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Surface & Coatings Technology 202 (2007) 391 397


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A comparative study of the corrosion protective properties of chromium and


chromium free passivation methods
Robert Berger a,, Ulf Bexell a , T. Mikael Grehk a , Sven-Erik Hrnstrm b
a
Dalarna University, Department of Materials Science, SE-781 88 Borlnge, Sweden
b
SSAB Swedish Steel AB, 781 84 Borlnge, Sweden
Received 22 January 2007; accepted in revised form 4 June 2007
Available online 12 June 2007

Abstract

Commercially available passivation methods for white-rust protection of hot-dip galvanized steel have been investigated. The passivations
were either based on trivalent chromium or chromium free. A chromate based conversion coating was used for reference. The treated panels were
tested with regard to white rust protection and paintability. The surface chemistry of the conversion coatings was monitored with scanning Auger
electron spectroscopy and X-ray photoelectron spectroscopy. Coating thicknesses were measured using Auger electron sputter depth profiling.
The passivations were applied with a thickness recommended by the supplier and thus showed large variation. The thickness of the chromium
free passivation (Cr-free) is approximately 75 nm. The coating contains the active ions; H3O+, Ti4+, Mn2+, Zn2+, PO3 4 . The passivation based on
trivalent chromium (Cr-III) is approximately 30 nm thick and contains the active ions; H3O+ Cr3+, PO3 4 , F. The chromate based passivation (Cr-
VI) is approximately 5 nm thick and contains the active ions Cr6+/Cr3+, F.
The Cr-free and the Cr-III passivations showed similar white rust protection in the corrosion tests. The corrosion resistance was good although
it did not fully reach the level of the Cr-VI passivation. The results from the tests of the painted panels showed that the powder paint worked well
on all three passivations. The solvent born paint worked best on the passivation based on trivalent chromium. The water born paint showed poor
resistance to blistering in the Cleveland humidity test for all three passivations. In this test the passivation with hexavalent chromium showed
slightly better results than the chromate free passivations.
2007 Elsevier B.V. All rights reserved.

Keywords: Corrosion; Galvanized steel; Passivation; SAM; XPS

1. Introduction The fact that Cr3+ is not as strong an oxidizer as Cr6+ makes it
less harmful for human exposure. However, trivalent chromium
The toxicity of hexavalent chromium is well-known. Workers compounds such as Cr2O3 and Cr(OH)3 could oxidize to
exposed to the substance on a daily basis are more likely to hexavalent chromium under certain conditions [16]. It could
develop lung cancer and allergy [1,2]. Despite extensive therefore be argued that the development of new passivations
research on other types of metal salts for replacing hexavalent should strive to towards chromium free products.
chromium as passivation for hot-dip galvanized steel (HDG) Inorganic pre-treatments for painting of galvanized steel are
there still does not exist any less harmful alternative. Instead new often based on phosphating in combination with a sealer. The
concepts, as for example, organic [37], inorganic [811] and phosphating process consists of dissolution of metal ions from
combinations of the both [1215], have been developed. In most the substrate and precipitation of metal phosphates on the
cases these concepts are based on barrier effects, where the metal surface. Firstly, the reaction begins when the acidic zinc
surface is protected from oxygen and water by a dense coating. phosphate solution comes in contact with the HDG surface and
One method for replacing hexavalent chromium in passiva- causes an electrochemical attack, as seen in Eq. (1).
tions for hot-dip galvanized steel is to use trivalent chromium.
Zn 2H Zn2 H2 1

Corresponding author. Tel.: +46 23 778660; fax: +46 23 778601. Under normal circumstances the HDG steel is alkaline cleaned
E-mail address: rbr@du.se (R. Berger). before a pre-treatment is applied. This process removes surface
0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.06.001
392 R. Berger et al. / Surface & Coatings Technology 202 (2007) 391397

carbon and most of the aluminum oxide present on a fresh HDG tertiary phosphates in the solution can be a combination of Zn3
surface [17]. This step is important because both aluminum and (PO4)2, Zn2Mn(PO4)2 and ZnMn2(PO4)2 [19].
carbon inhibit the zinc dissolution and the associated hydrogen In this contribution, two commercial chromate free passiva-
evolution [18]. The resulting HGD surface is covered with zinc tions and one chromate based passivation were investigated. A
oxide/hydroxide and small quantities of aluminum oxide/ passivation is different from a pre-treatment since the main
hydroxide. As the phosphating process progresses the surface purpose with the passivation is to offer temporary transport- and
oxide/hydroxides are dissolved as described in Eqs. (2)(5). storage corrosion protection of the surface, and not to function as a
pre-treatment before painting. However, in this case the chemistry
ZnOH2 2H Zn2 2H2 O 2 of the chromate free passivation solutions show similarities to a
standard phosphating pre-treatment solution and therefore the
ZnO 2H Zn2 H2 O 3 proposed dissolution/precipitation mechanisms, (1)(10), could
be used to describe the reactions which are taking place during
AlOH3 3H Al3 3H2 O 4 these passivation treatments. The reactions that take place during
the chromate treatment are summarized in Eq. (11) [20].
Al2 O3 6H 2Al3 3H2 O 5

3+ 3Zn Cr2 O2
7 2H 5H2 O3ZnOH2 2CrOH3
The Al ions can react with F ions in the phosphate bath
and form soluble fluoroaluminate according to Eq. (6). 11

Al3 6F AlF3
6 6 All passivations were evaluated in terms of their white rust
protection ability and also tested for compatibility towards
Due to the consumption of hydrogen ions in reactions (1) different paint systems. The ability of the passivations to
(5) the pH value increases as well as the concentration of metal withstand white rust formation was evaluated in stack tests and
ions close to the galvanized surface. Because of the increase in humidity chamber tests. These two tests are designed to
pH metal ions cannot stay soluble in the phosphate solution and resemble the environments which the HDG steel might be
thus enabling firstly primary phosphates to precipitate. exposed to during storage and shipping. The paint compatibility
of the passivations was evaluated in a Cleveland condensation
Me2 2H2 PO
4 MeH2 PO4 2 7 test and a Volvo Indoor Corrosion Test (VICT). The chemical
As soon as the solubility product for the secondary and composition of each passivation coating was monitored with
tertiary phosphates is reached in the near surface region they are SAM and XPS. The coating thicknesses and depth distribution
precipitated according to Eqs. (8)(10), see Fig. 1. of elements were measured with SAM depth profiles.

MeH2 PO4 2 MeHPO4 H3 PO4 8


2. Experimental
3MeH2 PO4 2 Me3 PO4 2 4H3 PO4 9
2.1. Sample preparation
3MeHPO4 Me3 PO4 2 H3 PO4 10
HDG steel sheets, skin-passed and non skin-passed, of
At this stage, phosphoric acid is released and can react with Sendzmir type (coating mass: 275 g/m2 and steel thickness:
the HDG surface again and form Me(H2PO4)2. The pH rise and, 0.5 mm) were supplied by SSAB Tunnplt AB, Sweden. The
depending on the metal ions present in the phosphate solution chromium free passivation (Cr-free), Passerite 5004 W,
and the process chemistry involved, different types of metal contained the active ions; H3O+, Ti4+, Mn2+, Zn2+, PO43, F.
phosphate precipitations are possible. The complexity of the The passivation based on trivalent chromium (Cr-III), Passerite
phosphate reaction is illustrated by the case where a chromium 6001, contained the active ions; H3O+ Cr3+, PO43, F. The
free, manganese modified, pre-treatment is used. Here, the chromate based passivation (Cr-VI), Candopass 960, contained
the active ions Cr6+/Cr3+, F. The oil (Anticorit 3802-39S) was
an anti-corrosion oil. Both the Cr-free and the Cr-III passiva-
tions were supplied by Henkel surface technologies, Germany.
The Cr-VI passivation was supplied by Candor, Sweden and the
oil was supplied by Fuchs, Germany. Cr-free and Cr-III treated
panels were prepared in the laboratory by Henkel, Germany.
Before application the panels were degreased in an alkaline
solution (Ridoline C72, 15 g/l, 60 C 5 s treatment time) in order
to improve the wettability of the surface, followed by rinsing in
deionised water and a drying step. The passivation was applied
by spin coating for 6 s at 550 rpm. Finally the samples were
dried at 75 C. In the production line, however, no degreasing is
Fig. 1. Surface and bath reactions taking place during the Cr-free and the Cr-III needed since the passivation is applied immediately after the
passivations. galvanizing step. The Cr-VI passivation was applied with spray
R. Berger et al. / Surface & Coatings Technology 202 (2007) 391397 393

and squeeze technique in the HDG production line at SSAB


Tunnplt AB, Sweden. The oil was applied with a cloth at the
laboratory in SSAB Tunnplt AB, Sweden. The coverage of the
Cr-VI passivation was approximately 10 mg Cr/m2 and the
coverage of the oil was 0.81.0 g/m2. All paints and paintjobs
were provided by Becker Industrial Coatings, Sweden.

2.2. Test methods

The corrosion protective ability of the passivations was


investigated in a wet pack test and a humidity test. The samples
(100150 mm) in the wet pack test were pressed together using
paper clips. 0.3 ml deionised water was applied between each steel
sheet. The samples were stored in an excicator at room temperature Fig. 2. Test cycle for Volvo indoor corrosion test.
at 90% relative humidity. The contact surfaces were visually
examined for white rust after 1, 2 and 3 weeks, respectively. Once a in order to separate metal from metal oxide/hydroxide components
sample had been examined it was discarded. In the humidity test, in the sputter depth profiles. The XPS experiments were performed
freely hanging, HDG samples (100150 mm) were placed in a using a PHI Quantum 2000 instrument with monochromatic Al
humidity chamber. The temperature in the chamber was 40 C and K radiation (1486.6 eV). Detailed spectra were recorded for the
the relative humidity was 100%. The samples were visually relevant elements. The peaks in the spectra were then fitted and
examined for white rust after one, two and three weeks, respectively. analyzed using the software FitXPS [21]. Voight functions and
The corrosion protective ability of the painted samples was parabolic background signals were employed for all curves used in
investigated with two techniques, Cleveland condensation test the fit. All spectra were calibrated so that the binding energy of the
and Volvo indoor corrosion test (VICT). The following three C 1 s peaks was 284.8 eV.
paint systems were evaluated
3. Results and discussion
Polyester powder paint, free from triglycidyl isocyanurate
(TGIC). 3.1. SAM
Solvent born, oven cured, alkyd paint with primer (KE301)
and topcoat (DJ300). The SAM depth profiles in Fig. 3. show large variations in the
Water born, air dried, alkyd paint with primer (AD621) and surface film thickness for the passivated samples. The profiles
topcoat (AG650). were recorded on top of dendrite arms, on non skin-passed
samples, prior to exposure to a corrosive environment. The
In the Cleveland condensation test painted panels were thickest film was found on the Cr-free passivation. This film was
exposed to continuous condensation from water according to approximately 75 nm thick, whereas the Cr-III film was 30 nm
ISO 6270. The test ran for up to 1000 h. Blistering of the paint was thick. The film on the Cr-VI sample was barely 5 nm thick and the
examined according to SS-EN-ISO 4628-2. Paint adhesion was oxide film on the blank HDG sample was approximately 3 nm.
tested with grid scribe lines which rendered 25 squares of 1 mm2 Depth profiles recorded on the passivated samples after three
in size. Adhesive tape was used to remove poorly attached paint weeks wet-pack testing showed no significant changes neither in
before evaluation. The VICT test (Volvo Corporate Standard film composition nor in film thickness, except for the areas stained
1027, 1375) is a mild cyclic corrosion test that runs for twelve by white rust, which showed predominant Zn and O contributions.
weeks. Every 84th hour the samples were taken out of the test The variation in chemical composition with depth obtained from
chamber to be submerged in sodium chloride solution (1 wt.%) the SAM depth profile measurements showed that the outermost
for one hour. In the test chamber the samples were exposed to surface of the sample treated with the Cr-free solution predomi-
cyclic variation of the relative humidity, alternating between 90% nantly contained oxygen, titanium and phosphorus. These three
and 45%. The temperature was kept at 35 C, see Fig. 2. elements were present in the entire surface layer. Manganese was
detected 10 nm from the outermost surface. Therefore, the
2.3. Surface analyzes precipitation of manganese complexes must have stopped before
the last titanium and phosphate complexes precipitated, which were
SAM spectra were recorded with a PHI 660 scanning Auger the last to precipitate. Zinc could not be detected on the surface.
microprobe. The accelerating voltage was 10 kV and the beam Instead, most of the zinc (Zn2+) complexes were located at the
current was 400 nA. Depth profiles were obtained using 3.5 or coating/substrate interface approximately 70 nm from the surface.
1.5 kVAr+ ion sputtering. The sputter rate was calibrated utilizing The depth profiles from the Cr-III treated sample showed a
the known thickness of a Ta2O5 sample and measuring the time it predominance of oxygen and chromium on the surface.
took to sputter through the oxide (when the O-signal had decreased Phosphorus was also present on the surface. The Zn2+ profile
to half of its initial value). Computer software from PHI-Matlab showed a similar behavior to the one in the Cr-free sample, and
was used to evaluate the SAM data and a LLS routine was used peaked at the coating/substrate interface.
394 R. Berger et al. / Surface & Coatings Technology 202 (2007) 391397

Fig. 3. SAM depth profiles recorded on non skin-passed passivated HDG steel. The sample labeled Blank HDG steel was not passivated but had been organically
cleaned for 2 min in acetone and methanol successively before the analysis.

The chromate free samples had only insignificant amounts of resolve and identify different compounds. For each surface
aluminum on the surface. Most of the aluminum was probably treatment, two spectra were recorded. One before corrosion
removed during the degreasing that took place before the testing (lower) and the other recorded after tree weeks of wet-
passivation was applied [17]. Remaining aluminum oxide/ pack testing (upper).
hydroxide could have been dissolved in the chromate free Differential surface charging was observed on all passivated
passivation solutions. surfaces during the XPS measurements. This is not uncommon
The Cr-VI sample had substantial amounts of carbon on the for insulating layers on top of conducting metals [22]. The main
surface. It is likely that the carbon comes from contaminations C 1s peak for Cr-free, Cr-III and Cr-VI was located at 285.9,
accumulated during the handling of the material in the steel mill. 286.4 and 285.6 eV, respectively. A rough compensation for the
The surface layer on the chromated sample is approximately charging effects was carried out by shifting the energy scale so
5 nm thick and is constituted mainly of aluminium oxide and that the main C 1 s peak obtained a binding energy of 284.8 eV.
smaller amounts of chromium and zinc compounds. This type of correction is by no means an absolute energy
The fourth sample in Fig. 3. shows the composition of blank calibration [23] and was used only to get an estimate of the BE.
HDG steel which was ultrasonically cleaned for 2 min in For this type of measurements it is instead the energy shifts
acetone and methanol successively before the analysis. between individual peaks that are of importance.
The blank HDG sample is covered by a 3 nm thick aluminium Three peaks were used in order to obtain a satisfactory fit for
oxide film and metallic aluminium was found at the oxide/substrate the O 1s spectra. The low energy peak, O(1), is believed to
interface. The sample showed only about 5 at.% of Zn2+ on the originate from metal oxide [24,25]. O(2) is ascribed to
surface, and the signal did not peak further away from the surface. hydroxide and oxygen in phosphate compounds in the
These results indicate that during the chromate free passivation phosphate containing passivations Cr-free and Cr-III [26]. The
treatments zinc has initially dissolved from the surface and then high energy peak, O(3), is attributed to oxygen in water. The
later precipitated at the interface between the metal and the exact positions for the three peaks are shown in Table 1. There
passivation layer. were distinct energy shifts between these three peaks from one
spectrum to another. As mentioned earlier, this could be
3.2. XPS explained in terms of differential surface charging effects. The
relative peak positions were, however, more or less consistent in
Fig. 4 shows detailed XPS spectra of the O 1s and the Cr 2p3/ all spectra. Therefore it still makes sense to compare individual
2 peaks, respectively. After subtracting a parabolic background peaks from different passivations. Only the peak representing
each spectrum was fitted with Voight-shaped curves in order to water deviated from this observation, i.e., it did not display the
R. Berger et al. / Surface & Coatings Technology 202 (2007) 391397 395

Fig. 4. XPS spectra showing normalized O 1s and Cr 2p3/2 photoelectron peaks, respectively. Two spectra were recorded for each passivation method. The lower curves
show data recorded before wet-pack testing and the upper curves represent data recorded on samples exposed to 3 weeks of wet-pack testing.

same energy separation towards the other two peaks in the peak decreased by roughly one third after the wet-pack test.
different spectra. This could be explained by the fact that the The decrease was most likely due to leaching and subsequent
systems studied are very complex. It is likely that there is crystal reduction of soluble Cr6+ within the chromate coating. The
water in the films, as well as water molecules incorporated in ability to distribute Cr6+ , to cut-edges and defects in the film,
the amorphous films in some manner, which could lead to long time after the coating has been applied and cured is a
broadening and shift in BE of the water peak. prerequisite for the self-healing mechanism of chromate
The O 1s spectrum for the Cr-VI treated surface is dominated coatings. The final peak, Cr(3), is located at almost the same
by hydroxide. There were also significant amounts of oxide and binding energy as the chromate peak. However, the shift
water on the surface and the spectrum bares resemblance to between Cr(3) and Cr(1) is approximately 1.7 eV, which is
corresponding spectra recorded on blank, alkaline degreased 0.4 eV smaller than the shift observed between Cr(1) and Cr
HDG samples [17]. This proves that the Cr-VI passivation only (2). This deviation indicates that Cr(2) and Cr(3) have different
slightly modifies the surface layer of the HDG steel, which is in origins and Cr(3) is therefore not believed to represent Cr6+ ,
agreement with the SAM results. The two chromate free instead this peak could come from chromium phosphate and
surfaces on the other hand are both dominated by thick metal fluoride compounds present in the outermost surface of the Cr-
oxide films, which are believed to act as diffusion barriers for III sample [25].
oxygen and water, thereby lowering the rate of oxygen
reduction on the metal surface. Phosphate complexes are also
found on the chromate free surfaces and these further contribute Table 1
to the stability of the film. Only small amounts of water are XPS binding energies for the O1s component
detected on the Cr-free and Cr-III surfaces, which could be a Treatment Time for measurement Binding energy
result of the drying step during the sample preparation. O(1) O(2) O(3)
The Cr2p3/2 spectra were fitted with three peaks, Cr(1)
Cr-free Before wet-pack test 531.3 532.6 533.8
577.0 (577.5 for Cr-III) 0.1 eV, Cr(2) 579.1 0.1 eV and Cr After 3 weeks wet-pack test 531.3 532.6 533.8
(3) 579.2 0.1 eV. The low binding energy peak, Cr(1), which Cr-III Before wet-pack test 531.3 532.7 533.5
was dominant in all spectra is likely to have contributions from After 3 weeks wet-pack test 531.5 532.9 533.7
Cr2O3, CrOOH and Cr(OH)3. The hexavalent chromium, Cr-VI Before wet-pack test 530.2 531.7 533.0
After 3 weeks wet-pack test 530.2 531.6 533.1
found on Cr-VI treated samples, is represented by Cr(2). This
396 R. Berger et al. / Surface & Coatings Technology 202 (2007) 391397

Fig. 5. Graphs showing the amount of white rust developed during the wet pack test (upper) and the humidity test (lower) on (a) non skin-passed and (b) skin-passed
HDG surfaces, after 1, 2 and 3 weeks respectively. The SEM inserts show the general surface morphology for skin-passed and non skin-passed surfaces.

The results from the XPS measurements show one important The alkaline degreasing that takes place before the chromate
distinction between the Cr-VI and the two chromate free free passivations are applied removes most of the surface carbon
passivated surfaces. The Cr-VI treated samples display active and aluminium oxide from the galvanized surfaces. This
transformation of the surface chemistry, i.e. reduction of Cr6+
species, when exposed to a corrosive environment. The Table 2
chromate free films on the other hand show no changes in Results from the Cleveland condensation test using ISO 4628-2
surface chemistry, and in terms of corrosion protection the PE powder Solvent born alkyd Water born alkyd
chromate free films have to rely merely on barrier protection paint paint paint
and chemical stability. Cr-free Adhesion 1 0 1 0
Blisters 2 00 44 54
Blisters at 00 51 44
3.3. Corrosion tests
scribe
Adhesion after 0 5 5
The results from the wet-pack test and the humidity test are seen test
in Fig. 5. Both Cr-free and Cr-III passivations gave better white rust Coating 48 79 99
protection on skin-passed surfaces compared to non skin-passed thickness (m)
Cr-III Adhesion 0 1 0
ones. In the wet-pack test these two passivations were roughly
Blisters 00 24 55
equally efficient and the amount of white rust developed after three Blisters at 00 12 00
weeks was approximately five times more (20%) on non skin- scribe
passed surfaces compared to skin-passed (4%). This trend was Adhesion after 0 3 5
consistent with the humidity chamber test as well. Although in this test
Coating 85 84 106
test the Cr-free passivation was more effective than Cr-III. The
thickness (m)
amount of white rust developed after three weeks in the humidity Cr-VI Adhesion 0 1 0
chamber on skin-passed and non skin-passed surfaces treated with Blisters 00 44 33
Cr-free passivation was 1 and 3%, respectively, compared to 3 and Blisters at 00 42 00
15%, respectively, for samples treated with the Cr-III passivation. scribe
Adhesion after 0 5 5
The panels treated with the Cr-VI passivation showed very good
test
resistance to white rust corrosion both in the wet-pack and the Coating 56 76 96
humidity test and these panels were therefore practically free from thickness (m)
white rust stains. The anti-corrosion oil provided good protection in 1
0 = good, 5 = poor.
the wet-pack test but failed in the humidity chamber since the oil 2
00 = low blister density-small blister size, 55 = high blister density-large
was rinsed away and the panels thus became heavily corroded. blister size.
R. Berger et al. / Surface & Coatings Technology 202 (2007) 391397 397

Table 3 cycled through high and low humidity, which enabled the
Results from Volvo indoor corrosion test system to recover during the dryer periods, whereas in the
PE pulver Solvent born alkyd Water born alkyd Cleveland test the humidity was always 100%.
paint paint paint
Cr-free Surface Ok Ok Ok 4. Conclusions
Scribe 0.5 mm 1 0.5 mm 1 Ok
Cr-III Surface Ok Ok Ok
HDG steel surfaces passivated with two chromate free
Scribe Ok Ok Ok
Cr-VI Surface Ok Ok Ok passivations, Cr-free and Cr-III, have been characterized and
Scribe Ok Ok Ok evaluated in terms of chemical composition, white rust
1
Propagation of corrosion front from scribe. protection, and paintability. A standard chromate containing
passivation for HDG steel was used for reference. The study
ensures that the surface chemistry of the skin-passed and non revealed that
skin-passed surfaces is very similar prior to the application of
the passivation. The fact that the skin-passed surfaces The chromate free passivations produced relatively thick and
experienced better corrosion properties than the non skin- stable oxide/phosphate coatings on the metal surface. No
passed surfaces for the chromate free passivations can therefore evidence indicated that these surfaces possessed self-
not be correlated to dissimilarities in the surface chemistry, i.e. healing mechanisms, as is the case for the Cr-VI surface.
different acid-base properties, of the samples. It has been shown The chromate free passivations tested could be used to
that increased surface roughness improves the fineness of replace chromate conversion coatings in mild corrosive
conventional phosphate pre-treatment coatings [27]. There is environments. Though extra care must be taken since these
however no documented evidence that the surface morphology surfaces will lack self-healing properties and thus become
should have any influences on the performance of thin sensitive to scratching.
passivation systems, as the ones studied in this paper. A powder based polyester paint could be used with the
Painted panels were evaluated in a Cleveland condensation test chromate free-pretreatments with satisfactory results.
and in a VICT. Three different paint systems, sintered polyester
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