Cathodic phosphate coating containing nano zinc particles on

magnesium alloy

NIU Li-yuan(牛丽媛)
Zhejiang Industry and Trade Polytechnic, Advanced Material Research and Development Center,
Wenzhou 325003, China
Received 12 June 2008; accepted 5 September 2008

Abstract: A technology for preparation of a cathodic phosphate coating mainly containing nano metallic zinc particles and phosphate
compounds on magnesium alloy was developed. The influence of cathodic current density on the microstructure of the cathodic
phosphate coating was investigated. The results show that the crystals of the coating are finer and the microstructures of the outer
surface of the coatings are zigzag at the cathodic density of 0.2−0.5 A/dm2. The content of nano metallic zinc particles in the coating
decreases with the increase of the thickness of the coatings and tends to be zero when the coating thickness is 4.14 μm. The cathodic
phosphate coating was applied to be a transition coating for improving the adhesion between the paints and the magnesium alloys.
The formation mechanism of the cathodic phosphate coating was investigated as well.

Key words: cathodic phosphate coating; magnesium alloy; formation mechanism

to accelerate the phosphatization of the magnesium alloy

1 Introduction
Studies on the surface treatments to prevent the
corrosion of the magnesium alloys have been developed
quickly in the recent years[1−3]. Chemical conversion
films of the magnesium alloy were widely used to the
base film of paint for ensuring good contact between the
paint and the magnesium alloy substrate[4]. The
chromate conversion treatment was a traditional method
to obtain anticorrosion film of metal[5−6]. However, in
the interests of pollution control, there is a tendency to
replace the chromium passivating baths by the
chromium-free treatment baths.
The phosphate coatings were the most promising
substitutes to the chromate coating that can create good
bonding between the paint film and the metal[7]. Based
on this consideration, the zinc phosphating process has
been widely used in the automobile industry as a
pretreatment method on the metal surface[8−9]. There
were some reports on the phosphating processes of
magnesium alloys being revealed in these years[10−12].
However, few investigations have been made for the
electrochemical phosphating process of the magnesium
alloys.
In the present study, a small cathode current was used
samples. In the previous studies, chlorate, sodium
metanitrobenzene sulphonate[13], nitrate[14−15] and
nitrite[16] were used to be the accelerating agents in the
phosphating baths. However, the poisonous accelerator
such as nitrate and nitrite gave out poisonous gases, and
the excessive accumulation of dissolution production of
accelerators would shorten the life of the phosphating bath.
In this test, the cathodic phosphate coatings were
prepared in a simple phosphating bath without
accelerators. Micro performance and adhesion
characteristic of the coatings were estimated and the
formation mechanism of the coating was investigated.
2 Experimental
AZ91D magnesium alloy samples with the size of
50 mm×50 mm×3 mm were used in the experiments.
The samples were degreased in a 10.5% KOH and rinsed
in de-ionized water to remove all the alkali before the
phosphating treatment. The cleaned specimens were then
treated in the phosphating bath and dried. The
phosphating temperature ranged from 20 to 30 ℃. The
detailed process in this study is listed in Table 1.
Two graphite plates (100 mm×50 mm×5 mm)
were applied to the anodes at two sides of the magnesium

Corresponding author: NIU Li-yuan; Tel: +86-577-88313017; E-mail: ccnly@sina.com

s366 NIU Li-yuan/Trans. Nonferrous Met. Soc. China 18(2008)
Table 1 Cathodic phosphating process of AZ91D magnesium alloy
Stage Operation Composition /(g·L−1) Condition
1 Degreasing Potassium hydroxide 10.5 5−10 min, 60−70 ℃
2 Water rinse 1 min, 20−30 ℃
3 Distilled water rinse 1 min, 20−30 ℃
85% phosphoric acid 15.5−17.8 pH 1.85−2.25
Zinc oxide 2.5−3.9 20−30 ℃
4 Cathodic phosphating
Sodium fluoride 1.5−1.8 Cathodic current density:
Sodium dodecylsulfate 0.03−0.05 0.2−0.5 mA/cm2
5 Water rinse 1 min, 20−30 ℃
6 Distilled water rinse 1 min, 20−30 ℃
7 Drying 10 min, 60−70 ℃

alloy plates. The zinc ions were provided by the supplement
of zinc oxide. The operation temperature was 20−30 ℃.
The adhesion tests were conducted according to the
ISO2409 standard. Adhesion of the paint was divided to
six classifications from 0 classification (best) to 5th
classification (worst) in the ISO2409 standard. For
comparison, the cathodic phosphate coatings (obtained
according to Table 1), the normal phosphate coatings[16]
and the chromate conversion coatings[5] were applied to
the transition coating between the paints and the
magnesium alloy.
3 Results and discussion
3.1 Morphology and composition of cathodic
phosphate coating
Fig.1 shows the SEM morphologies of the cathodic
phosphate coating on the AZ91D magnesium alloy
obtained from the phosphating bath at 0.5 mA/cm2. It can
be seen in Fig.1(a) that the diameter of the crystals of the
phosphate coating is 1−5 μm. The visible crystals in
Fig.1(a) are phosphate compounds of the coatings and
they are usually more than 10 μm in a normal
phosphating process. The metallic zinc particles cannot
be clearly seen because they are too small.
Fig.1(b) shows the cross-section image of the
cathodic phosphate coating. It can be seen that the
microstructure of the coating is zigzag, which helps to
improve the adhesion between the paint and the
magnesium alloy.
The composition of the phosphate coating is
determined by the energy spectrum and XRD pattern
(Fig.2). According to the energy spectrum, the coating
consists of Zn, P, O, Mg and Al. The XRD pattern shows
that coating consists of mainly metallic zinc particles and
various phosphate compounds including Zn3(PO4)2⋅4H2O,
AlPO4 and MgZn2(PO4)2.
The grain sizes of the coatings were measured
through the Sherrer equation. The FWHM (full wave at
half maximum) of the plane was used for the
measurement of the crystals size. In Fig.2(b), the FWHM
of the diffraction peak of the zinc plane (2θ=43.34˚) is
0.235, hence the average size of the metallic zinc and the
coating is about 28.2 nm.
Fig.3 shows the relation between the metallic zinc
content and the coating thickness. It can be seen that the
increase of the thickness from 0.53 to 4.14 μm causes a
decrease of the metallic zinc content from 46.4% to 0.
The external layer of the coating (beside magnesium
alloy base) has the highest concentration of the metallic
zinc particles. The outer layer of the cathodic phosphate
coating on the magnesium alloy mainly consists of the
phosphate compounds without zinc particles.

Fig.1 SEM morphologies of cathodic phosphate coating on 3.2 Influence of phosphate coatings on paint adhesion
AZ91D: (a) Surface image; (b) Cross-section image The results of the adhesion test of the paint coatings
 NIU Li-yuan/Trans. Nonferrous Met. Soc. China 18(2008) s367

Fig.3 Variation of zinc content with increase of coating

thickness

adhesion on the magnesium alloy. This is because the

Fig.2 Composition analysis of phosphate coatings formed from
baths at 0.5 mA/cm2: (a) Energy spectrum; (b) XRD pattern
on the phosphate coatings and chromate conversion
coatings are listed in Table 2. According to ISO2409, “0”
classification means the best adhesion performance.
Table 2 shows that the adhesion classifications of
the paints are “0” when the cathodic phosphate coatings
are the transition coatings of cataphoric paints (about 20
μm in paint thickness) and powder paints (about 60 μm
in paint thickness). Therefore, the cathodic phosphate
coating leads to an evident improvement of the paint
cathodic phosphate coating has the zigzag structure
(Fig.1(b)).
When the normal phosphate coatings and the
chromate conversion coatings are the transition coatings
of cataphoric paint, the adhesion classifications of the
paints are “0” and “1”, respectively.
Also, the adhesion of powder paints based on the
normal phosphate coatings of magnesium alloy is worse
(“1” classification). The crystals of the normal phosphate
coatings of the magnesium alloy[16] were larger than
those cathodic phosphate coatings.
The adhesion of the powder paints based on the
chromate conversion coatings of the magnesium alloy is
the worst (“2” classification) because the surface of
chromate conversion coating of the magnesium alloy is
not uneven.
3.3 Formation mechanism of cathodic phosphate
coating
In the process of the cathodic phosphating, there are
many micro-anodes and micro-cathodes on the surface of
the magnesium alloy.

Table 2 Results of adhesion tests

Paint Transition coating Classification (5 samples) Average classification

Cathodic phosphate coatings 0, 0, 0, 0, 0 0
Cataphoric paint
Normal phosphate coatings 0, 1, 0, 1, 0 0
(about 20 μm in thickness)
Chromate conversion coatings 1, 0, 1, 1, 1 1
Cathodic phosphate coatings 0, 0, 0, 0, 0 0
Powder paint (about 60 μm in
Normal phosphate coatings 1, 0, 1, 1, 2 1
thickness)
Chromate conversion coatings 2, 3, 2, 1, 1 2
s368 NIU Li-yuan/Trans. Nonferrous Met. Soc. China 18(2008)
On the micro-anode sites of the magnesium alloy
surface, Mg and Al are dissolved:
Mg → Mg 2 + + 2e (1)
3+
Al → Al + 3e (2)
At the same time, metallic zinc particles are
generated at the sites of the Mg atoms:
Zn 2 + + 2e → Zn (3)
At the micro-cathode sites, hydrogen is given out:
2H + + 2e → H 2 (4)
The reduction of Reaction (4) results in the increase
of local pH at the metal and solution interface, which
facilitates the precipitation of insoluble phosphate
compounds. Therefore, the formation reactions of
insoluble phosphates occur as follows:
3Zn 2 + + 2H 2 PO 4− + 4H 2 O + 4e →
Zn 3 (PO 4 )2 ⋅ 4H 2 O + 2H 2 (5)
Al3+ + PO 34− → AlPO4 (6)
Mg 2+ + 2Zn 2+ + 2PO 34− → MgZn 2 (PO 4 )2 (7)
A cathodic current accelerates the reduction reaction
on the surface of the magnesium alloy samples
(Reactions (3), (4) and (5)). The growth of the crystals of
the zinc particles and the phosphate compounds inhibits
each other. As a result, the coating crystals become finer.
There is an electrochemical replacement reaction
between magnesium and zinc, causing the deposition of
the zinc particles (Reactions (1) and (3)). With the increase
of the coating thickness, the surfaces of the magnesium
alloy substrate are covered gradually. Therefore, the
content of the zinc particles decreases with the increase
of the coating thickness and tends to be zero.
4 Conclusions
1) Finer cathodic phosphate coatings are formed on
the AZ91D magnesium alloy in the phosphating bath at
0.2−0.5 A/dm2. The optimal bath compositions are:
15.5−17.8 g/L of 85% phosphoric acid; 2.5−3.9 g/L of
zinc oxide; 1.5−1.8 g/L of sodium fluoride; 0.03−0.05
g/L of sodium dodecylsulfate.
2) Zn3(PO4)2·4H2O, AlPO4, MgZn2(PO4)2 and zinc
particles are the main compositions of the cathodic
phosphate coating. The average grain size of the metallic
zinc in the film is about 28.2 nm and the content of the
metallic Zn particles in the coating decreases with the
increase of the coating thickness.
3) The cathodic phosphate coatings were applied to
a transition coating of the magnesium alloy for
improving the adhesion between the paints and the
magnesium alloy. The results show that phosphate
coatings obtained at 0.2−0.5 A/dm2 exhibit the best
adhesion performance, which is suitable to not only the
cataphoric paint but also the power paint.
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(Edited by LI Xiang-qun)