeof waterborne
fillers on the acrylic
In this paper,
waterborne we studied
acrylic cathodic the coating/metal interface corrosion process of waterborne
corrosionacrylic
coatings with zinc phosphate usingdisbonding process,
EIS and localized especially
EIS (LEIS). involving the interface
Furthermore, we studied the effects
coatings with zinc
mechanism phosphate
of cathodic andusing
anodicEIS and localized
processes, have notEIS been(LEIS). Furthermore,
comprehensively we studied the effects
studied.
of active pigments
of active pigments
In
on on
this paper,
coating/metal
coating/metal
we
interface corrosion
interface corrosion
studied the coating/metal interface and
anddisbonding
corrosion
disbonding
process of
processes
processes
waterborne
in waterborne
in waterborne
acrylic
acrylic coatings.
acryliccoatings
coatings. with zinc phosphate using EIS and localized EIS (LEIS). Furthermore, we studied the effects
of active pigments on coating/metal interface corrosion and disbonding processes in waterborne
2. Resultsacrylic coatings.
2. Results

2.1. The 2. Results

2.1. Coating Adhesion
The Coating Test
Adhesion Test
Figure 2.1.1 The
Figure 1Coating
shows showstheAdhesion
adhesion
the Test values
adhesion valuesof
of0%0% and 8%zinc
and 8% zincphosphate
phosphate coatings.
coatings. TheThe adhesion
adhesion values values
werewere the same
the same in1 shows
in the
Figure the
0%0% and and
the 8%8% zinc
zinc
adhesion phosphate
phosphate
values coatings.
coatings.
of 0% and Adding
Adding
8% zinc phosphate zinc
zincphosphate
phosphate
coatings. did did
The adhesionnot affect the the
not affect
values
initialinitial
coatingcoating
were mechanical
the same
mechanical 0% performance.
in theperformance.
and 8% zincThe The
phosphatecoating fractures
coatings.
coating Adding
fractures after
zinc
after the pull-off
phosphate
the did
pull-off experiments
not affect the areare
experiments shown
shown initial
in coating
Figure 2. mechanical performance. The coating fractures after the pull-off experiments are
in Figure 2.
shown in Figure 2.

Figure 1. The adhesion values of 0% and 8% zinc phosphate coatings.

Figure 1. The adhesion values of 0% and 8% zinc phosphate coatings.
Figure 1. The adhesion values of 0% and 8% zinc phosphate coatings.

Figure 2. The fractures after the pull-off experiments in (a1,a2) 0% and (b1,b2) 8% zinc phosphate
coatings.
Figure 2. The fractures after the pull-off experiments in (a1,a2) 0% and (b1,b2) 8% zinc phosphate
Figure 2. The fractures after the pull-off experiments in (a1 ,a2 ) 0% and (b1 ,b2 ) 8% zinc
coatings.
phosphate coatings.
Materials 2017, 10, 654 3 of 13

Figure 2 shows
Materials the adhesive fracture in the samples without and with 8% zinc phosphate
2017, 10, 654 3 of 13 coating.
The fracture mode for the 8% zinc phosphate coating after the pull-off experiment, which is the mixture
of the coatingFigure
body2 andshows the adhesive
adhesive fracture
interlayer in the samples
fractures, showedwithout
strongand with 8%This
adhesion. zinc result
phosphate
is the same
Materials 2017,
coating. The10, 654
fracture mode for the 8% zinc phosphate coating after the pull-off experiment, which3 of 13
is
with the sample without zinc phosphate coating, only the ratio of the coating body and adhesive
the mixture of the coating body and adhesive interlayer fractures, showed strong adhesion. This
interlayer fractures
resultFigure 2 is
is the same different.
showswiththe
theadhesive fracturezinc
sample without in phosphate
the samples without
coating, and
only thewith
ratio 8% zinc
of the phosphate
coating body
coating.
and The fracture
adhesive mode
interlayer for theis8%
fractures zinc phosphate coating after the pull-off experiment, which is
different.
2.2. Thethe
Coating Morphology
mixture of the coating body and adhesive interlayer fractures, showed strong adhesion. This
result
2.2. TheisCoating
the same with the sample without zinc phosphate coating, only the ratio of the coating body
Morphology
Figure 3 showsinterlayer
and adhesive the scanning electron
fractures microscope (SEM) section of the 8% zinc phosphate coating.
is different.
Figure 3 shows the scanning
Figure 3a shows the secondary electron morphologyelectron microscope
and(SEM) section
Figure of the 8%
3b shows the zinc phosphate
scattering electronic
coating.
2.2. The Figure Morphology
Coating 3a shows the secondary electron morphology and Figure 3b shows the scattering
morphology. The zinc phosphate coating has a homogeneous dispersion and combined with the resin
electronic morphology. The zinc phosphate coating has a homogeneous dispersion and combined
tightly. with
Moreover,
Figure 3adding
the resin shows zinc
tightly. the phosphate
scanning
Moreover, adding did
zincnot
electron show defects.
microscope
phosphate (SEM)
did section
not show of the 8% zinc phosphate
defects.
coating. Figure 3a shows the secondary electron morphology and Figure 3b shows the scattering
electronic morphology. The zinc phosphate coating has a homogeneous dispersion and combined
with the resin tightly. Moreover, adding zinc phosphate did not show defects.

Figure 3. The section morphology of the 8% zinc phosphate coating: (a) secondary electron morphology
Figure 3. The section morphology of the 8% zinc phosphate coating: (a) secondary electron morphology
and (b) back scattering morphology.
and (b) back scattering morphology.
Figure 3.4The
Figure section
shows themorphology of the 8% zinc
macromorphology phosphate
of the coatingcoating: (a) secondary
without and withelectron morphology
8% zinc phosphate in
and (b) back scattering morphology.
3.5% NaCl solution after various immersion days. At the beginning, the 0% and 8% zinc phosphate
Figure 4 shows the macromorphology of the coating without and with 8% zinc phosphate in 3.5%
coating morphologies were the same. However, after two days of immersion, the 0% zinc phosphate
NaCl solution
coating
after
Figure various
4 shows
generated theimmersion
obvious
days. At
macromorphology of the
corrosion. The coating
beginning,
the coating
generated
theand
without
serious
0%corrosion
and 8%
with zincphosphate
8% after
zinc phosphate
four days ofin coating
morphologies
3.5% were
NaCl
immersion, andthethesame.
solution after However,
various
defective after two
immersion
coating bubbled afterdays
days. eight of
At the immersion,
beginning,
days. the thephosphate
0%
In the 8% zinc 0% zinc phosphate
and 8% coating, rust coating
zinc phosphate
coating
generated
occurredmorphologies
obvious
aftercorrosion.
four days were the same.
ofThe coating
immersion However,
and afterafter
generated
increased two days
serious of immersion,
eightcorrosion
days, but no thefour
after 0% zinc
bubbling phosphate
days
was of immersion,
observed.
coating generated obvious corrosion. The coating generated serious corrosion after four days of
and the defective coating bubbled after eight days. In the 8% zinc phosphate coating, rust occurred
immersion, and the defective coatinga bubbled
0% Zn3(POafter
4)2 eight days.
b 8%InZnthe 8%4)zinc
3(PO 2 phosphate coating, rust
after four days of immersion and increased after eight days, but no bubbling was observed.
occurred after four days of immersion and increased after eight days, but no bubbling was observed.

a 0% Zn3(PO4)2 b 8% Zn3(PO4)2
0 day

0 day

1 day

1 day

2 days

2 days

Figure 4. Cont.
Materials 2017, 10, 654 4 of 13
Materials 2017, 10, 654 4 of 13
Materials 2017, 10, 654 4 of 13

4 days
4 days

8 days

8 days

Figure 4. The macromorphology of (a) 0% and (b) 8% zinc phosphate coating scratches with different
Figure 4. The macromorphology of (a) 0% and (b) 8% zinc phosphate coating scratches with different
immersion days.
immersion
Figuredays.
4. The macromorphology of (a) 0% and (b) 8% zinc phosphate coating scratches with different
The microstructures
immersion days. after immersion are shown in Figure 5. The coating defects without zinc
phosphate bubbled in 3.5% NaCl solution after eight days, and that with 8% zinc phosphate did not
The microstructures after immersion are shown in Figure 5. The coating defects without
bubble. These results indicated
The microstructures that the coating
after immersion with zinc
are shown phosphate
in Figure 5. Thecan improve
coating the disbonding
defects without zinc
zinc phosphate bubbled in 3.5% NaCl solution after eight days, and that with 8% zinc phosphate
resistance.bubbled in 3.5% NaCl solution after eight days, and that with 8% zinc phosphate did not
phosphate
did not bubble. These results indicated that the coating with zinc phosphate can improve the
bubble. These results indicated that the coating with zinc phosphate can improve the disbonding
disbonding resistance.
resistance.

Figure 5. Microstructures of coating with (a) 0% zinc phosphate and (b) 8% zinc phosphate immersed
for eight days in 3.5% NaCl solution.

2.3.Figure
The Electrochemical Behavior
5. Microstructures of Zincwith
of coating Phosphate Coating
(a) 0% zinc phosphate and (b) 8% zinc phosphate immersed
Figure 5. Microstructures of coating with (a) 0% zinc phosphate and (b) 8% zinc phosphate immersed
for eight days in 3.5% NaCl solution.
for 2.3.1.
eightMacroscopic
days in 3.5%Electrochemical
NaCl solution.Behavior
2.3. TheFigure
Electrochemical Behavior
6 shows the of Zinc
EIS results Phosphate
of coatings Coating in 3.5% NaCl solution. The drop in the low
immersed
2.3. Thefrequency
Electrochemical Behavior
impedance value of
ofZinc Phosphate
the 0% Coating
zinc phosphate coating indicates the fast corrosion along the
2.3.1. Macroscopic
coating/metal Electrochemical
interface. Behavior impedance value of 0% zinc phosphate coating was
The high-frequency
2.3.1. Macroscopic
reduced afterElectrochemical Behavior
two days of immersion, indicating that the corrosive medium in the coating/metal
Figure 6 shows the EIS results of coatings immersed in 3.5% NaCl solution. The drop in the low
interface was diffused and that disbonding of the coating occurred. However, for the coating with
frequency
Figure impedance
6 shows value
the the
EIS of the of
results 0%coatings
zinc phosphate
immersedcoating
in indicates
3.5% NaClthe solution.
fast corrosionThealongdrop the
8% zinc phosphate, low-frequency impedance value declined within one day of immersion, but in the
coating/metal
low frequency interface.
the valueimpedance The high-frequency
value of the
remained unchanged after0%
onezinc impedance
day.phosphate value of 0%
coatingimpedance
The low-frequency zinc phosphate
indicates value
the fast coating
wascorrosion was
fitted in along
reduced
Figure after
the coating/metal7a. Attwo days of
interface. immersion,
The
the beginning, high-frequency
the indicating
low-frequency that thevalues
impedance
impedance corrosive
value themedium
of of 0%
0% zinc
and 8%in the
zinccoating/metal
phosphate coating was
phosphate
interface
coatingswas diffused
were andand
assessed, thatthat
disbonding
of the of zinc
8% the coating
phosphateoccurred.
coating However,
remained for theone
after coating
day with
of
reduced after two days of immersion, indicating that the corrosive medium in the coating/metal
8%immersion.
zinc phosphate, the low-frequency
As immersion impedance
time increased, value declined
the low-frequency within one
impedance day of
value of immersion,
the 8% zincbut
interface was diffused and that disbonding of the coating occurred. However, for the coating with
thephosphate
value remained
coating wasunchanged
an order of after one day.
magnitude Thethan
higher low-frequency
the value of theimpedance value was
0% zinc phosphate fitted in
coating.
8% zinc phosphate,
Figure 7a. At
To study thethe
the
zinc
low-frequency
beginning,
phosphatethe
impedance
low-frequency
coating,
value
impedance
the equivalent
declined
values
circuit was
within
fittedofinthe 0%one
Figure and day of immersion, but
7b. 8% zinc phosphate
the value remained
coatings unchanged
were assessed, afterofone
and that theday. Thephosphate
8% zinc low-frequencycoatingimpedance
remained after value onewas dayfitted
of in
Figure 7a. At the beginning, the low-frequency impedance values of
immersion. As immersion time increased, the low-frequency impedance value of the 8% zinc the 0% and 8% zinc phosphate
coatings were assessed,
phosphate coating was andanthat of the
order 8% zinc phosphate
of magnitude higher thancoating
the value remained
of the 0%after one day ofcoating.
zinc phosphate immersion.
To study the
As immersion timezinc phosphatethe
increased, coating, the equivalent
low-frequency circuit was
impedance fittedofinthe
value Figure
8% 7b.
zinc phosphate coating
was an order of magnitude higher than the value of the 0% zinc phosphate coating. To study the zinc
phosphate coating, the equivalent circuit was fitted in Figure 7b.
Materials 2017, 10, 654 5 of 13
Materials 2017, 10, 654 5 of 13
Materials 2017, 10, 654 5 of 13

Figure 6. The electrochemical impedance spectroscopy (EIS) of (a1-Nquist, a2-Bote) 0% and (b1-Nquist,
Figure The
6. 6.
Figure electrochemical
The electrochemicalimpedance
impedancespectroscopy
spectroscopy (EIS)
(EIS) of
of (a -Nquist,aa2-Bote)
(a11-Nquist, 2 -Bote)
0%0%and
and(b(b1 -Nquist,
1-Nquist,
b2-Bote) 8% zinc phosphate coatings.
b2 -Bote) 8% zinc phosphate coatings.
b2-Bote) 8% zinc phosphate coatings.

Figure 7. (a) Low-frequency impedance value and (b) equivalent circuit of EIS of the 0% and 8% zinc
Figure
Figure 7. 7.
(a)(a) Low-frequencyimpedance
Low-frequency impedancevalue
value and
and (b)
(b) equivalent
equivalentcircuit
circuitofofEIS
EISofofthe
the0%
0%and 8%8%
and zinc
zinc
phosphate coatings.
phosphate coatings.
phosphate coatings.
Figure 7b shows the equivalent circuit to fit the impedance spectrum. In Figure 7b, Rs is the
Figure 7b shows the equivalent circuit to fit the impedance spectrum. In Figure 7b, Rs is the
solution
Figureresistance,
7b showsQ c is the coating capacitance, and Rc is the coating resistance. Also, Qdl is the
the equivalent circuit to fit the impedance spectrum. In Figure 7b, Rs is
solution resistance, Q c is the coating capacitance, and Rc is the coating resistance. Also, Qdl is thethe
capacitance
solution of
resistance, the double layer
Qc is the between
coating the coating/metal
capacitance, interfaces
and Rcinterfaces that
is the coating can characterize
resistance. Also,the coating
capacitance of the double layer between the coating/metal that can characterize the Q dl is the
coating
disbonding condition. Rct is the charge transfer resistance. In general, a high Rct reflects low corrosion
capacitance of the double layer between the coating/metal interfaces that can characterize
disbonding condition. Rct is the charge transfer resistance. In general, a high Rct reflects low corrosion the coating
because the exchange current is directly associated with the electrochemical process of corrosion;
disbonding condition. R is the charge transfer resistance. In general, a high R
because the exchange ctcurrent is directly associated with the electrochemical ctprocess of corrosion; reflects low corrosion
therefore, Rct can show the degree of corrosion of the coating. The values of Qdl and Rct are shown in
because the Rexchange
therefore, ct can show current is directly
the degree associated
of corrosion of the with theThe
coating. electrochemical
values of Qdl and process
Rct areofshown
corrosion;
in
Figure 8. As immersion time increased, the Qdl values of 0% and 8% zinc phosphate coatings increased
Figure 8.RAs
therefore, immersion
can show time
the increased,
degree of the Q
corrosion dl values
of the of 0% and
coating. 8%
The zinc phosphate
values of Q coatings
and R increased
are shown in
and the Rct dl
ct of both decreased, thereby showing serious corrosion between coating/metal interfaces.
ct
and
Figure the R
8. As the of both
immersion decreased, thereby showing serious corrosion between coating/metal interfaces.
Qdl valuetime increased,
8% zinc the Qdl values of 0% and 8% zinc phosphate coatings
that of increased
ct
However, of the phosphate coating was significantly lower than the 0%
andHowever,
the R ct ofthe Qdl decreased,
both value of thethereby
8% zinc showing
phosphateserious
coatingcorrosion
was significantly
between lower than that ofinterfaces.
coating/metal the 0%
zinc phosphate coating, and its Rct value was significantly higher than the Qdl value of 0% zinc
zinc phosphate
However, the Qdl coating,
value ofand the its
8%Rzinc
ct value was significantly
phosphate coating was higher than the Q
significantly dl value
lower than of that
0% zinc
of the
0% zinc phosphate coating, and its Rct value was significantly higher than the Qdl value of 0% zinc
Materials 2017, 10, 654 6 of 13
Materials 2017, 10, 654 6 of 13

phosphate coating.
phosphate coating. Therefore,
Therefore, the
the added
added zinc
zinc phosphate
phosphate into
into the
the coating
coating slowed
slowed down
down the
the corrosion
corrosion
reaction
reaction at the
at the
Materials coating
2017,coating defect.
10, 654 defect. 6 of 13

phosphate coating. Therefore, the added zinc phosphate into the coating slowed down the corrosion
reaction at the coating defect.

Figure 8. Qdl
dl and
and RRctctvalues
valuesof
of0%
0%and
and8%
8%zinc
zincphosphate
phosphatecoatings.
coatings.
Figure 8. Qdl and Rct values of 0% and 8% zinc phosphate coatings.
2.3.2.
2.3.2. Microscopic
Microscopic Electrochemical
Electrochemical Behavior
Behavior
2.3.2. Microscopic Electrochemical Behavior
Figure
Figure 99 shows
shows thethe point
point measurements
measurements of of the
the local
local alternating
alternating current
current impedance
impedance of of the
the (a)
(a) 0%
0%
and (b) 8% Figure
zinc 9 shows the coating
phosphate point measurements
distances of the
from local
the alternating
scratch defect current
at 1600 impedance
µm in 3.5%of NaCl
the (a)solution.
0%
and (b) 8% zinc phosphate coating distances from the scratch defect at 1600 µm in 3.5% NaCl solution.
Afterand
the(b) 8% zinc phosphate
immersion, theLEIScoating
LEIS distances
value thefrom
of 0% 0% the scratch
zinc defect atcoating
phosphate 1600 µmdecreased
in 3.5% NaCl solution.
After the immersion, the value of the zinc phosphate coating decreased in 3.5% in 3.5%whereas
NaCl, NaCl,
After the immersion, the LEIS value of the 0% zinc phosphate coating decreased in 3.5% NaCl,
whereas
that of that
the ofzinc
8%thatthe phosphate
8% zinc phosphate coating remained
coating remained relatively relatively stable after immersion
stable after for solution
6 h. The
whereas of the 8% zinc phosphate coating remained relatively stableimmersion for 6 for
after immersion h. The
6 h. The
solution
penetratedpenetrated the coating without zinc phosphate and corrosion occurred under the coating.
solutionthe coating the
penetrated without zinc
coating phosphate
without and corrosion
zinc phosphate occurred
and corrosion under under
occurred the coating. However,
the coating.
However,
the coating the coating
with 8% with
zinc 8% zinc
phosphate phosphate
resisted theresisted
medium the medium
permeability permeability
of the
However, the coating with 8% zinc phosphate resisted the medium permeability of the coating.
of
coating.the coating.

Figure 9. The point measurements of localized EIS (LEIS) of 0% (a 1-Nquist, a2-Bote) and 8%
Figure 9. The point measurements of localized EIS (LEIS) of 0% (a 1 -Nquist, a2 -Bote) and 8%
(b1-Nquist, b2-Bote) zinc phosphate coatings immersed in 3.5% NaCl solution.
(b1 -Nquist, b2 -Bote) zinc phosphate coatings immersed in 3.5% NaCl solution.
Figure 9. The point measurements of localized EIS (LEIS) of 0% (a 1-Nquist, a2-Bote) and 8%
(b1-Nquist, b2-Bote) zinc phosphate coatings immersed in 3.5% NaCl solution.
Materials 2017, 10, 654 7 of 13
Materials 2017, 10, 654 7 of 13

Figure
Figure 10
10 shows
shows the
the map
map measurement
measurement of of LEIS
LEIS of
of the
the 0%
0%zinc
zincphosphate
phosphate coating
coating immersed
immersed in in
3.5%
3.5% NaCl solution. At the initial stage of immersion, the impedance value of the coating defect
NaCl solution. At the initial stage of immersion, the impedance value of the coating defect in
in
contact
contactwith
withthe
theelectrolyte
electrolytesolution waswas
solution significantly below
significantly the impedance
below value in
the impedance the intact
value in thecoating.
intact
As immersion
coating. time increased,
As immersion the wholethe
time increased, area of impedance
whole was reduced.
area of impedance was The impedance
reduced. modulus
The impedance
value of the coating defect and around dropped rapidly after immersion for 6 h. The
modulus value of the coating defect and around dropped rapidly after immersion for 6 h. The coating coating defect
was corroded
defect severelyseverely
was corroded and the and
area the
around
area the coating
around thedefect was
coating exfoliated.
defect The solution
was exfoliated. Themedium
solution
penetrated the bottom of the coating, followed by corrosion.
medium penetrated the bottom of the coating, followed by corrosion.

(a) (b)

(c) (d)
Figure 10.
Figure 10. The
The map
map measurements
measurements of of LEIS
LEIS of
of the
the 0%
0% zinc
zinc phosphate
phosphate coating
coating immersed
immersed in
in 3.5%
3.5% NaCl
NaCl
solution: (a) 3D of 0 h; (b) 2D of 0 h; (c) 2D of 3 h; (d) 2D of 6 h.
solution: (a) 3D of 0 h; (b) 2D of 0 h; (c) 2D of 3 h; (d) 2D of 6 h.

Figure 11 shows the map measurements of LEIS of the 8% zinc phosphate coating immersed in
Figure 11 shows the map measurements of LEIS of the 8% zinc phosphate coating immersed in
3.5% NaCl solution. At the initial stage of immersion, the impedance value of the coating defect was
3.5% NaCl solution. At the initial stage of immersion, the impedance value of the coating defect was
significantly below the impedance value in the intact coating, which was the same as the 0% zinc
significantly below the impedance value in the intact coating, which was the same as the 0% zinc
phosphate coating. As immersion time increased, the impedance of the coating defect did not change
phosphate coating. As immersion time increased, the impedance of the coating defect did not change
and the coating defect around it slightly increased, which was completely different from the 0% zinc
and the coating defect around it slightly increased, which was completely different from the 0% zinc
phosphate coating. The added zinc phosphate coating prevented the diffusion of corrosive medium
phosphate coating. The added zinc phosphate coating prevented the diffusion of corrosive medium in
in the lateral of coating/metal interfaces and slowed down the corrosion.
the lateral of coating/metal interfaces and slowed down the corrosion.
After the immersion test in 3.5% NaCl solution, Raman spectroscopy of rust and corrosion
After the immersion test in 3.5% NaCl solution, Raman spectroscopy of rust and corrosion product
product in the defect of the 8% zinc phosphate coating were measured. As shown in Figure 12, the
in the defect of the 8% zinc phosphate coating were measured. As shown in Figure 12, the corrosion
corrosion product was made up by the composition of γ-Fe2O3, α-FeOOH, γ-FeOOH, and iron
product was made up by the composition of γ-Fe2 O3 , α-FeOOH, γ-FeOOH, and iron phosphate.
phosphate.
Materials 2017, 10, 654 8 of 13
Materials 2017, 10, 654 8 of 13
Materials 2017, 10, 654 8 of 13

(a) (b)
(a) (b)

(c) (d)
(c) (d)
Figure 11. The map measurements of LEIS of the 8% zinc phosphate coating immersed in 3.5% NaCl
Figure 11.
Figure The map
11. The map measurements
measurements of of LEIS ofof the 8%
8% zinc phosphate
phosphate coating
coating immersed
immersed in
in 3.5%
3.5% NaCl
NaCl
solution: (a) 3D of 0 h; (b) 2D of 0 h; LEIS
(c) 2D ofthe
3 h; (d) zinc
2D of 6 h.
solution: (a)
solution: (a) 3D
3D of
of 00 h;
h; (b)
(b) 2D
2D of
of 00 h;
h; (c)
(c) 2D
2D of
of 33 h;
h; (d)
(d) 2D
2D of
of 66 h.
h.

Figure 12. Raman analyses of rust and corrosion product in the defect of the 8% zinc phosphate coating.

3. Discussion
Figure
Figure12.12.Raman
Ramananalyses
analysesofofrust
rustand
andcorrosion
corrosionproduct
productin
in the
the defect
defect of
of the
the 8%
8% zinc
zinc phosphate
phosphate coating.
coating.
In comparing the EIS results of the 0% and 8% zinc phosphate coatings (Figure 6) at an 85 ± 5 µm
3. defects on the coatings, the metals were shown to corrode at the defect areas. At the beginning of
3. Discussion
Discussion
immersion, the low-frequency impedance value decreased in both, but as immersion time increased,
Inthecomparing
In comparing the EIS
EIS results
the impedance
low-frequency of
resultsvalue theof0%
of the 0% and
theand 8% phosphate
8%
8% zinc zinc phosphate
zinc phosphate coatings
coatingcoatings
remained (Figure
(Figure 6)10
6)
stable at at5 Ohm·cm
at an 85
an 85 ±
± 25,5 µm
µm
defects
defects on
which the coatings,
wascoatings,
on the higher thanthe metals
thethat were
of thewere
metals shown
0% zinc to
phosphate
shown corrode at the
(Figureat7a).
to corrode defect
theMoreover, areas.
defect areas. At
the RctAt the
value
the of beginning
the 8% of
beginning of
immersion,
immersion, the
the low-frequency
zinc phosphate
low-frequency impedance
coating was significantly
impedancehighervalue decreased
valuethan in
in both,
that of the
decreased 0% zinc
both, but
but as
asimmersion
phosphate coatingtime
immersion (Figure
time increased,
8a).
increased,
the The added zinc
the low-frequency
low-frequency phosphate value
impedance
impedance in the of
value coating
the 8%
of the slowed
8% down the corrosion
zinc phosphate
zinc phosphate coating reaction
coating remained
remained at stable
the coating
stable at 10
at 10defects.
55 Ohm·cm
Ohm·cm2,,
2

which The Qdlhigher

value of thethat
8% zinc phosphate coating was significantly lower than thatRof the 0%ofzinc
which waswas higher thanthan that ofof the
the 0%
0% zinc
zinc phosphate
phosphate (Figure
(Figure 7a).7a). Moreover,
Moreover, the the Rctct value
value of the the 8% 8%
zinc phosphate
phosphate coating
coating (Figure
was 8b), showing
significantly that
higher the
than added
that ofzinc
the phosphate
0% zinc slowed
phosphate down the
coating coating
(Figure 8a).
zinc phosphate coating was significantly higher than that of the 0% zinc phosphate coating (Figure 8a).
disbonding. The reason for this may be that, when the corrosive medium permeated the coating/metal
The
The added
added zinczinc phosphate
phosphate inin the
the coating
coating slowed
slowed down
down the
the corrosion
corrosionreaction
reactionat
at the
the coating
coatingdefects.
defects.
The
The QQdldl value
value of
of the
the 8%
8% zinc
zinc phosphate
phosphate coating
coating was
was significantly
significantly lower
lower than
than that
that of
of the
the 0%
0% zinc
zinc
phosphate coating (Figure 8b), showing that the added zinc phosphate slowed down
phosphate coating (Figure 8b), showing that the added zinc phosphate slowed down the coating the coating
disbonding. The reason for this may be that, when the corrosive medium permeated the coating/metal
Materials 2017, 10, 654 9 of 13
Materials 2017, 10, 654 9 of 13
interfaces, the zinc phosphate was partly dissolved and produced metal substrate phosphate. Zinc
phosphate with the composition of γ-Fe2O3, α-FeOOH, γ-FeOOH, and iron phosphate (Figure 12) can
disbonding. The reason for this may be that, when the corrosive medium permeated the coating/metal
serve as the protective film. The protective film contained carboxyl and hydroxyl groups, which can
interfaces, the zinc phosphate was partly dissolved and produced metal substrate phosphate. Zinc
strengthen the combination of the coating and substrate [29].
phosphate with the composition of γ-Fe2 O3 , α-FeOOH, γ-FeOOH, and iron phosphate (Figure 12) can
serve as the protective film. The protectiveFe Fe 2  2e carboxyl and hydroxyl groups, which (1)
 contained
film can
strengthen the combination of the coating and substrate [29].
O 2  2H 2 O  4e   4OH  (2)
Fe → Fe2+ + 2e− (1)
Zn3  PO4 2  2H2O  4OH  3Zn  OH 2  2HPO42 (3)
O2 + 2H2 O + 4e− → 4OH− (2)
2 2  
Zn3 (PO4 )Fe  HPO 4 − FePO 4  H  e
2 + 2H2 O + 4OH → 3Zn(OH)2 + 2HPO4
2− (4)
(3)
In comparing the LEIS of the Fe20% + HPO4 − →phosphate
+ and 8%2zinc +
+ e− the low-frequency impedance
FePO4 + Hcoatings, (4)
value of the 8% zinc phosphate coating defect declined slowly and the 0% zinc phosphate coating
defectIn declined
comparing the LEIS
visibly of the9).
(Figure 0%These
and 8% zinc phosphate
results show thatcoatings,
the water theabsorption
low-frequency of theimpedance
8% zinc
value of the 8% zinc phosphate coating defect declined slowly and
phosphate coating was decreased significantly. When the corrosion medium penetrated the 0% zinc phosphate coating defect
the
declined visibly (Figure 9). These results show that the water absorption of the
coating/metal interfaces, part of the zinc phosphate dissolved and reacted with Fe to form stable iron 8% zinc phosphate
coating
phosphateswasthat
decreased
can block significantly.
the mediumWhen the [30].
diffusion corrosion medium penetrated the coating/metal
interfaces, part of the zinc phosphate dissolved
The impedance values of the 8% zinc phosphate and reacted with increased
coating Fe to formas stable
the iron phosphates
immersion time
that can block the medium diffusion [30].
increased (Figure 11), because the chemical activation of zinc phosphate enhanced the wet coating
The impedance
adhesion. The spread values
of theofcorrosive
the 8% zinc phosphate
medium coating
in the increasedinterface
coating/metal as the immersion time increased
was prevented and the
(Figure 11), because the chemical activation of
coating defect corrosion reaction and disbonding were slowed. zinc phosphate enhanced the wet coating adhesion.
The spread of the
The failure corrosive medium
mechanisms of the 0%inand the8%coating/metal
zinc phosphate interface
coatings was
areprevented and the13.coating
shown in Figure When
defect corrosion reaction and disbonding were slowed.
the 0% zinc phosphate coating with the defect (Figure 13a) was exposed to corrosive media, the
The failure
corrosion reaction mechanisms
occurred rapidly of theon 0%theand 8% zinc phosphate
coating/metal coatings
interface and greware shown Furthermore,
suddenly. in Figure 13.
When the 0%disbanded
the coating zinc phosphate
from coating
the defect.withHowever,
the defectthe(Figure 13a)defect
coating was exposed
with zincto corrosive
phosphate media, the
has two
corrosion reaction occurred rapidly on the coating/metal interface and grew
aspects of protection (Figure 13b). First, when the corrosion medium permeates the coating/metal suddenly. Furthermore,
the coatingthe
interfaces, disbanded from the
zinc phosphate anddefect. However,
Fe generates stablethe coating
iron defectand
phosphates with zinc phosphate
inhibits the anodichas two
process
aspects of protection
of corrosion. Second,(Figure 13b). First,
zinc phosphate canwhen the corrosion
combine with the medium
carboxyl permeates
and hydroxyl the coating/metal
groups of the
interfaces,
coating, through which a stable protective film was formed by the zinc phosphate, the
the zinc phosphate and Fe generates stable iron phosphates and inhibits anodic
coating andprocess
metal
of corrosion.
substrate. AllSecond,
of thesezinc phosphate
reactions can can combine
inhibit with the
the cathode carboxyl
reaction anddamaging
from hydroxyl groups of the prevent
the coating, coating,
through whichmedium
the corrosion a stable protective film was formed
from a horizontal by the
diffusion, andzinc
slowphosphate,
down the coating
coating anddefect
metal corrosion
substrate.
All of these reactions
and disbonding. can inhibit the cathode reaction from damaging the coating, prevent the corrosion
medium from a horizontal diffusion, and slow down the coating defect corrosion and disbonding.

Schematic of
Figure 13. Schematic of the
the failure mechanism of styrene-acrylic with 0% (a) and 8% (b) zinc phosphate.
Materials 2017, 10, 654 10 of 13
Materials 2017, 10, 654 10 of 13

4. Materials
4. Materials and Methods
and Methods

4.1. Sample Preparation

This work used waterborne acrylic resin made in a chemical plant in Beijing, and the zinc
phosphate was 800 mesh produced in Guangxi Research Institute of Chemical Industry. Industry. A total of
wt.%ofofzinc
8 wt.% zinc phosphate
phosphate composite
composite coating
coating was prepared
was prepared using high-speed
using high-speed shearingshearing mixing.
mixing. The zinc
The zinc phosphate
phosphate was15dried
was dried for min atfor ◦
50 15C,min
and at
then50the
°C,film-forming
and then the film-forming
agent, agent, wetting
wetting dispersant, flash
dispersant,
rust flashphosphate,
agent, zinc rust agent,and
zincaphosphate,
certain amountand aofcertain
water amount of water
were added were added
successively. Thesuccessively.
above fillers
The above
were addedfillers werestirred
and then addedusing
and then stirred
a glass bar using
stirrer.aAfter
glass adding
bar stirrer.
the After
aboveadding above fillers,
fillers, the solution was
the solution
manually was using
stirred manually stirred
a glass using
rod for a glass rod 10
approximately formin
approximately 10 min and
and then dispersed usingthen dispersed
a high-speed
using a high-speed
shearing dispersion shearing
machinedispersion
(America Red machine
Devil(America Red Devil
5400, Trenton, NJ, 5400,
USA)Trenton,
for 30 minNJ, to
USA) for
obtain
30 min to obtain
component component
A. Acrylic A. Acrylic
resin and resin and
a defoaming a defoaming
agent were mixed agent were mixed
manually usingmanually using
a glass rod anda
glasswith
then rod aand then with
magnetic a magnetic
stirrer stirrer
at 360 r/min for at
30 360
minr/min for 30
to obtain min to obtain
component component
B. Finally, componentB. Finally,
A was
component
mixed A was mixed
with component with component
B using B using
a glass rod for a glass
effective rod for effective
distribution, followed distribution,
by magnetic followed
stirringbyat
magnetic
180 r/minstirring at 180
for 30 min r/min for
to obtain the30 min toas
coating, obtain
shown theincoating, as shown
the Figure 14. in the Figure 14.

Figure 14. Flowchart to illustrate the process of preparing the coating.

The metal substrate surface was burnished with a no. 240 sandpaper, cleaned with acetone, and
dried. The
then dried. The above
abovecoating
coatingwas
wasbrushed
brushedonto
onto the
the metal
metal substrate
substrate surface.
surface. TheThe coating
coating thickness
thickness for
for the
the morphology
morphology observation,
observation, adhesion
adhesion test,
test, andand
EISEIS was
was 8585
±±55µm;
µm;whereas,
whereas,that
thatfor
forthe
the LEIS
LEIS was
20 ±
± 22 µm.
µm. Both
Both were
were cured
cured for
for 15 days at room temperature. The length and width of the coating
defects for the EIS test were 10 mm and 120 µm, respectively, and those for the LEIS were 1 mm and
µm, respectively,
120 µm,
µm, respectively,
respectively,and
andwere
wereimplemented
implementedby byaatool
toolknife
knifemade
madeof ofLB30N
LB30Nsteel.
steel.

4.2. Test
Test Methods
Methods
According
AccordingtotoISO4624
ISO4624 standard [31],[31],
standard PosiTestdrawing was used
PosiTestdrawing was to determine
used the adhesion
to determine strength
the adhesion
of the organic
strength of thecoating. The 20-mm
organic coating. The diameter dollies were
20-mm diameter degreased
dollies using acetone
were degreased and then
using acetone andglued
then
to the surface
glued of the coated
to the surface of theplates
coatedusing a two-component
plates epoxy-based
using a two-component cyano-acrylate
epoxy-based adhesive.
cyano-acrylate
After adhesive
adhesive. Aftercuring, a testing
adhesive curing,apparatus
a testing was attached
apparatus wastoattached
the loading fixture
to the and fixture
loading was strained at
and was
5strained
mm/min at 5until the coating
mm/min material
until the coatinghad detached
material hadfrom the substrate.
detached from the substrate.
The micromorphology of the coated section sampled was performed using using SEM
SEM (QUANTA
(QUANTA 250,
FEI, Hillsboro, OR, USA). The macromorphology and micromorphology of the coating defects were
obtained using a digital camera and stereomicroscope.
stereomicroscope.
Materials 2017, 10, 654 11 of 13
Materials 2017, 10, 654 11 of 13

Raman spectra from 100 cm−1 to 1000 cm−1 were used to analyze the composition of the corrosion
products of the
Raman defect
spectra of 100
from 8%−zinc
the cm 1 to 1000 cm−1 were
phosphate coating.
usedIttowas measured
analyze by the Renishaw
the composition DXP780
of the corrosion
Raman
products(Renishaw,
of the defectLondon,
of theUK).
8% zinc phosphate coating. It was measured by the Renishaw DXP780
RamanThe(Renishaw,
macroscopic electrochemical
London, UK). studies on the coating specimens were conducted using a
PARSTAT-2273 electrochemical
The macroscopic workstation
electrochemical studies(Princeton Instruments,
on the coating Trenton,
specimens wereNJ, USA) with
conducted an
using
electrolytic
a PARSTAT-2273cell device as shown workstation
electrochemical in Figure 15. A three-electrode
(Princeton Instruments, cellTrenton,
system NJ,
wasUSA)
used with
in this
an
experiment. The system was assembled with the coating sample as the working electrode,
electrolytic cell device as shown in Figure 15. A three-electrode cell system was used in this experiment. a saturated
calomel electrode
The system (SCE) (Rex,
was assembled Shanghai,
with the China)asasthethe
coating sample reference
working electrode,
electrode, and platinum
a saturated as the
calomel electrode
auxiliary electrode. The EIS measurements were taken in a 3.14 cm 2 area for the coating samples in
(SCE) (Rex, Shanghai, China) as the reference electrode, and platinum as the auxiliary electrode. The EIS
3.5% NaCl solution
measurements were intaken
the frequency cm2 area
in a 3.14range of 100 kHz–0.01
for the coatingHz and a disturbance
samples alternating
in 3.5% NaCl solutionpotential
in the
voltage
frequencyof range
20 mV. ThekHz–0.01
of 100 fitting ofHzEIS
anddata was conducted
a disturbance usingpotential
alternating ZSimpWin3.2. All
voltage of 20EIS
mV.tests were
The fitting
conducted at 22 °C.
of EIS data was conducted using ZSimpWin3.2. All EIS tests were conducted at 22 C. ◦

Figure
Figure 15.
15. Macroscopic
Macroscopic electrochemical
electrochemical test
test devices.
devices.

The LEIS studies on coating specimens were conducted using LEIS components in a M370 micro
The LEIS studies on coating specimens were conducted using LEIS components in a M370 micro
electrochemical workstation (Bio-Logic, Seyssinet-Pariset, France) The LEIS probe made from a
electrochemical workstation (Bio-Logic, Seyssinet-Pariset, France) The LEIS probe made from a 100-µm
100-µm diameter platinum wire was used as an auxiliary electrode, the coating sample was the
diameter platinum wire was used as an auxiliary electrode, the coating sample was the working
working electrode, and an SCE was used as the reference electrode. The distance between the probe
electrode, and an SCE was used as the reference electrode. The distance between the probe and
and the sample was approximately 100 µm and the disturbance alternating potential voltage was
the sample was approximately 100 µm and the disturbance alternating potential voltage was 10 mV.
10 mV. To ensure the stability of the measurement system, the working electrode was placed in the
To ensure the stability of the measurement system, the working electrode was placed in the solution for
solution for 20 min until the fluctuation was less than 10 mV. Thereafter, the potential was set as a
20 min until the fluctuation was less than 10 mV. Thereafter, the potential was set as a fixed potential to
fixed potential to ensure that the measurement was under open circuit potential. The LEIS used two
ensure that the measurement was under open circuit potential. The LEIS used two kinds of test modes,
kinds of test modes, as described below:
as described below:
Point measurement mode: measurement frequency range was 10,000–0.05 Hz; distance from
Point measurement mode: measurement frequency range was 10,000–0.05 Hz; distance from
defects was approximately 1600 µm.
defects was approximately 1600 µm.
Map scanning mode: testing scope was 3100 × 1000 µm with a step length of 100 µm; according
Map scanning mode: testing scope was 3100 × 1000 µm with a step length of 100 µm; according
to previous studies [32], 5 kHz was selected to characterize the coating disbonding.
to previous studies [32], 5 kHz was selected to characterize the coating disbonding.
5. Conclusions
5. Conclusions
Zinc phosphate particles were dispersed evenly in the coating and combined closely with the
Zinc phosphate particles were dispersed evenly in the coating and combined closely with the
waterborne acrylic resin. No defects in the coating were found, and the initial adhesion of the coatings
waterborne acrylic resin. No defects in the coating were found, and the initial adhesion of the coatings
with and without zinc phosphate remained. These results showed that zinc phosphate and
with and without zinc phosphate remained. These results showed that zinc phosphate and waterborne
waterborne acrylic resin have good compatibility. The experimental results of EIS revealed that
acrylic resin have good compatibility. The experimental results of EIS revealed that adding zinc
adding zinc phosphate did not change the electrochemical process of the coating failure but
phosphate did not change the electrochemical process of the coating failure but effectively slowed
effectively slowed the corrosion degree of the coating defects. The anode and cathode electrochemical
the corrosion degree of the coating defects. The anode and cathode electrochemical processes were
processes were characterized via LEIS. Adding zinc phosphate inhibited the anode process of the
characterized via LEIS. Adding zinc phosphate inhibited the anode process of the bare metal in the
bare metal in the defect and slowed the corrosion reaction of the anodic metal. Simultaneously, zinc
defect and slowed the corrosion reaction of the anodic metal. Simultaneously, zinc phosphate enhanced
phosphate enhanced the wet adhesion of coating, and was beneficial for preventing the lateral
the wet adhesion of coating, and was beneficial for preventing the lateral diffusion of the corrosive
diffusion of the corrosive medium into the coating/metal interface. Moreover, it slowed down the
Materials 2017, 10, 654 12 of 13

medium into the coating/metal interface. Moreover, it slowed down the disbonding of the intact
coating around the defect. The results showed that adding zinc phosphate to the waterborne acrylic
coating can highly improve corrosion resistance.

Acknowledgments: The authors wish to acknowledgement the financial support from National Basic Research
Program of China (973 Program) (No. 2014CB643300) and National Natural Science Foundation of China
(Grant Nos. 51371036).
Author Contributions: Dongdong Song and Xiaogang Li conceived and designed the experiments; Hongxia Wan
and Dawei Zhang performed the experiments; Dongdong Song and Hongxia Wan analyzed the data; Jin Gao and
Cuiwei Du contributed reagents/materials/analysis tools; Hongxia Wan wrote the paper.
Conflicts of Interest: We declare that we do not have any commercial or associative interest that represents
a conflict of interest in connection with the work submitted.

References
1. Francisco, J.S.; Capelossi, V.R.; Aoki, I.V. Evaluation of a sulfursilane anticorrosive pretreatment on
galvannealed steel compared to phosphate under a waterborne epoxy coating. Electrochim. Acta 2014,
124, 128–136. [CrossRef]
2. Santos, D.; Raminhos, H.; Costa, M.R.; Diamantino, T.; Goodwin, F. Performance of finish coated galvanized
steel sheets for automotive bodies. Prog. Organ. Coat. 2008, 62, 265–273. [CrossRef]
3. Liu, M.; Mao, X.; Zhu, H.; Lin, A.; Wang, D. Water and corrosion resistance of epoxy–acrylic–amine
waterborne coatings: Effects of resin molecular weight, polar group and hydrophobic segment. Corros. Sci.
2013, 75, 106–113. [CrossRef]
4. Standardization, I.O.F. Corrosion of Metals and Alloys-Corrosivity of Atmospheres- Classification; ISO: Geneva,
Switzerland, 1992; Volume 9223.
5. Pathak, S.S.; Sharma, A.; Khanna, A.S. Value addition to waterborne polyurethane resin by silicone modification
for developing high performance coating on aluminum alloy. Prog. Organ. Coat. 2009, 65, 206–216. [CrossRef]
6. Gao, X.-Z.; Liu, H.-J.; Cheng, F.; Chen, Y. Thermoresponsive polyaniline nanoparticles: Preparation,
characterization, and their potential application in waterborne anticorrosion coatings. Chem. Eng. J. 2016, 283,
682–691. [CrossRef]
7. Rahman, O.U.; Kashif, M.; Ahmad, S. Nanoferrite dispersed waterborne epoxy-acrylate: Anticorrosive
nanocomposite coatings. Prog. Organ. Coat. 2015, 80, 77–86. [CrossRef]
8. Liu, S.; Gu, L.; Zhao, H.; Chen, J.; Yu, H. Corrosion resistance of graphene-reinforced waterborne epoxy
coatings. J. Mater. Sci. Technol. 2016, 32, 425–431. [CrossRef]
9. Li, J.; Ecco, L.; Delmas, G.; Whitehouse, N.; Collins, P.; Deflorian, F.; Pan, J. In-situ afm and eis study of
waterborne acrylic latex coatings for corrosion protection of carbon steel. J. Electrochem. Soc. 2015, 162,
C55–C63. [CrossRef]
10. Lewis, O.D.; Critchlow, G.W.; Wilcox, G.D.; Dezeeuw, A.; Sander, J. A study of the corrosion resistance of
a waterborne acrylic coating modified with nano-sized titanium dioxide. Prog. Organ. Coat. 2012, 73, 88–94.
[CrossRef]
11. Fürbeth, W.; Stratmann, M. The delamination of polymeric coatings from electrogalvanised steel—A
mechanistic approach. Part 1: Delamination from a defect with intact zinc layer. Corros. Sci. 2001, 43,
207–227. [CrossRef]
12. Leng, A.; Streckel, H.; Stratmann, M. The delamination of polymeric coatings from steel. Part 1: Calibration
of the kelvinprobe and basic delamination mechanism. Corros. Sci. 1998, 41, 547–578. [CrossRef]
13. Leng, A.; Streckel, H.; Stratmann, M. The delamination of polymeric coatings from steel. Part 2: First stage of
delamination, effect of type and concentration of cations on delamination, chemical analysis of the interface.
Corros. Sci. 1998, 41, 579–597. [CrossRef]
14. Leng, A.; Streckel, H.; Hofmann, K.; Stratmann, M. The delamination of polymeric coatings from steel
part 3: Effect of the oxygen partial pressure on the delamination reaction and current distribution at the
metal/polymer interface. Corros. Sci. 1998, 41, 599–620. [CrossRef]
15. Ecco, L.G.; Li, J.; Fedel, M.; Deflorian, F.; Pan, J. Eis and in situ afm study of barrier property and stability of
waterborne and solventborne clear coats. Prog. Organ. Coat. 2014, 77, 600–608. [CrossRef]
Materials 2017, 10, 654 13 of 13

16. Wan, H.; Song, D.; Li, X.; Zhang, D.; Gao, J.; Du, C. Failure mechanisms of the coating/metal interface in
waterborne coatings: The effect of bonding. Materials 2017, 10, 397. [CrossRef]
17. Kukackova, H.; Vraštilová, A.; Kalendova, A. Non-toxic anticorrosive pigments intended for applications in
high-solids and waterborne paints. Phys. Procedia 2013, 44, 238–246. [CrossRef]
18. Zubielewicz, M.; Gnot, W. Mechanisms of non-toxic anticorrosive pigments in organic waterborne coatings.
Prog. Organ. Coat. 2004, 49, 358–371. [CrossRef]
19. Shao, Y.; Jia, C.; Meng, G.; Zhang, T.; Wang, F. The role of a zinc phosphate pigment in the corrosion of
scratched epoxy-coated steel. Corros. Sci. 2009, 51, 371–379. [CrossRef]
20. Chromy, L.; Kamińska, E. Non-toxic anticorrosive pigments. Prog. Organ. Coat. 1990, 18, 319–324. [CrossRef]
21. Mahdavian A., A.; Attar, M.M. Investigation on zinc phosphate effectiveness at different pigment volume
concentrations via electrochemical impedance spectroscopy. Electrochim. Acta 2005, 50, 4645–4648. [CrossRef]
22. Naderi, R.; Attar, M.M. Application of the electrochemical noise method to evaluate the effectiveness of
modification of zinc phosphate anticorrosion pigment. Corros. Sci. 2009, 51, 1671–1674. [CrossRef]
23. Gimeno, M.J.; Puig, M.; Chamorro, S.; Molina, J.; March, R.; Oró, E.; Pérez, P.; Gracenea, J.J.; Suay, J.J.
Improvement of the anticorrosive properties of an alkyd coating with zinc phosphate pigments assessed by
nss and acet. Prog. Organ. Coat. 2016, 95, 46–53. [CrossRef]
24. Lu, X.; Zuo, Y.; Zhao, X.; Tang, Y. The influence of aluminum tri-polyphosphate on the protective behavior of
mg-rich epoxy coating on az91d magnesium alloy. Electrochim. Acta 2013, 93, 53–64. [CrossRef]
25. Hao, Y.; Liu, F.; Han, E.H.; Anjum, S.; Xu, G. The mechanism of inhibition by zinc phosphate in an epoxy
coating. Corros. Sci. 2013, 69, 77–86. [CrossRef]
26. Bethencourt, M.; Botana, F.J.; Cano, M.J.; Osuna, R.M.; Marcos, M. Degradation mechanism of an acrylic
water-based paint applied to steels. Prog. Organ. Coat. 2003, 47, 164–168. [CrossRef]
27. Cao, J.; Shao, Y.; Zhang, T.; Meng, G. Roles of zinc phosphate on the corrosion of the scratched epoxy coating.
J. Chin. Soc. Corros. Protect. 2009, 29, 437–441.
28. Shi, Q.; Shao, Y.; Zhang, T.; Meng, G.; Chen, Q. Protection dimension of scratched zinc phosphate/epoxy
coating. J. Chin. Soc. Corros. Protect. 2011, 31, 389–394.
29. Romagnoli, R.; Vetere, V.F. Heterogeneous reaction between steel and zinc phosphate. Corros. Houst. TX
1994, 51, 116–123. [CrossRef]
30. Caprari, J.J.; Sarli, A.R.D.; Amo, B.D. Zinc phosphate as corrosion inhibitive pigment of waterborne epoxy
paints used for steel protection. Pigment Resin Technol. 2000, 29, 16–22. [CrossRef]
31. Standards, S. Paints and Varnishes—Pull-Off Test for Adhesion (ISO 4624:2002); CEN/TC 139—Paints and
varnishes; ISO: Geneva, Switzerland, 2016.
32. Jorcin, J.B.; Aragon, E.; Merlatti, C.; Pébère, N. Delaminated areas beneath organic coating: A local
electrochemical impedance approach. Corros. Sci. 2006, 48, 1779–1790. [CrossRef]

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