Encapsulation of triethanolamine as organic corrosion inhibitor into nanoparticles

and its active corrosion protection for steel sheets

Hana Choi
a
, Yon Kyun Song
b
, Kyoo Young Kim
a
, Jong Myung Park
a,

a
Graduate Institute of Ferrous Technology, Pohang University of Science and Technology (POSTECH), Pohang 790-784, Republic of Korea
b
Surface Technology Research Group, POSCO Technical Research Laboratories, Gwangyang 545-090, Republic of Korea
a b s t r a c t a r t i c l e i n f o
Article history:
Received 11 July 2011
Accepted in revised form 11 October 2011
Available online 19 October 2011
Keywords:
Self-healing
Hollow coreshell
Encapsulation
Corrosion inhibitor
Triethanolamine
Triethanolamine (TEA), a corrosion inhibitor for zinc and steel, was introduced into nano-sized particles as
nanoreservoirs to increase longevity of inhibitive property and prevent degradation caused by direct addition
of corrosion inhibitor into coating layer. TEA-incorporated nanoparticles with average particle size around
400450 nm were successfully synthesized by sequential emulsion polymerization, occupying around 5% of
total solid weight of particles during a neutralization process. Encapsulated TEA was released from the cap-
sule inside when the pH level of environment became acidic or alkaline due to an acidbase interaction or
ionization of seed material in specic conditions. In the corrosion tests, the encapsulated TEA decreased
the corrosion rate of steel substrate owing to its adsorption on steel surface and the resistance of coating
layer against corrosive environment was much higher and remained its resistance as immersion time in-
creased when TEA was incorporated in coating layer in the encapsulated form. Based on the scanning vibrat-
ing electrode technique (SVET) result, anticorrosive ability of the encapsulated TEA seemed to improve due
to the spontaneous passivation of exposed metal on the defected region of coated steel.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Organic amine corrosion inhibitors have been widely used for cor-
rosion protection of metal from aggressive environments due to their
economic and effective corrosion retarding capability in various in-
dustrial elds. They are added in small concentrations into corrosive
electrolyte to form a thin passive lm on the surface of the metal sub-
strate, retarding the access of the corrosive species to the metal. The
main inhibitive mechanism is considered to be adsorption on metal
surface followed by the formation of a passive and protective layer
[1,2]. It is well known that organic amines with low molecular mass
and high water solubility have enhanced adsorption and corrosion in-
hibition properties [35]. Corrosion inhibitors are usually included in
pickling or cooling uids, antifreezing liquids and concretes to retard
the corrosion process of the metal substrate. They are generally incor-
porated into the environment, but cannot be used directly to metals
themselves. In the case of steel applications such as an automotive
body, corrosion inhibitors are not considered as fundamental solution
for steel corrosion protection except for the surface treatment with
inhibitors.
Because of the restrictions of a corrosion inhibitors available envi-
ronment, organic coating is more widely used for the protection of
steel products in both wet and dry conditions with an excellent
insulated lm on the surface which blocks the penetration of corro-
sive ions, water and oxygen. However, the organic layer also obstructs
the path of electron and causes several problems in post-processes
such as welding. In addition, when coated steel substrates with de-
fects meet corrosive environments, the organic coating is unable to
serve as a protective lm for the metal and thus causes coating de-
lamination or blistering. Eventually, the corrosion of metal substrate
accelerates due to the decrease of the anodic-to-cathode area ratio.
In order to compensate drawbacks of the organic coating system, ex-
tensive efforts have been devoted to the development of self-healing
coating systems which can recover coating defects by themselves on
demand.
One simple approach is the addition of corrosion inhibitors direct-
ly into the polymer coating binder to provide additional active corro-
sion protection and to hinder the corrosion activity in defect sites. The
coatings can release active and healing species after certain changes
in the coating integrity. The active agents such as corrosion inhibitors
can be introduced into the different parts of the coating layer, such as
pretreatment, primer and topcoat layers. Healing agents are effective
only if their solubility in the defect environment is in the right range.
Very low solubility can cause a lack of the active healing agent at the
substrate interface and as a result, the healing effect will be weak. On
the contrary, if the solubility is too high, the active agents will be
available too short of a time span to be effective. Moreover, high sol-
ubility leads to blistering and delamination of the active surface due
to osmotic pressure causing water to be transported through the
coating. Additionally, the release of inhibitors from coatings will be
Surface & Coatings Technology 206 (2012) 23542362
Corresponding author. Tel.: +82 54 279 9017; fax: +82 54 279 9299.
E-mail address: jongpark@postech.ac.kr (J.M. Park).
0257-8972/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2011.10.030
Contents lists available at SciVerse ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ sur f coat
relatively fast and uncontrollable [68]. Therefore, direct addition of
corrosion inhibitor into coating formulations can cause uncontrolla-
ble release of corrosion inhibitors leading to the fast exhaustion of
the active anticorrosion potential and osmotic blistering of the poly-
mer lm [9]. An active protection or self-healing system is considered
as new coating system to extend lifetime of steel products because of
their ability to activate the corrosion inhibiting action only when
necessary. Self-healing is dened as the healing ability of damaged
materials autonomously without any external trigger [10]. Currently,
self-healing systems have been developed to recover mechanical
strength of cracked barrier coating or release active inhibitive agent
by stabilizing corrosion activity of defected area on metal surface
[10,11]. In new advanced corrosion protection coating systems, various
methods to store and discharge active agents are employed; for in-
stance, nanoporous metal oxide multilayer materials like titania [12],
ion-exchanged particles [13] and nanocontainers [14,15] to ensure
good barrier properties and an effective self-healing mechanism [16].
In this paper, we stored organic corrosion inhibitors in modied
hollow latex nano-reservoirs which have been mainly used in coating
applications to enhancing the coating opacity [1719]. One of the def-
inite advantages of our system is that it makes better use of applica-
tion by replacing any other corrosion inhibitors with needs. We
focused on corrosion prevention of cold-rolled steel with both barrier
protection and inhibitive protection. In order to incorporate the self-
healing properties into the developed coating system, triethanol-
amine was used as the corrosion inhibitor for steel.
2. Experimental procedure
2.1. Capsule synthesis
Nano-sized polymeric capsules as nanoreservoirs for carrying
triethanolamine (TEA) as a corrosion inhibitor were fabricated by se-
quential emulsion polymerization. The core latex was obtained from
KCC Co. (South Korea), and the average particle diameter was
100 nm. The main components of the core latex were methyl methac-
rylate, butyl acrylate and methacrylic acid with the ratio of 63:9:28.
Potassium persulfate (Samchun Chemical) was used as a free radical
initiator and Rhodapex CO-436 (ammonium nonylphenol ether
sulfate) from Rhodia Inc. was used as an anionic emulsier for emul-
sion polymerization. The polymerization process was carried out
under nitrogen atmosphere, and deionized water (DI water) was
used throughout all of the experimental processes. All chemicals
were used without further purication.
Firstly, 60 g of the core latex particles was dispersed in 430 g of DI
water in a round-bottomask at 80 C. Then, 0.5 g of sodiumpersulfate
dissolved in 15 g of DI water was fed into the ask to initiate radical re-
action within 5 min. The rst shell layer with intermediate hydrophilic-
ity was synthesized on the hydrophilic core latex particles, and the main
components of this layer and seed materials were same but different in
ratio as described in Table 1. This intermediate layer was employed for
better encapsulation of hydrophobic polymer shell on the hydrophilic
core polymer. After holding at 80 C for 1 h, a stable monomer pre-
emulsion containing 98 g of styrene was dropped into the reactor at
the rate of 2.27 g/min. Once the formation of the polystyrene outermost
shell is completed, penetration of TEA into the core through the shell is
difcult since the stable and rigid polystyrene shell prevents the amine
from reaching into the acidic center part. Therefore, TEA was simulta-
neously fed with styrene pre-emulsion mixture for rst 15 min to
maximize the neutralization degree (TEA capsule). Standard blank
nanoparticles with the same physical property as TEA capsule except
for the absence of the basic corrosion inhibitor were also fabricated as
reference (REF1) to compare the active anticorrosion performance of
encapsulated corrosion inhibitor. REF1 particles were solid compared
to the hollow structure of TEA capsules. Another reference capsules
were prepared to study the effect of the hollow structure on the
corrosion behavior of the capsule-containing coating layer. In this
case, ammonia solution (28%, Samchun Chemical) was used instead of
TEA to make hollowpolymer capsules (REF2). Because, unlike TEA, am-
monia was very volatile at the high baking temperature, as described in
the Section 2.3, the REF2 capsules embedded in the coating layer
remained hollow without any active agents inside.
2.2. Characterization
Polymeric capsules were collected for further analysis by ltering
the obtained latex with 0.2 m cellulose lter paper and rinsed with
DI water and ethyl alcohol to remove the remained TEA and unreacted
monomers on the surface of the capsules. The ltered capsules were
then dried in ambient condition for several hours. Transmission elec-
tron microscope (TEM, Philips CM 200) and scanning electron micro-
scope (SEM, Hitachi SU-6600) were used for visualization of the
synthesized nanocapsules and comparison of size and shell shape. Sam-
ples were coated in a few nanometers of Pt sputtering method to pre-
vent the charge-up of the specimen surface. Quantitative analysis was
done using thermogravimetric analysis (TGA, TA instruments) and
gas chromatographymass spectrometry (GCMS, Thermoelectro
Polaris Q). In the case of TGA, a sample amount of 1030 mg was put
in an alumina pan and the thermograms were recorded from 25 C to
600 C with a heating rate of 5 C/min in nitrogen atmosphere. For
the determination of TEA contents with GCMS, nanoparticles were
dissolved in tetrahydrofuran (THF, Sigma Aldrich) at about
5000 ppm, and 25 l of N,O-bis(trimethylsilyl)triuoroacetamide
(Fluka) was added into 1 ml of this solution for silylation. Silylation is
a common and versatile method to derivatize polar organic amines. N,
O-bis(trimethylsilyl)triuoroacetamide was used as the silylation re-
agent, which lead to the formation of trimethylsilyl (TMS) derivatives.
In the silylation procedures, reactions took place at 60 C for 60 min
[20,21]. TEA concentration in nanocapsules was identied by compari-
son of retention time, and a Trace GC 2000 was used to obtain mass
spectra equipped with a 60 m DB-5 capillary column (Agilent, Palo
Alto, CA) and a Polaris Q Ion Trap MS (Thermoquest, San Jose, CA).
The initial oven temperature was 50 C and the temperature was main-
tained at 50 Cfor 5 min, andthen increased to 250 Cwith10 C/min of
heating rate and held for 5 min. Calibration samples were prepared in
the concentration range from 25 to 300 ppm in THF, and the working
sample was 10,000 ppm.
2.3. Release behavior of corrosion inhibitor depending on pH
Corrosion inhibitor should be easily released into electrolytes to
protect the metal substrate against corrosion when pH is shifted
Table 1
Synthesis recipe for standard polymeric capsule (REF1) and neutralized capsule with
ammonia (REF2) and TEA (TEA capsule).
Step Chemicals REF1 REF2 TEA
capsule
1 DI water 435 g
Core latex 60 g
2 DI water 15 g
Sodium
persulfate
0.5 g
3
(1st shell formation)
Butyl acrylate 4.2 g
Methyl
methacrylate
51 g
Methacrylic acid 1.8 g
4
(2nd shell formation)
DI water 38 g
Styrene 98 g
Sodium
persulfate
0.5 g
Surfactant 0.33 g
5
(Injection of base/corrosion inhibitor)
Aqueous NH
3
20 g
TEA 0.15 M
2355 H. Choi et al. / Surface & Coatings Technology 206 (2012) 23542362
due to anodic and cathodic reactions when corrosion proceeds or the
environment changes. Release behaviors in different pH environ-
ments were investigated. To simulate the different electrolyte condi-
tions, hydrochloric acid solution (0.1 M HCl), potassium hydroxide
solution (0.1 M KOH) and neutral DI water were used to manipulate
the pH of the solution to 1.71, 5.63 and 10.85. Nanoparticles in pow-
der form were rinsed with DI water and ethyl alcohol before use and
then packed in the molecular porous membrane tubing (Spectra/
Por3 dialysis membrane). Dried nanoparticles were sealed in mem-
brane tubes with clips, submerged in a pH adjusted solution, and col-
lected 0.5, 1, 12, 18, 24, 72, 96 and 120 h after submersion. The
obtained solutions were analyzed by liquid chromatography and
mass spectrometry (LCMS).
2.4. Coating process
The corrosion inhibitive efciency of encapsulated TEA was evaluat-
ed. Commercial cold-rolled steel (CRS) sheets with thickness of
0.783 mm were supplied from POSCO. The specic chemical composi-
tion of specimen is detailed in Table 2. Synthesized nanocapsules in
emulsion state were added in polyurethane resin with curing agent
(Cymel 325, Cytec Industries) and wetting agent (Byk-348, BYKchemie).
Since total solid content affects the coating thickness after curing, solid
volume ratio of the coating solution was maintained at a similar level.
In the case of REF1, total shell thickness and average particle size of
unneutralized capsules were much smaller than those of neutralized
ones (TEA capsule), and the core latex was different from that of TEA
capsule. When the coreshell latex was swollen by base, the inside of
the capsule became hollow and the particle diameter increased. During
this process, capsule properties are totally changed with formation of
micro-/nanopores on the shell and the decrease of the shell thickness.
It degraded the barrier property of coating layer to supply more penetra-
tion path of corrosive ions when capsules are employed in organic coat-
ing. For offsetting condition differences, reference nanoparticles for
coating were neutralized with ammonia solution (REF2) with same
method as TEA capsule fabrication.
Concentration of incorporated capsules was 33.3 wt.% of total solid
in the coating system. The coating process was performed by using a
bar coater (no. 20). Before curing, specimens were rst baked at
105 C using an induction oven to prevent coating failure caused by
the difference of boiling temperature between water and resin.
After evaporating water, samples were cured at the peak metal tem-
perature of 170 C in the induction oven. The coating thickness and
the cross-section of the specimens were observed by scanning trans-
mission electron microscopy (STEM, Jeol 2100F) after making speci-
mens by focused ion beam (FIB, Seiko SMI 3050 SE).
2.5. Corrosion tests
Conventional corrosion evaluation of coated steel has been con-
ducted using salt spray test, cyclic corrosion test and immersion
test. However, in our coating system, excess electrolytes or sever rins-
ing disturb the action of inhibition due to low concentration or loss of
corrosion inhibitors from coating layer. Quantity of TEA in organic
coating is few ppm compared to total solid in the coating layer. In
order to observe effect of encapsulated corrosion inhibitor clearly,
semi-immersion tests were performed by forming a thin lm with
10 ml of electrolytes (3.5% NaCl solution) on the specimens in a
petri dish. In this case, the penetration of oxygen was much easier
and partial pressure of oxygen in electrolyte was higher than that of
the conventional immersion test. At the end of the experiments, the
coating layer was peeled off and the scribed zone was analyzed
with a micro-image analyzer (Sometech videoscope). The samples
were cut into a size of 50 mm50 mm and all the edges were sealed
with non-conductive tape to prevent cut edge corrosion. Scanning vi-
brating electrode technique (SVET, Applicable Electronics Inc)
employing microelectrode (MicroProbes Inc.) with a black Pt coating on
tip was conducted in 0.05 M NaCl solution (conductivityb196 S/cm).
The microelectrode was scanned with a distance of 150 m above the
specimens and all processes of the experiments were controlled by the
ASET software. Electrochemical impedance spectroscopy (EIS) measure-
ments were performed using a Gamry reference 600 in 0.05 MNaCl solu-
tion. Specimens were xed in a commercial at cell with a saturated
calomel reference electrode and a platinum mesh counter electrode,
and working electrode area was 1 cm
2
. EIS measurements were carried
out at the open circuit potential with a 10 mV amplitude sinusoidal volt-
age in the frequency range of 0.0110,000 Hz and Bode diagrams were
plotted.
For semi-immersion tests and SVET measurements, articial de-
fects were created by a ceramic tip to investigate the inhibitive and
self-healing protection at the small active area.
3. Results and discussion
3.1. Synthesis of latex polymeric capsules
Hollow latex particles loaded with TEA were formed by the fol-
lowing three stages:
Stage 1. Fabrication of amphiphilic rst shell on the carboxylated
seed materials
Stage 2. Synthesis of hydrophobic second shell to give stability on the
nanoparticles
Stage 3. Capsule swelling by neutralization of seed materials with
basic amine corrosion inhibitor (TEA)
Our capsulated corrosion inhibitor system composes of a soft
inner seed core material and hard outer thermoplastic polymer
layer. The seed latex formed by copolymerization of MMA and MA
with small amount of BA (63:28:9, w/w) is hydrophilic, and the aver-
age size is 100 nm as shown in Fig. 1. The center of each capsule is
brighter than the surrounding sheaths due to different chemical com-
position of each part because styrene has darker contrast due to high
electron density of benzene ring [22]. It is surrounded by about 20 nm
of the rst shell which is amphiphilic and act as the buffer layer be-
tween hydrophilic inner seed and hydrophobic outer shell for the
concentric coreshell growth. The same chemicals of the seed mate-
rials were used in the rst shell layer, but the relative ratio of each
chemical was adjusted in a proper way. It is for next multi-stage po-
lymerization to synthesize the hydrophobic polymer onto the hydro-
philic acid-containing core. The concentric coreshell morphology is
not the thermodynamically preferred one and thus the kinetics and
thermodynamic factors are optimized by changing compositions
and polymerization conditions to obtain the desired morphology
[23,24]. The outermost hydrophobic layer is composed of polystyrene
and the shell thickness is 100130 nm. Fig. 1 (a) represents the
standard nano-sized particles (REF1) not containing any corrosion
inhibitor. The most denite change after the addition of TEA as the
basic corrosion inhibitor is the increase of seed and shell layer
size as shown in Fig. 1 (b). In REF1, the total size of the capsule is
300350 nm, while TEA capsule shows 400450 nm in size. The
seed layer is increased by 100 nm to 300 nm because of the osmotical
swelling caused by the diffusion of water with TEA through the outer
polymeric layer. The attraction derived from acid-basic neutralization
was used as the driving force to diffuse TEA into the core of the cap-
sule. The chemical composition of the core polymer is designed to
be ionizable when pH of solution changes to alkaline. Therefore, the
Table 2
Chemical composition of cold-rolled coil sheet.
C P S Si Mn Ni Cr Mo
(%) 0.0022 0.0062 0.0040 0.004 0.088 0.01 0.01 0.00
2356 H. Choi et al. / Surface & Coatings Technology 206 (2012) 23542362
subsequent swelling process imbibes water into the center of the par-
ticle. The water leaves a void upon evaporation during the drying of
the coating formulation and less volatile TEA stays inside of the cap-
sule [23]. Fig. 1 (c) and (d) show the morphologies of REA1 capsule
and TEA capsule. REF1 capsule has a smooth surface and the size of
each particle is quite uniform.
3.2. Characterization of encapsulated TEA in the nanocapsules inside
In order to conrm the presence of TEA, thermogravimetric analy-
sis was performed and TGA weight loss curve for polymeric capsule
without/with corrosion inhibitor is presented in Fig. 2. When compar-
ing the thermal degradation behavior of two types of polymeric nano-
particles, TEA capsule showed different weight loss characteristics at
180 C and 400 C, and 2.35 wt.% of TEA capsule was degraded be-
tween 180 C and 250 C while 0.85% of REF1 was degraded. Because
the boiling point of TEA is 330335 C, most of TEA evaporates
through the pores at 335 C. When assuming that the properties of
polymeric outer shell layer and the thermal property of TEA are not
changed by the incorporation of TEA, the degradation before 335 C
is mainly due to the evaporation of encapsulated TEA. At 335 C, the
TEA capsules showed a 6 wt.% weight loss, while REF1 showed 3%
weight loss. Thus, the total amount of TEA deposit in the capsules
was estimated to be about 3 wt.% of the powdered capsule.
For more precise quantitative analysis of encapsulated TEA, the
analysis by using GC/MS was carried out. In general, amines tend to
be adsorbed and decomposed on the columns, and readily give tailed
elution peaks, ghosting phenomena and low detector sensitivity
[25,26]. Derivatization is a popular method for overcoming this prob-
lem. N,O-bis(trimethylsilyl)triuoroacetamide is a powerful silylating
reagent and reacts not only with amino groups but also with hydroxyl
and carboxyl groups under anhydrous reaction conditions. The
byproduct of the reagent is volatile and thus does not interfere in
analysis. In general, the silylation reaction occurs in the following
order, alcohols>phenols>carboxylic acids>amines>amides [20].
In the case of TEA, three hydroxyl groups can be trimethylsilated by
replacing \OH with \O\Si\(CH
3
)
3
.
Dissolved TEA capsules in THF and standard solutions of TEA were
prepared with concentration of 10,000 ppm for sample and 25, 50,
100, 200 and 300 ppm for calibration. Loaded amount of TEA in nano-
particles was calculated by peak area of the characteristic peak of TEA
which was conrmed by mass spectrometry with comparison of
mass/charge (m/z) and checked again by retention time of standard
and working sample. Peak area of standard samples showed linear
distribution and linear trendline was obtained by linear tting func-
tion of Origin 8.0. From the trendline, the quantitative concentration
of encapsulated TEA depending on different input was calculated
and the result was shown in Fig. 3.
When 0.08 M TEA was introduced to the synthesized reactor, total
encapsulated TEA was 219.02 ppm in 10,000 ppm of powdered cap-
sule/THF, indicating that TEA occupied 2.19% in total weight of one
capsule. TEA ratio in capsule increased from 2.19% to 5.04% as the in-
troduced amount of TEA increased from 0.08 M to 0.15 M. However,
a b
c d
Fig. 1. Transmission electron micrograph of reference polystyrene nanoparticles without corrosion inhibitor (REF1 capsule) (a) and nanoparticles after injecting of corrosion inhib-
itor (TEA capsule) (b). Scanning electron micrograph of REF1 (c) and TEA capsule (d).
Fig. 2. TGA curve of REF1 capsule and TEA capsule.
2357 H. Choi et al. / Surface & Coatings Technology 206 (2012) 23542362
encapsulated TEA did not increase more than 5.22% even though
0.2 M TEA was added during neutralization process, meaning maxi-
mum incorporation of TEA was between 0.15 M and 0.2 M.
3.3. Release behavior of encapsulated TEA depending on different pH
condition
When localized corrosion occurs, reduction and oxidation reactions
can occur to cause pH distribution on the cathode/anode areas. In the
case of local corrosion in an organic coating system, the defected region
of coating layer can be the local anode, whereas the undamaged region
is the local cathode. Oxygen reduction in the cathodic area makes cath-
ode alkaline usually above pH 8 and forms reactive species which dete-
riorates adhesion between metal and polymer layer [27,28]. Due to pH
variation in defected or corroded area, the corrosion inhibitor incorpo-
rated into nanocontainers is released through microchannels formed
on the surface of polymeric sheath by osmotic swelling. The ability to
release the healing agent in a target region is one of the most required
properties in the encapsulated corrosion inhibitor system since it is di-
rectly related to the anticorrosion efciency of the system. In order to
investigate the release behavior of the corrosion inhibitor during the
corrosion process, each local corrosion system was simulated by sub-
merging nanoparticles into solutions of different pH as a function of
time. Acidic and alkaline solutions respectively represent localized cor-
rosion environments in anode and cathode. As shown in Fig. 4, TEA in-
corporated into nanocontainers was readily released from the capsule
inside in both acidic and alkaline condition, whereas relatively more
corrosion inhibitor remained inside the nanoreservoirs in the neutral
environment. The amount of released TEA did not depend on reaction
time in the solution, meaning that the release of corrosion inhibitor in-
stantly occurred when pHof the surrounding condition was changed. In
the study on a coreshell polymeric nano- or microcapsule fabrication
for drug delivery, it was reported that carboxylic groups and amine spe-
cies are not ionizable in a neutral condition, but they can be charged and
then dissolve in aqueous phase if pH level of outside solution becomes
acidic or alkaline [2932]. According to the result of LCMS, TEA was re-
leased in an alkaline condition as well as in an acidic environment. Ini-
tially, TEA exists inside nanocapsules in a salt form with the latex core.
The higher pHof the environment, the stronger the degree of hydrolysis
of the salt. Thus, TEA with weak basicity would be free fromthe interac-
tion with core material and nally released into an electrolyte. When
the environment was changed to a low pH condition, strong attraction
between amine and acid in the electrolyte mainly affected the release
of amine species. Therefore, release efciency of encapsulated amine
would have a minimumnear neutral conditions. When painted steel lo-
cally corrodes, the metal substrate beneath the coating layer is exposed
and becomes partially anode and cathode with a different pH distribu-
tion along the exposed area. Near the anode/cathode region, electro-
lytes become acidic and alkaline, and ionizable groups can release into
electrolytes. The interaction between TEA and ions in electrolyte with
pH variation makes it possible to release TEA from nanoparticles into
the corrosive environment. Released TEA is adsorbed on the surface of
exposed metals to form the passive and protective layer against corro-
sion, and it retards corrosion of steel by repairing damaged regions in
the coating layer.
3.4. Inhibitive behavior of encapsulated TEA on steel
The inhibitive ability of aliphatic and aromatic amines is due to the
donation of unshared -electron pair on the nitrogen atom [33,34].
TEA can act as a corrosion inhibitor in many metals such as zinc and
steel. However, its high solubility in water hinders long-term corro-
sion protection, especially when it is added into coating systems di-
rectly. Encapsulated corrosion inhibitor can guarantee the longevity
of corrosion protection by controlling the release of corrosion inhibi-
tor on demand. Synthesized nanocapsules with TEA were incorporat-
ed into a polyurethane resin and then coated on CRS at a dry lm
thickness of about 1012 m. The coated specimen for cross-section
analysis was prepared by FIB and observed using STEM as shown in
Fig. 5. Only a part of the total coating layer is shown in Fig. 5 since
FIB could not treat the thick organic coating layer due to the depth
limitation of the equipment during preparation for the STEM sample.
The total coating layer was analyzed by SEM attached with FIB and
the upper part of coating layer of about 5 m thickness was sliced
and analyzed with STEM. It was shown that nanocapsules were well
dispersed through the coating layer and not transformed during cur-
ing process in high temperature.
Fig. 3. Quantitative analysis of encapsulated TEA in nanoparticles depending on differ-
ent input of TEA with GCMS.
Fig. 4. pH-dependent release behavior of TEA capsule in different pH range. Fig. 5. Cross-sectional view of coated specimen.
2358 H. Choi et al. / Surface & Coatings Technology 206 (2012) 23542362
The anticorrosive effect of encapsulated TEA was evaluated using
semi-immersion tests. In the coated specimens, total amount of TEA
was expected to be less than 1% and in the conventional immersion
test, it was not adequate for inhibitive action because of its diluted
concentration in large electrolyte. To avoid concentration limitations,
a small amount of electrolyte was used for corrosion test. In this
semi-immersion tests, very thin electrolyte lmwith 10 ml of NaCl so-
lution was formed on the surface of each specimen in a petri dish, and
specimens were sealed to prevent evaporation of electrolyte to keep
the constant volume of electrolyte and electrolyte level. Metal sub-
strates were articially exposed to observe the corrosion process at
the scribed region. The corrosion process and surface change of coated
specimens containing REF1, REF 2 and TEA capsules are shown in
Fig. 6. All specimens started to corrode right after immersion and the
corrosion rate of REF1- and REF2-contailing specimens was much fas-
ter than that of TEA capsules-containing specimen in the early stage of
the immersion (Fig. 6 (b)). Red rust was formed at the scribed region
and also at the non-scribed zone. In a day, the specimens without
TEA were corroded over almost the whole surface, while the TEA
capsule-containing specimen was corroded only at the X-cut region
(Fig. 6 (c)). After 3 days of immersion, a much larger amount of rust
was observed in the specimens with REF1 and REF2 than in the TEA
capsule-containing specimen (Fig. 6 (d)). After removing the remain-
ing coating layers, the scribed area was observed using an optical mi-
croscope (Fig. 6 (e)). Corrosion reaction dominantly occurred under
the coating nearby the scribed region. In the specimens with REF1
and REF2, red rust was observed in many places while it was rarely ob-
served in the specimen with TEA capsule, indicating better corrosion
protection due to encapsulated TEA, as can be seen in Fig. 6 (e). Corro-
sion products were analyzed with X-ray photoelectron spectroscopy
(XPS) and Fourier transform infrared spectroscopy (FTIR). However,
any difference in corrosion products between specimens with and
without TEA was not detected by two analysis methods. It seemed
that none or very small amount of TEA took part in the reaction be-
tween the metal and ions, or the differences were not detected due
to the shift in energy state being too small to distinguish the TEA-
adsorbed peak from non-adsorbed one or its insufcient concentra-
tion below detection resolution of the equipment.
In anorganic coating system, corrosion protection of the initial stage
is important because once metal corrosion begins, corrosion at this
point is accelerated causing catastrophic degradation of the coated
steel. Self-healing efciency determines corrosion rate of early stage of
corrosion. For the investigation of corrosion behaviors in the initial
points of corrosion by using SVET, specimens with an articial defect
were cut in the same size, and the edges were sealed and then im-
mersed in 0.05 M NaCl solution for 30 min. After 30 min, the rst mea-
surement of current density over the surface of the substrate was
conducted, and the second experiment followed after 3 h of immersion.
In the case of REF2 capsule, further SVET measurement was not carried
out because the bulky corrosion products formed on the surface can
cause damage on the microtip probe. For the TEA-containing specimen,
additional SVET measurement was performed 2 h after the rst mea-
surement. At the scribed zone, the current density along the defected
region was increased due to the corrosion process in the specimen
without corrosion inhibitor (REF2), resulting active anode and cathode
on the surface of exposed metal to appear as shown in Fig. 7. In the case
of the specimen with TEA capsules, the current distribution was rela-
tively even on the entire surface of the sample and the highest current
density at the locally corroded region was much smaller than that of
the REF2-containing specimen. The suppression of corrosion activity
in the TEA-containing system occurred within a fairly short amount of
time after immersion into the electrolytes. This spontaneous passiv-
ation and suppression of corrosion activity on the defect region are
well in accord with the reduction of corrosion process in the previous
semi-immersion result of the specimen containing TEA capsules.
In order to corroborate the results of the semi-immersion and
SVET tests, EIS experiments were performed on coated specimens in
a 0.05 M NaCl solution. Fig. 8 shows the Bode plots of the EIS tests
after 2, 12, 24, 36 and 48 h (for the REF2-containing specimen) and
2, 12, 24, 48, 96 and 144 h (for the TEA-containing specimen) of im-
mersion in the electrochemical test cell. At the initial state of immer-
sion within 2 h of interaction between organic coating layer and
corrosive species in electrolyte, the total impedance (Z
mod
) of both
specimens showed similar values with around order of 6. However,
after 1 day, the resistance of coating layer for the specimen containing
TEA dramatically degraded below 10
5
, and constantly decreased with
respect to time. In TEA-containing specimen, the total impedance was
gradually increased from 810
5
to 510
6
for 2 days. This may indi-
cate that there was a self-healing action of encapsulated TEA released
from nanocapsules by forming passive lms on exposed metal sub-
strate. After 2 days in electrolyte, the value of Z
mod
started to decrease
but remained higher than that of the initial experiment (after 2 h
from immersion). As conrmed in the SVET measurement, TEA re-
leased in the corrosive environment passivated the damaged metal
Fig. 6. a) Experimental setup of semi-immersion test in 3.5% NaCl solution. Top-view of specimens containing 33.3% of REF1, REF2 and TEA capsule b), c) and d) after 12, 24 and 72 h
after immersion and e) magnied images of scribed region after peeling off the coating layer.
2359 H. Choi et al. / Surface & Coatings Technology 206 (2012) 23542362
Fig. 7. Current density maps taken in the same area of specimens with REF2 capsule after (a) 30 min and (b) 3 h of immersion, and TEA capsule after (c) 30 min, (d) 3 h and (e) 5 h of immersion in 0.05 M NaCl solution. Scanned area:
6.06.0 mm2. Current density legend: A/cm
2
.
2
3
6
0
H
.
C
h
o
i
e
t
a
l
.
/
S
u
r
f
a
c
e
&
C
o
a
t
i
n
g
s
T
e
c
h
n
o
l
o
g
y
2
0
6
(
2
0
1
2
)
2
3
5
4

2
3
6
2
surface and retarded further corrosion by adsorbing on the metal
surface.
In the very early stage of corrosion process within 30 min, the
total impedance (Z
mod
) of the TEA-containing specimen was not
much lower than that of the specimens without neutralization.
When nanoparticles were swollen after neutralization, shell thickness
decreased due to an increase of core of the particle and characteristics
of the shell polymer such as porosity were changed. As a result of
acidbase interaction, highly carboxylated polymers in the center of
the particles formed polyelectrolyte salts resulting in hollow core
shell structures. Accordingly, it would provide a bad inuence on
the barrier property of the coating layer and in the initial stage of
EIS tests, specimens with neutralized nanocapsules (REF2 and TEA
capsule) showed lower total impedance value compared with
unswollen particles. In addition, amine species attracted water into
the organic coating layer and deteriorated barrier properties of the
coating. In REF2, ammonia mostly evaporated during the baking pro-
cess in the induction oven and did not have a bad inuence on the
coating quality any more. TEA, on the other hand, when added direct-
ly to the coating solution, will remain in the dried lm even after cur-
ing at over 170 C, and had a chance to deteriorate the coating layer,
degrading barrier properties. On the contrary to this, nanoparticles
neutralized with TEA did not deteriorate the stability of the coating
layer, and the coating resistance had even increased with the increase
of immersion time. TEA was expected to compensate the decrease of
barrier protection caused by the hollow capsule structure because it
acts as the corrosion inhibitive agent to retard a steel corrosion by
adsorbing on the steel surface. SVET and EIS tests results revealed
TEA showed the rapid passivation on the metal surface in the early
stage of corrosion and it was mainly contributed to the better corro-
sion protection of TEA capsules-containing specimens in all corrosion
tests. However, the inhibitive mechanism of TEA is not completely
understood yet and a further investigation will be followed.
4. Conclusions
Nanocapsules were used as nanocarriers of amine-type corrosion
inhibitor TEA for long-term and self-healing corrosion protection of
a steel substrate.
Nano-polymer capsules with corrosion inhibitor, TEA, were suc-
cessfully fabricated using multi-stage emulsion polymerization.
After neutralization with TEA, the average size of nanocontainers
increased from 350 nm to 450 nm due to osmotic swelling. Approx-
imately, 5 wt.% of TEA was stored in the center of nanocapsules
when 0.15 M of TEA was fed during fabrication.
TEA was released more rapidly in both low and high pH environ-
ments than a neutral environment, which demonstrates higher pos-
sibility of its effective adsorption on anodic and cathodic sites
generated by the onset of corrosion reaction of defected metal
substrate.
In the semi-immersion corrosion tests and electrochemical tests
such as EIS and SVET measurement, specimens with encapsulated
TEA showed outstanding corrosion inhibition behavior. The notice-
able corrosion protection ability of nanocapsules loaded with TEA
was thought to be due to the passivation of metal surface.
Acknowledgments
This work was nancially supported by POSCO. We appreciated
the assistance of Ki Hwan Kim in the operation of TEM and Eul Ho
Shin in the analysis of LCMS at Research Institute of Industrial
Science and Technology (RIST).
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