Surface & Coatings Technology 276 (2015) 8–15

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Surface & Coatings Technology

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

Effects of inorganic sealant and brief heat treatments on corrosion

behavior of plasma sprayed Cr2O3–Al2O3 composite ceramic coatings
Fang Shao ⁎, Kai Yang, Huayu Zhao, Chenguang Liu, Liang Wang, Shunyan Tao
The Key Laboratory of Inorganic Coating Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, PR China

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

Article history: In the present study, Cr2O3–Al2O3 composite coatings were fabricated by atmospheric plasma spraying (APS)
Received 11 March 2015 technique. Aluminum phosphate with small fraction of Al2O3 nanoparticles was applied as high-temperature
Revised 18 June 2015 sealant to enhance the anti-corrosion performance of the coatings. The inorganic sealant significantly reduced
Accepted in revised form 21 June 2015
the open pore of the as-sprayed coatings and showed low shrinkage after heat treatment (600 °C, 30 min).
Available online 23 June 2015
Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and salt spray tests were used to
Keywords:
assess anti-corrosive characteristics of the coatings. The sealants resulted in an augment of corrosion resistance
Cr2O3–Al2O3 coatings properties of the coatings both before and after heat treatment, indicating effective sealing and good high
Sealing temperature applicability. The sealed Cr2O3–Al2O3 composite coatings have a potential use in severe corrosion
Aluminum phosphate condition.
Corrosion resistance © 2015 Elsevier B.V. All rights reserved.
Plasma spraying

1. Introduction Commercial sealants are usually based on organics such as epoxy,

In the recent period, the booming ocean economy requires ad-
vanced corrosion preventing technologies for marine and offshore
facilities [1]. Atmospheric plasma spraying (APS) is a versatile tech-
nology to produce protective coatings for facilities in extensive ap-
plications [2,3]. Various types of wear and corrosion are the most
frequent conditions the surface coatings have to withstand [4]. Ce-
ramic coatings such as metal oxides (Al2O3, Cr2O3, ZrO2, TiO2, etc.)
are remarkable coating materials to improve wear, cavitation, fretting
and corrosion resistance. They are especially useful in applications
where high temperature is required simultaneously. However, owing
to their lamellar structure and rapid solidification, plasma sprayed coat-
ings usually have plenty of cracks and voids. These structural defects
provide paths for corrosive species to corrode the substrate, leading
to a deleterious effect when these coatings have to perform in an
aggressive environment (e.g., seawater). Thus, post-treatments of the
as-sprayed coatings are necessary to reduce porosity and enhance the
corrosion resistance of the coatings. Laser remelting [5,6] and high
temperature treatments [7] have been applied, but the high thermal
inputs may induce microstructural changes of the substrate material,
in some cases even lead to cracking of the coatings due to the large
residual stress. In consideration of the economic and technical benefits,
sealants are widely used [8,9].
⁎ Corresponding author.
E-mail address: shaofang@mail.sic.ac.cn (F. Shao).
phenolic, silicone and acrylic resin [10]. Moreover, nanoparticles have
been dispersed into the polymers to improve the mechanical properties
and corrosion resistance [11]. Despite their good permeability, organic
sealants have poor wear resistance, and they can hardly meet the high
temperature applications (above 500 °C) [12]. In a practical application,
the oxide ceramic coatings are frequently subjected to elevated temper-
ature due to the high frictional heat and operating conditions. To
overcome this limitation, inorganic sealants were studied. Sol–gel
sealing treatments were carried out, the reduction of porosity was
however small, indicating insufficient protection [13]. The reasons can
be ascribed to the low solid yield and large shrinkage during heat treat-
ment. If the sealant has a high curing shrinkage, especially when it can
penetrate and adhere well into the coating, it may create local tensile
fields, thus causing easier and larger particle detachments during the
wear process [14]. Solid phases, such as fine powders or fibers were
used as advanced filler to increasing the solid content [15]. On the
other hand, it has been reported that aluminum phosphate sealing
leads to obvious pore decrease and better wear resistance when used
in Al2O3 and Cr2O3 coatings [16,17]. In earlier studies our group found
that Cr2O3–Al2O3 composite coatings show lower porosity and better
mechanical properties (such as hardness, fracture toughness, bending
strength) than the individual Cr2O3 and Al2O3 coatings [18,19]. The
Cr2O3–Al2O3 composite coatings have promising application in some
facilities, such as the friction clutch used in shipboard aircraft, where
the coatings are often under conditions of severe wear and high temper-
ature due to the high frictional heat. However, the ocean environment
brings forward higher demand for corrosion resistance. As far as we
know, few research has been done on the corrosion characteristics of

http://dx.doi.org/10.1016/j.surfcoat.2015.06.045
0257-8972/© 2015 Elsevier B.V. All rights reserved.
 F. Shao et al. / Surface & Coatings Technology 276 (2015) 8–15 9

plasma-sprayed Cr2O3–Al2O3 composite coatings, much less the 2.3. Characterization

inorganic sealing effects. Therefore it is important to study the proper-
ties of the sealed Cr2O3–Al2O3 composite coatings before and after
high temperature treatments.
In this paper, Cr2O3–Al2O3 composite coatings were prepared via
APS technique. In addition, aluminum phosphate with a small fraction
of Al2O3 nanoparticles was applied as inorganic sealant. The coatings
with and without sealing treatment were heated at 600 °C to determine
the high temperature applicability. The corrosion behavior was charac-
terized by potentiodynamic polarization, electrochemical impedance
spectroscopy and salt spray test. Based on the results of the analyses,
an attempt was made to discuss the corrosion process of the Cr2O3–
Al2O3 composite coatings.
2. Experimental procedure
2.1. Plasma spraying
304 stainless steel was used as the coating substrate. Prior to depo-
sition, substrates of 30 × 30 × 5 mm3 were sandblasted after ultrasonic
cleaning in ethanol. A bond layer NiCr and working layer Cr2O3–Al2O3
(CA hereafter) were produced with a Multicoat™ atmospheric
plasma-spraying system equipped with a F4-MB plasma gun (Sulzer
Metco AG, Switzerland). Commercial fused and crushed Cr2O3–Al2O3
feedstock powders were available. The median particle diameter (D50)
is about 30 μm, and the fraction of Al2O3 phase in the powders is approx-
imately 30 wt.%. The coatings were prepared with the optimized param-
eters as shown in Table 1. The thickness of the as-sprayed coatings was
controlled to be about 350 μm.
The phase composition was done using a powder X-ray diffraction
(XRD, D/max 2550 V, Rigaku Tokyo, Japan). The microstructure was
characterized using a scanning electron microscope (SEM, TM3000,
HITACHI, Japan) with affiliated energy-dispersive spectrometer. The
accelerated voltage for EDS was 15 KV. The electrochemical corrosion
tests of coating samples were performed in a three electrode cell using
a platinum mesh electrode as a counter, a saturated calomel electrode
(SCE) as reference electrode and the coating samples as the working
electrode. The exposed area of the coating samples was 1 cm2. The
experiment was conducted in unstirred 3.5 wt.% NaCl solution. Electro-
chemical systems Ametek 1287 & 1260 were used for the corrosion
tests. The corrosion potential and the corrosion current density were
obtained through the linear analysis of Tafel approximation. Electro-
chemical impedance spectroscopy (EIS) curves of the coated samples
were acquired at the open circuit potential (Eocp) after 30 min of immer-
sion, which had been determined earlier. The frequency range varied
from 10− 2 Hz to 106 Hz. The polarization curves were obtained at a
scan rate of 0.2 mV/s and a scan range of 0.2 V–0.4 V vs Eocp. Repeated
tests were performed to ensure the reproducibility of the results.
The salt spray test was conducted following the Chinese National
Standard GB/T 10125-2012. The coatings were exposed to a salt fog gen-
erated from a (50 ± 5) g/L NaCl solution with a pH value of 6.5–7.2 at
(35 ± 2)°C. The exposure duration lasted for 96 h.
3. Results and discussion
3.1. Phase structure

2.2. Sealing of the coating Fig. 1 shows the X-ray diffraction patterns of the as-sprayed CA
coating. All peaks can be assigned to a solid solution (Cr, Al)2O3. Since
The plasma-sprayed CA coatings were sealed by aluminum phos- Cr2O3 and α-Al2O3 are isostructural, they can easily form continuous
phate with small fraction of Al2O3 nanoparticles. Aluminum phosphate solid solution in which the solute is completely incorporated in the
was prepared from the solution of aluminum hydroxide (Al(OH)3) lattice [21]. The peak positions are close to those of pure α-Cr2O3
and orthophosphoric acid (85% H3PO4) diluted with about 20 wt.% of [ICDD PDF 38-1479]. The only difference is that the location of peaks
deionized water [20]. The Al(OH)3:H3PO4 ratio was 1:4.2 by weight, shifts to higher 2θ angles, towards the positions for α-Al2O3 [ICDD PDF
which corresponded to the molar ratio P/Al of about 3. The solution 46-1212] due to the reduction of lattice parameters. While γ-Al2O3
was mixed and slightly heated on a magnetic stirrer until it became is usually dominant in the Al2O3 coatings deposited by APS, the XRD
clear. Then, 5 wt.% Al2O3 nanoparticles were added to the solution and result of CA indicates that the α-phase is fully stabilized, which can be
stirred to get a well dispersed sealant. The samples were immersed attributed to the substitution of Al ions in alumina by Cr.
into the sealants at 50 °C for about 30 min with an ultrasonic bath and
then standing at ambient temperature and atmospheric pressure for
12 h. Thereafter, the impregnated coatings were heat-treated for 2 h
at 100 °C, followed by 2 h at 200 °C, and 2 h at the final curing temper-
ature of 250 °C. The excess sealant was ground off by polishing, ensuring
that the true surface of the coating was exposed for microscopic analysis
and corrosion tests. The obtained samples were labeled as CA-S. To
determine the high temperature resistance, the samples with and
without sealing treatment were heated at 600 °C for 30 min and the
samples were denoted as CA-SH and CA-H, respectively.

Table 1
Plasma-spraying operating parameters.

Parameters Bond coat Top coat Unit

Arc current 600 650 A

Primary plasma gas (Ar) 57 45 slpm
Secondary plasma gas (H2) 5 10 slpm
Carrier gas (Ar) 3.5 3.5 slpm
Powder feed rate 18 35 g/min
Nozzle diameter 6 6 mm
Powder injector diameter 2.0 1.8 mm
Powder injector distance 5.0 5.0 mm
Fig. 1. XRD patterns of the as-sprayed CA coating. The dash line represents the standard
Spray distance 120 110 mm
line-graph corresponding to α-Cr2O3 [ICDD PDF 38–1479].
10 F. Shao et al. / Surface & Coatings Technology 276 (2015) 8–15

Fig. 2. The polished cross-section morphologies of (a) CA, (b), (c) CA-S coatings; (d) EDS analysis of the region marked with white crosses in (c).

3.2. Morphology and elemental analysis Fig. 3a, b are the cross-sectional SEM images of CA-H and CA-SH,
respectively. Compared with Fig. 2, it can be found the 600 °C heat treat-
The microstructure of the coating was determined by the cross- ment has no obvious effect on the morphology of coatings except a
sectional SEM micrograph of the coatings. As shown in Fig. 2a, the slightly denser structure. Sealed defects can also be detected in CA-SH
unsealed coating has relatively high porosity and some micro cracks. coating as shown in Fig. 3c. The EDS results are shown in Fig. 3d and
After sealing, it can be found that the topside of the coating exhibits Table 2. Similar effects of sealing on the elements were observed. The
less porosity, and the sealant has penetrated into the coating to a increase of Al and P in range A indicates the existence of sealant.
depth of about 90 μm from the surface (Fig. 2b). The SEM image at There was little shrinkage of the sealant, showing good thermo-stable
higher resolution exhibits the filled defects (Fig. 2c). Fig. 2d is the EDS performance.
patterns of range A and B (the inset image) in Fig. 2c. The chemical
compositions are listed in Table 2. There is the evident element of 3.3. Potentiodynamic polarization
phosphorus in the filled defects of CA-S coating (range A in Fig. 2c)
while in the dense area B, peaks corresponding to phosphorus were Table 3 exhibits the open-circuit potential (Eocp) of the four coating
barely observed. Meanwhile, the percent of Al and Cr elements in samples when the values were stable after immersion in 3.5% NaCl
range A have changed greatly compared with CA and range B. The solution for 30 min. Potentiodynamic polarization curves are shown in
significantly increased Al should originate from the sealant (aluminum Fig. 4. Values of the corrosion potential (Ecorr) and the corrosion current
phosphate and the Al2O3 nanoparticles). It strongly indicates that the density (Icorr) extracted from these curves by Tafel fitting using CView
sealant can be brought into the coatings through the structural defects softwore are also listed in Table 3. Icorr is an important parameter used
(e.g., voids, cracks and gaps between the lamellae). for evaluating the kinetics of the corrosion reaction. Corrosion protec-
tion is inversely proportional to the Icorr [22]. The Icorr of CA and CA-S
indicates a reduction in corrosion rate of about 10 times after sealing.
CA-H shows a slightly smaller Icorr than CA, which may be due to the
Table 2 denser structure. The Icorr of CA-SH is far less than that of CA-H while
Chemical composition (atom%) of the four different coatings corresponding to Figs. 2 almost equal to that of CA-S, signifying the good heat resistance of the
and 3. sealant.
Samples O Al Cr P From polarization curves, the open porosity (designated by Po) can
be calculated by the following equation:
CA 65.0 12.2 22.8 /
CA-S (A) 67.5 22.6 7.9 2.0
CA-S (B) 65.8 12.5 21.7 / IC
Po ¼  100% ð1Þ
CA-H 64.5 12.1 23.4 / IS
CA-SH (A) 65.9 24.1 8.6 1.4
CA-SH (B) 68.5 11.4 20.1 /
where Ic and Is indicate corrosion current density of the coated
 F. Shao et al. / Surface & Coatings Technology 276 (2015) 8–15 11

Fig. 3. The polished cross-section morphologies of (a) CA-H, (b), (c) CA-SH coatings; (d) EDS analysis of the region marked with white crosses in (c).

substrate and the bare substrate in the same electrolyte, respectively interconnected porosity was blocked. Further, epoxy resin could pene-
[8]. trate into the Al2O3–TiO2 coating by above 300 μm [26,27]. However,
Since the sealing efficiency (designated by Si) is related to Po, Eq. (2) the high temperature resistance of epoxy resin was poor (completely
can be derived to relate Si and Icorr. decomposed after heat treatment at 600 °C for 30 min in our experi-
ments). Sol-derived sealant can be used in conditions where the
temperature is above 1000 °C, but the porosity of the modified coatings
! " !# " !#
P 0o −P o Po Icorr is only decreased minimally (~12% to ~11%) after the sealing treatment
Si ¼  100% ¼ 1−  100% ¼ 1−  100% [15].
P 0o P 0o I0corr
After heat treatment, the coating samples shift the corrosion poten-
ð2Þ tial in the negative direction. Compared with CA-H, the Ecorr of CA-SH

where Po and P0o are the open porosity of the sealed and unsealed
coatings, and Icorr and I0corr are the corrosion current density of the sealed
and unsealed coatings, respectively [23]. The calculated Si of CA-S and
CA-SH is shown in Table 3. 89.1% open pores were sealed by modified
aluminum phosphate sealant. Further, it was observed that the open
porosity in CA-SH was reduced by 85.1% compared with CA-H. The
porosity variation between CA and CA-H can also be explained by
Eq. (2). The heat treated coating has an ~20% lower porosity, which is
consistent with our previous work [24]. Zhang et al. [25] studied the
effectiveness of sealing treatment with epoxy resin using similar
methods. Epoxy resin sealed Cr2O3–TiO2 coating well and 81% of

Table 3
Corrosion parameters obtained from potentiodynamic polarization measurements of the
four different coatings in 3.5% NaCl electrolyte.

Samples Eocp (mV) Ecorr (mV) Icorr (μA/cm2) Rp (KΩ cm2) Si (%)

CA −187 −203 11.0 4.2 /

CA-S −167 −209 1.2 39.2 89.1
CA-H −246 −255 8.7 6.5 /
Fig. 4. Potentiodynamic polarization curves of the four kinds of coatings in 3.5% NaCl
CA-SH −277 −300 1.3 30.1 85.1
electrolyte.
12 F. Shao et al. / Surface & Coatings Technology 276 (2015) 8–15
Fig. 5. Nyquist impedance plot for four kinds of coatings. Symbols represent experimental
data and solid lines stand for fitted data. The inset image is the equivalent circuit.
was further shifted in the negative direction by about 45 mV.
The change in Ecorr depends on the relative effect of the coating on the
anodic and cathodic reactions [28]. The negative shift in Ecorr in the
present case suggests that the heated coatings preferentially inhibits
the cathodic process, especially for the sealed samples.
The change trends of polarization resistances (Rp) reveal that CA-S
and CA-SH has better corrosion inhibition capability, which are consis-
tent well with the results of Icorr. Rp was calculated based on the Stern
and Geary relationship. It is worth noting that unlike CA and CA-H,
there was no passivation observed for the sealed coatings (CA-S and
CA-SH). This appearance is probably attributed to the fewer permeable
defects in sealed coatings [29].
3.4. Electrochemical impedance spectroscopy (EIS)
A number of works revealed that electrochemical impedance
spectroscopy (EIS) is a powerful, non-destructive technique for the
detection of electrochemical characterization of ceramic coatings in
the field of aqueous corrosion science [30–32]. The EIS data of the four
kinds of coatings are presented in the Nyquist plots in Fig. 5. The diam-
eters of Nyquist plots increased after sealing, indicating the decreased
corrosion. EIS spectra for coatings can be represented by simple equiva-
lent circuit shown in the inset of Fig. 5. Rs stands for the resistance of the
solution, Rpo is the resistance to current flow through the pores in the
coating, Rt indicates the charge transfer resistance, CPEc is the constant
Fig. 6. Bode plots of the four kinds of coatings. Symbols represent experimental data and solid lines stand for fitted data.
Fig. 7. Digital photos of the coatings after 96 h of the salt spray test: (a) CA, (b) CA-S,
(c) CA-H, (d) CA-SH.
phase element (CPE) of coatings and CPEdl is a double-layer capacitance
between the substrate/coating interface [33]. Here, CPE was used as a
substitute for the capacitor to fit more accurately the impedance data
of the electrochemical capacitance. The fitting curves are presented in
Fig. 5 as the solid lines for each spectrum. The element values of Rt
and Rpo can indicate the corrosion resistance and protectiveness of
coating, respectively [34]. The fitting values of Rpo corresponding to
CA, CA-S, CA-H and CA-SH are 146.2, 2252, 183.3 and 1408 Ω, respec-
tively. The relatively low Rpo values of CA and CA-H indicate that the
NaCl solution penetrates into the pores of the unsealed coatings. The
higher Rpo values of CA-S and CA-SH demonstrate the reduced porosity
after sealing. The improvement effect of sealing on the corrosion resis-
tance of coated samples can be further confirmed by the difference of
Rt. CA-S and CA-SH have much larger Rt (21,695 Ω and 28,627 Ω)
than CA and CA-H (4264 Ω and 5075 Ω), indicating that the electro-
chemical reaction speed was decreased [30].
In Bode plots the magnitude of the impedance |Z| and phase-angle
are plotted respectively as a function of frequency (f). Impedance at
 F. Shao et al. / Surface & Coatings Technology 276 (2015) 8–15 13

Fig. 8. EDS maps of Ni element of (a) CA-H, (b) CA-SH. The scale bar is 2 mm. The detected regions were marked by white rectangle in Fig. 7c and d.

the high frequency represents the performance of the coating in corro-
sion solution, while at the low-frequency, it is related to the corrosion at
the substrate/solution interface [35]. Compared with CA and CA-H, the
impedance of CA-S and CA-SH were enhanced over the whole frequency
range, as shown in Fig. 6. This indicates that the corrosion resistance of
the sealed coating are much greater than that of the unsealed coating.
3.5. Salt spray test
CA, CA-H, CA-S and CA-SH were subjected to the salt spray test to
further investigate the anti-corrosion performances of the coatings.
After 96 h testing, both CA and CA-H exhibit discoloration in the area
marked by the arrows, while there are no visible discoloration in CA-S
and CA-SH (Fig. 7). Further, as shown in Fig. 8, additional EDS maps
were used to study the corrosion behavior of the samples. There were
Ni enrichments in the discoloration area of CA-H (marked by white
rectangle in Fig. 7). On the contrary, the phenomenon was not observed
in CA-SH. The surface morphology of the coatings was also examined by
SEM after 96 h of the salt spray test, as shown in Fig. 9. Since the surface
morphologies and EDS results were very similar when the coatings
were heated or not, the coatings with heat treatment were discussed
here. The EDS analysis result (Fig. 9b) revealed that Ni and Fe elements
appeared nearby the discoloration area of CA-H. The chemical composi-
tions are listed in Table 4. It can be concluded that the corrosion

Fig. 9. (a) Top-view SEM image of CA-H after 96 h of salt spray test; (b) EDS results corresponding to the area marked with white rectangle in (a); (c) plane SEM image of CA-SH after 96 h
of salt spray test; (d) EDS analysis of the region marked with white cross and white rectangle (the inset image) in (c).
14 F. Shao et al. / Surface & Coatings Technology 276 (2015) 8–15
Table 4
Chemical composition (atom%) of CA-H and CA-SH coatings after salt spray test.
Samples O Al Cr P Na Cl
CA-H 57.1 5.5 28.6 / 2.2 1.7
CA-SH (A) 70.5 10.0 3.2 16.3 / /
CA-SH (B) 68.9 12.1 18.1 0.9 / /
products generated during the salt spray test. The atom percentage of
Ni is higher than Fe. In addition, some EDS results of the around places
show 3.5 atom% Ni but unobvious Fe peaks (0.7 atom%). If the electro-
lyte can easily permeate the NiCr bond coat and reach the substrate, gal-
vanic corrosion would be formed on substrate because the corrosion
potential of Ni is higher than that of Fe in NaCl. Fe will be the dominant
element in the corrosion products. Based on the above analyses, a pos-
sible process for the corrosion of CA and CA-H was proposed as follows:
the electrolyte penetrated into the coating following the defects, when
it reached the NiCr bond coat, corrosion occurred. With increasing cor-
rosion time, corrosion products such as nickel oxides and hydroxides
were accumulated in the NiCr/ceramic interface and appeared on the
surface of the top-coat through the pores or cracks. Further, electrolyte
may penetrate the bond coat, thus accelerating the corrosion of
substrate.
In contrast, no obvious peaks of Ni or Fe were detected in CA-SH.
Range B shown in Fig. 9c is Cr2O3–Al2O3 coatings while range A is filled
with sealant as proved by EDS results (Fig. 9d and Table 4). These results
were in complete agreement with those obtained by polarization test
and electrochemical impedance spectrum. The sealants prevented the
electrolyte from penetrating into the Cr2O3–Al2O3 coatings by closing
the available paths. Even after heat treatment, sealed coatings still
exhibit good corrosion resistance.
4. Conclusion
In the current work, Cr2O3–Al2O3 composite coatings were prepared
via APS technique. Aluminum phosphate with small fraction of Al2O3
nanoparticles was applied as high-temperature sealant. The phase
composition, microstructure and corrosion properties of the coatings
were investigated. Based on the experimental results, the following
conclusions can be drawn:
(1) The fused Cr2O3–Al2O3 feedstock leads to the complex (Al, Cr)2O3
phase coating. α-Phase is fully stabilized, which can attribute to
the plenty Cr2O3 in the fused feedstock.
(2) After sealing, the coatings present decreased porosity in the
topside. EDS analysis showed that sealant can indeed be brought
into the coatings. The sealing treatments significantly improve
the corrosion resistance as demonstrated by polarization, elec-
trochemical impedance spectroscopy and salt spray tests.
(3) The coatings with and without sealing treatment were heated at
600 °C for 30 min to determine the high temperature applicabil-
ity. Low volume shrinkage of the inorganic sealant was observed
after heat treatment. The sealed coatings exhibit nearly equal
anti-corrosion properties before and after heat treatment. The
heat treatment has a small effect on the corrosion behavior and
the sealing can inhibit the corrosion effectively.
Acknowledgments
The study is jointly supported by the National Nature Science Foun-
dation of China (51302299) and Shanghai Nature Science Fund Project
(13ZR1446000). Simultaneously, we are grateful to Prof. Shigang Xin
and Prof. Yuzhi Zhang for providing the support for this work.
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