383 Characterization of dark green passivation film on galvanized steel sheet

2013 Advanced Study Center Co. Ltd.

Rev. Adv. Mater. Sci. 33 (2013) 383-388
Corresponding author: Hong Wang, e-mail: Sddd69@163.com
CHARACTERIZATION OF DARK GREEN PASSIVATION
FILM ON GALVANIZED STEEL SHEET
Hong Wang
College of Mechanical and Electronic Engineering, Weifang University, Weifang, China
Received: October 17, 2013
Abstract. Galvanized Steel Sheet was dark green colored passivated in tetracid solution system
with acetic acid solution as stabilizer and silver salt solution as toner. The micro-morphology of
the film before and after passivation was observed by SEM. The composition of the film was
tested by EDS and its phase composition was analyzed by XRD. The corrosion resistance of the
passivated film was studied by neutral salt spray test. The results showed that the surface of the
specimen without passivation film was complete consecutive and coarse electrodeposited zinc
coating. The surface became homogeneous and smooth, and turned dark green with the uniform
colour and soft brightness but had chap structure. The film was composed of Cr, O, P, Zn, and a
small amount of Fe element. There were phases in the film, including CrPO
4
, Cr(OH)
3
, CrOOH,
Cr
2
O
3
, Zn(OH)
2
, 2ZnORCrO
3
RH
2
O, Zn
3
(PO
4
)
2
R4H
2
O, and Ag. Zinc coating, passivation film, and
Fe matrix combined closely, and no defects appeared such as crack. The total thickness of zinc
coating and passivation film reaches 12.423 m, and dark green passivation film is 1.734 m.
The passivation film could endure neutral salt spray test for 400 h, which met the demands of
national and enterprise standards.
1. INTRODUCTION
The blackishgreen passivation handicraft we
designed just has good compatibility with the
potassium chloride zinc plating handicraft one of
the green environmental protection electroplating
produces handicraft. The appearance of galvanized
sample treated by this passivation craft was
blackishgreen, colour was uniform and lustre was
gentle. The passivation film can endure neutral salt
spray test for 400 h. The passive film were
characterized in this paper to determine its
microstructure, phase composition and corrosion
resistance.
2. EXPERIMENTAL
2.1. Pretreatment and preparation of
substrate
No. 20 high quality carbon structural steel samples
were machined into rectangular blocks with 20202
mm
3
in size. Its superficial electroplated layer is
prepared by potassium chloride zinc plating
handicraft. The solution of the mixture (210~240)
gL
-1
KCl + (55~75) gL
-1
ZnCl + (25~30) gL
-1
H
3
BO
3
+ (12~18) mLL
-1
KZ-2000 Brightener was selected
as potassium chloride zinc plating solution. The
matrix was put into electrogalvanizing solution at
(5~50) C after degreasing and activating. The
solution pH was dominated by precise pH indicator
paper to 5.4~6.2. Current density was controled in
the range of 0.5 to 3.5Adm
-2
by rectifier. The
thickness of galvanized coating was determined by
TT210 coating thickness gauge no less than 15 m.
Chemical pure reagents were used in passiva-
tion solution. The formulation of blackishgreen pas-
sivation agent was 30 g/L CrO
3
+ 11 ml/L H
3
PO
4
+ 6
ml/L H
2
SO
4
+ 4 ml/L HNO
3
+ 4 ml/L stabilizer (The
main component was acetic acid) + 10 ml/L toner
(Silver salt solution) was selected as blackishgreen
passivation agent. The pH of blackishgreen passi-
384 H. Wang
vation agent was adjusted in the range of 1.0 to 1.5
by acetic acid [1,2].
After the galvanized sample was washed twice,
its surface light extraction was conducted in 1%
volume fraction of nitric acid, then it was washed by
clear water and deionized water in turn. Second,
the galvanized sample was Suspended motionless
in air for (60~120) s after it had been jittered slightly
in passivation solution tempering (20~30) C for
(35~60) s, then it was absterged by deionized water.
Finally, the blackishgreen passivation samples were
prepared successfully by isothermally dryed at
57 Cfor 15 min or atmospheric dryed.
2.1. Test method
During research of the blackishgreen colored
passivation films, the Surface morphologres of
coatings were identified by JSM-6700F field emission
scanning electron microscopy (FESEM) under the
test condition of accelerating voltage 3.0 kV, the
(a)
(b)
Fig. 1. Surface morphology of the specimens with
and without blackishgreen colored passivation film:
(a) Specimen without passivation film; (b) Specimen
with blackishgeen colored passivation film.
fracture surface morphology of coatings were iden-
tified by QUANTA200 environmental scanning elec-
tron microscope (ESEM). Elements of passivation
film were conformed by using X-ray energy disper-
sion spectrometer (EDS) through microdiffracion, line
and surface scanning under the test condition of
accelerating voltage 25 kV and emergence angle
35 degree. The phase composition was studied by
X-ray diffraction analysis (XRD) under the test con-
dition of grazing angle 0.0625 degree, copper target
(Cu-K

), pipe pressure 40 kV, pipe flow 35 mA, scan-

ning speed 3 degree per minute, and sample scan-
ning range from 30 to 90 degree. To evaluate the
corrosion protection of the blackish green passiva-
tion films on zinc-plated steel sheet, according to
GB/T6458-1986 (neutral salt spray, NSS), 5% NaCl
was atomized in a salt spray chamber at 35 C with
a solution of pH approximately 7. The tested sheets
were placed at an angle of 205 in the chamber,
exposed to the salt fog for a certain period.
3. RESULTS AND DISCUSSION
3.1. Surface morphologies and
composition analysis
Fig. 1 showed that the specimen without passivation
film had high surface roughness and many holes in
dendritic gap. Surface of the sample showed a
complete continuous layer of zinc electrodeposition.
The figure also showed that after passivation the
surface became clear smooth, roughness
decreased, but there were structural chap.
Fig. 2 and Table 1 showed that the Chemical
Constituents were different between the smooth
region A and the chap place B of passivation film.
The element contents of Zn and Fe were lower
significantly in the place of A than B, however the
contents of O, P, S, Cr were higher. The passivation
film was uniform dense in the smooth region, it was
thinner in the chap place and contained more Zn
and Fe.
3.2. Fracture surface morphology and
composition analysis
Fig. 3 showed that Zinc coating, passivation film
and Fe matrix combined closely, and no defects
appeared such as crack. The total thickness of zinc
coating and passivation film reaches 12.423 m,
and dark green passivation film is 1.734 m.
Passivation film was uniform and dense, galvanized
coating presented beautiful equiaxed zinc spangle.
Fig. 4 showed that the distribution intensity of
Chromium, oxygen, phosphorus was significantly
385 Characterization of dark green passivation film on galvanized steel sheet
Fig. 2. EDS patterns of different positions on blackishgreen colored passivation film in Fig. 1.
Element O P S Cr Zn Fe
Position A wt.% 35.73 4.42 2.24 8.35 48.06 1.21
at.% 66.41 4.25 2.07 4.78 21.86 0.64
Position B wt.% 14.40 1.67 0.85 2.51 79.02 1. 56
at.% 42.69 2.37 1.17 2.13 53.41 1.23
comparison wt.% 59.70 62.22 62.05 69.94 -64.42 -28. 93
at.% 35.71 44.24 43.48 55.44 -144.33 -92.19
Table 1. Element distribution comparison between the smooth region and the chap place of passivation
film.
Fig. 3. Fracture surface SEM morphology of
specimen with blackishgreen colored passivation
film.
higher and S was slightly higher in passivation film
than in zinc coating, however the distribution
intensity of Zinc, Chlorine was higher in zinc coat-
ing than in passivation film. Chlorine occured in the
galvanized layer, due to use of the electro-galva-
nized zinc chloride-based environmental protection
technology, the main group was divided into the bath
KCl, ZnCl, H
3
BO
4
, and thus Cl-residue presenced
in the zinc coating. Oxygen, sulfur, and phosphorus
in the zinc layer is a result of brightener added in
Zinc plating process while remaining in the
galvanized layer. Chromium, Oxygen, Phosphorus,
and Zinc element was significantly higher in the
passivation film than in the galvanized layer that were
composed of blackishgreen colored passivation film.
3.3. XRD analysis of passive film
Fig. 5a presents X-ray diffraction patterns of dark
green passivation samples. As shown, there were
Zn diffraction peaks in the diffraction pattern. We
believed that these peaks were produced by electro-
galvanized layer coated on the iron matrix. To this
purpose, detection of X-ray diffraction was done on
the galvanized samples without passivation. Test
386 H. Wang
results are shown in Fig. 5b. The six diffraction
peaks were all Zn peak in Spectrum 5b, and all the
diffraction peaks were relatively sharp, indicating
high crystallinity of Zn [3].
Jade5.0 software was used to analyze the data
of XRD experiments, The X-ray diffraction pattern
showed that there were green and gray blue sticky
precipitate CrPO
4
, Cr(OH)
3
, and CrOOH, dark green
crystal of chrome green Cr
2
O
3
, they did not dissolve
in water, which together formed gel compounds col-
(a) (b) (c) (d)
(e) (f) (g) (h)
Fig. 4. Fracture surface EDS surface scan analysis of specimen with blackishgreen colored passivation
film: (a) Fracture surface SEM morphology of specimen; (b) Chromium; (c) Oxygen; (d) Phosphorus; (e)
Sulfur; (f) Zinc; (g) Chiorine; (h) Iron.
Fig. 5. XRD patterns of the specimens with and without blackishgreen colored passivation film: (a) Specimen
with blackishgeen colored passivation film; (b) Specimen without passivation film.
loidal film of large network structure [4]. At the same
time,there were also excellent anti-corrosion
2ZnOCrO
3
H
2
O and Zn
3
(PO
4
)
2
4H
2
O which adsorbed
or embedded in the gel film. Other, there were metal
Ag that forned as the toner was reduced by
contacting with the metal Zn coating, its inclusion
in the passivation layer increased the black degree
of film, which photographic film as a very fine silver
grains scattered on a dark color in the same light-
sensitive film. It is like a very fine silver grain in pho-
387 Characterization of dark green passivation film on galvanized steel sheet
tographic film scattered on the light-sensitive film
displaying in black [5]. All these phases common
formed the dark green passivation film with high
corrosion resistance.
3.4. Neutral salt spray test of
passivation film
The results showed that: The time for corrosion prod-
ucts of specimen without passivation film appear-
ing was 8 h. High surface roughness and many holes
in dendritic gap that easily lead to corrosive media
enriching in the defect and manifested as localized
corrosion preferentially occurred [6]. The time for
corrosion products of specimen with blackishgeen
colored passivation film appearing was 400 h, al-
though the passive film was thinand there were chap
places, But it could effectively suppress the early
stages of corrosion of zinc coating and Change the
corrosion process [7]. Mao-zhong, et al. [8] studies
had shown iron metal enrichment in Zinc coating/
passivation film interface could inhibit the corrosion
reaction. When the corrosion medium corroded to
the coating surface through the passive film, Zn
2+
would react with water to Zn(OH)
2
that in turn de-
composed into ZnO and water, in other words, the
corrosion medium would oxide Zinc in the Zinc coat-
ing. Ferrous metals containing in the coating inhib-
ited the Zn(OH)
2
decomposition. When the concen-
tration was high enough, the reaction could be com-
pletely inhibited. Zn(OH)
2
that uniform coveraged at
the surface of the zinc coating which structure was
more compact relative ZnO inhibited the corrosion
reaction to some extent. In other wordes, the sur-
face cracked structure would enhance the corro-
sion resistance of blackishgeen colored passivation
film. It was shown that the blackishgeen colored
passivation film on the Zinc coating could signifi-
cantly improve the corrosion resistance of zinc coat-
ing. The time for white corrosion products of speci-
men with blackishgeen colored passivation film ap-
pearing was far more than the national standard
96 h and enterprise standard 200 h requirements.
From neutral salt spray test results, dark green
passivation film had high corrosion resistance,
because of the protective effect from magnesium
chromate and its hydrates of trivalent chromium and
hexavalent chromium. Trivalent chromium compound
acted as a framework in the dark green passivation
film by its insoluble in water and high strength.
Hexavalent chromium compounds film-forming
attached trivalent chromium compounds by its
soluble in water and soft. When the passive film
had mild injury, hexavalent chromium compounds
in the humid air was soluble in water and generated
chromic acid that reacted with the exposed zinc
coating. In other words, this was re-passivation to
achieve self-repair and maintain the corrosion
resistance of the membrane [2].
Divalent zinc ions in passive film came from the
zinc coating. Zinc dissolved in the interface layer
between metal and passivation solution by the
presence of acid and oxidation of chromic anhydride
after the zinc coating immersing passivation
solution. In this interface layer, pH rapidly increased,
and simultaneous hexavalent chromium reduced to
trivalent chromium that formed colloidal skeleton of
film in alkaline membrane, then the pH could not
too high, otherwise the colloidal membrane was
dissolved by hydrogen ions. It must be strictly
controled that the pH value in the range of 1 to 1.5
to form pH gradient in the film, in order to achieve
the balance between membrane dissolution in
solution side and membrane formation in Zinc
surface side, at the same time, black metal ions
also spreaded to the passivation film. This process
should be completed within 35~60 s, zinc layer
would be Continuous consumption that coule result
unnecessary losses if you continued to extend the
time. After the samples leaved the passivation
solution, the passive film proper stayed 60~120 s in
the air that was conducive to the continuation of the
surface passivation film forming reactions and
membrane thickening.
4. CONCLUSIONS
(1) The Appearance of blackishgeen colored passi-
vation film prepared by passivation technique devel-
oped was glossy, homogenous, dense dark green.
The time for white corrosion products of specimen
with blackishgeen colored passivation film appear-
ing in neutral salt spray test was far more than the
national standard 96 h and enterprise standard 200
h requirements.
(2) Sample surface before passivation presents a
complete electro-galvanized layer. After passivation
the sample surface becomes clear smooth, but there
were chaps, the chap place of passivation film was
thin and rich in zinc and iron, surface chaps did not
affect the corrosion resistance of passive film.
(3) Zinc coating, passivation film and Fe matrix
combined closely, and no defects appeared such
as crack. Dark green passive film mainly contained
chromium, oxygen, phosphorus, zinc, and
composed by CrPO
4
, Cr(OH)
3
, CrOOH, Cr
2
O
3
,
Zn(OH)
2
, 2ZnOCrO
3
H
2
O, Zn
3
(PO
4
)
2
4H
2
O, and Ag.
388 H. Wang
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