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 Mater. Res. Express 7 (2020) 086402 https://doi.org/10.1088/2053-1591/ababbe

PAPER

Titanium, zirconium and vanadium conversion coatings (TZVCCs) on

OPEN ACCESS
AZ91D magnesium alloy sheets
RECEIVED
27 June 2020
Wen Zhu1, Furui Chen1, Aihua Yi1, Zhongmiao Liao2, Wenfang Li1,3 , Kang Li1, Ken Chen1, Guofeng Liang1,
REVISED
28 July 2020
JinTao Guo1 and Qing Wu1
1
School of Material Science and Engineering, Dongguan University of Technology, Dongguan, Guangdong, 523000, People’s Republic of
ACCEPTED FOR PUBLICATION
3 August 2020 China
2
School of Materials and Energy, Guangdong University of Technology, Guangzhou, Guangdong, 510006, People’s Republic of China
PUBLISHED 3
12 August 2020
Author to whom any correspondence should be addressed.
E-mail: mewfl[email protected]
Original content from this Keywords: magnesium alloy, titanium/zirconium/vanadium, chemical conversion coating, corrosion resistance
work may be used under
the terms of the Creative
Commons Attribution 4.0
licence.
Any further distribution of
Abstract
this work must maintain This paper reports the preparation, characterization, and corrosion resistance of an eco-friendly
attribution to the
author(s) and the title of titanium/zirconium/vanadium-based conversion coating (TZVCC) on an AZ91D magnesium alloy
the work, journal citation
and DOI.
sheet. The TZVCC microstructure and composition were investigated by SEM, EDS, and XPS. The
corrosion behavior of treated and untreated magnesium alloy sheets was observed by potentiody-
namic polarization and EIS. The coatings are found to be rapidly formed on the alloy exterior within
90 s and optimal conversion treatment time at 50 s. The primary components of the TZVCC were
MgO, Mg(OH)2, V2O5, V2O3, MgF2, TiO2, ZrO2 and metal-organic complexation. The coating was
also shown to markedly enhance the corrosion resistance performance of magnesium alloys.

1. Introduction

Magnesium alloys show remarkable potential for various transportation, aviation, aerospace, digital-3C, and
biomedicine applications due to their high strength, light weight, low density, and strong biological
compatibility [1–6]. Magnesium alloys are electrochemically active, however, and vulnerable to corrosion in
natural environments with the service life of such alloys can be reduced substantially by material corrosion.
Therefore, it is urgent to improve corrosion resistance performance and practicality.
Among the numerous surface modification methods available today, chemical conversion coatings are
highly versatile corrosion inhibitor that can be easily applied and low in cost. As an intermediate layer, a
conversion coating enhances not only the corrosion resistance of a given material but also can improve metal the
adhesion to an overlaid paint layer. Traditionally, magnesium alloy conversion treatments have been prepared
using hexavalent chromium compound solutions [7]. Hexavalent chromate (Cr (VI)) is poisonous and
carcinogenic and produces environmentally hazardous waste products [8–10]. The use of Cr (VI) has been
completely prohibited in Europe since 2017 which has created an urgent demand for novel chromate-free and
ecological conversion treatment techniques [11]. Chromate-free treatments have been developed using several
compounds such as phosphate [12], permanganate [13], molybdate [14], vanadate [15], zirconate [16] and
combinations thereof [17]. However, there is currently no complete substitution available today due to the
color-free and corrosion-prone nature of most chromate-free conversion coatings.
Previous researchers have successfully developed golden Ti/Zr/V conversion coatings (TZVCCs) composed
of metal oxides (e.g., TiO2, ZrO2, V2O5 and Al2O3), metal fluorides (e.g., ZrF4 and AlF3), and metal organic
complexation on 6063 aluminum alloy [18–20]. TZVCC formed on aluminum alloy 6063 shows excellent
corrosion resistance and adhesion performance for epoxy coatings. In the present study, a similar TZVCC was
prepared on AZ91D magnesium alloy and its morphology, composition, and corrosion resistance investigated
by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), x-ray photoelectron
spectroscopy (XPS), and electrochemical corrosion workshop analyses.

© 2020 The Author(s). Published by IOP Publishing Ltd

Mater. Res. Express 7 (2020) 086402 W Zhu et al

Table 1. Elemental contents of AZ91D magnesium alloy.

Elements Al Zn Mn Si Cu Ni Mg

Wt/% 8.8 0.85 0.25 0.05 0.02 0.005 Bal.

2. Experimental process

2.1. Coating preparation

The substrate metal used in this study was AZ91D magnesium alloy, the main compositional elements are listed
in table 1. The specimens subjected to SEM and electrochemical testing were 20×20×2 mm in size and those
for XPS were 10×10×2 mm. The sheets were ground mechanically and sequentially with 400#, 800#, 1000#
waterproof SiC paper and then washed with distilled water. After degreasing samples in NaOH (40 g l−1) and
Na2SiO3 (40 g l−1) alkaline solution at 25 °C for 2 min, they were washed with distilled water and immersed in a
Ti/Zr/V-based aqueous solution composed of H2TiF6, H2ZrF6, NaVO3, and tannic acid (TA; at 2, 0.8, 2, and
2 g l−1, respectively) for treatments of 10, 30, 50, 70, and 90 s. The solution pH value and conversion temperature
were controlled to 2.8 and 30 °C, respectively. The treated sheets were washed once more with distilled water and
dried in a vacuum at 35 °C for 24 h.

2.2. Characterization methods

The morphology and composition of TZVCCs formed on treated sheets were investigated by SEM on a field
emission Nova-nano SEM-230 scanning electron microscope with EDS (FEI Co., Hillsboro, OR, USA). The
TZVCC layer thickness was measured using an optical film thickness meter (OPTM-A2, Otsuka Electronics Co.,
Ltd, Osaka, Japan). XPS was carried out on a Thermo K-Alpha instrument (Thermo Fisher Scientific Inc.,
Waltham, MA, USA) equipped with a standard Al-Kα x-ray source and a hemisphere electron energy analyzer in
an extreme vacuum chamber, with 10−9 bar base pressure. All spectral binding energies were corrected per the
reference standard binding energy of the C-1s peak at 284.6 eV.
Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization analyses were conducted
on a CHI660D electrochemical workstation which had three electrodes: a working electrode (area 1 cm2),
saturated reference calomel electrode and platinum foil counter electrode. The electrolyte was a 3.5-wt% NaCl
solution at room temperature. Specimens were first immersed in electrolyte for ∼30 min to obtain a stable open
circuit potential-time curve (OCPT). The EIS measurements were collected from 100 kHz to 0.01 Hz using a
5-mV amplitude sinusoidal voltage perturbation superimposed on a direct current potential set at the open
circuit potential (OCP). The obtained impedance data was fitted using ZVIEW software and a corresponding
equivalent circuit fitting diagram was accordingly established. Potentiodynamic polarization was performed at a
scan rate of 1 mV s−1 between −2.0 and −1.0 V in relation to the OCP. The electrochemical workstation
software was used to collect Ecorr and Icorr and all specimens examined separately on the workstation.

3. Results

3.1. TZVCC characterizations

3.1.1. Optical images and coating thickness
Optical photos and coating thickness of specimens treated in the Ti/Zr/V-based solution for various conversion
treatment times showed that specimen color gradually darkened from light-yellow to golden-yellow and
ultimately to brown-yellow as the treatment time progressed from 10 s to 90 s (figure 1). A golden-yellow-color
TZVCC was obtained at the 50 s time point. With further treatment beyond this point, the specimens became
browner and their compactness began to degrade. The thickness was observed to gradually increase with
increased treatment time, but beyond 50 s, this effect grew less pronounced.

3.1.2. SEM observations and EDS analysis

SEM images of the substrate and TZVCCs obtained at various treatment times showed that substrate surfaces
without any treatment contained several granules, long grooves, and scratches caused by brittle particles
fracturing and/or debris embedded in the substrate as it was processed (figure 2(a)) [21]. After 10 s of Ti/Zr/
V-based solution treatment, the defects remaining in the substrate surface decreased significantly as a thin
TZVCC layer developed on substrate surfaces (figure 2(b)). After a 30 s treatment, defects in the substrate surface
were completely covered by a coating, which contained several typical micro-cracks (figure 2(c)).
After a 50 s treatment, the coating was uniform and cracks, caused by internal stress from the shrinkage
during the drying process, were uniformly distributed on the substrate surface (figure 2(d)) [22]. Several white

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Mater. Res. Express 7 (2020) 086402 W Zhu et al

Figure 1. Thickness of specimens immersed in Ti/Zr/V based solution for different conversion treatment times of 10, 30, 50, 70 and
90 s.

granules were randomly dispersed on the coating surface, which were attributabled to adsorption of organic
complexes generated by aging of the conversion solution or to reactions between the substrate and surrounding
conversion fluid. Optical images of longer treatment times showed that, with increased treatment time to 70 or
90 s, the coating became more coarse due to deeper cracks and more white surface particles, which also drove
down the resulting corrosion resistance, as discussed below (figures 2(e) and (f)). In summary, the present SEM
analysis revealed that the optimal conversion treatment time for TZVCC formed on this magnesium alloy was
50 s.
EDS spectra were used to analyze the elemental compositions of the white granules on the TZVCC surfaces
(figure 3) and the white granules found to be composed of Mg, C, O, Ti, Zr, V, and F, from EDS analytical results.
The Mg proportion was as high as 53.31 at.% in these samples, which probably originated from the substrate.
The presence of the Ti, Zr, and V indicated that TZVCC played a role in the granule formation observed here
while the C and O signals indicated metal-organic complexation and oxide and/or hydroxide in the granules.

3.1.3. XPS analysis

The elemental chemical states in 50-s TZVCC specimens were determined by XPS analyses, which showed that
the TZVCC layer was mainly composed of Mg, O, C, Ti, Zr, V, and F (figure 4(a)). High-resolution Mg 2p, Ti 2p,
Zr 3d, V 2p, F 1s, C 1s, and O 1s elemental XPS spectra are shown in figures 4(b)–(h), respectively. The Mg 2p
spectrum was decomposed of three peaks located at 49.6, 49.7, and 50.0 eV, corresponding to Mg(OH)2, MgO,
and MgF2, respectively (figure 3(b)) [23–25]. Two components with binding energies at ∼457.7 and 458.2 eV
were curve-fitted from the Ti 2p spectrum and corresponded to Ti-complexation compounds and TiO2,
respectively [26–28]. The Zr region in the XPS spectrum of Zr 3d was composed of two peaks at 181.5 and
183.8 eV, which were attributed to Zr-complexation compounds and ZrO2, respectively [27–29]. The
photoelectron peak of V 2p derived from two different V oxidation states, with the two peaks at 515.83 and
516.28 eV, assigned to V2O3 and V2O5, respectively [29–32]. The F1s peak at 684.7 eV was attributed to MgF2
[24, 26, 27]. The observed C1s peak was divided into two peak components with 284.0 and 286.9 eV binding
energies. The first peak at ∼284.0 eV was caused by pollution during XPS measurement and the second can be
ascribed to –C*6H2– [23, 24]. According to these XPS analyses, the coating was composed of MgO, Mg (OH)2,
MgF2, V2O3, V2O5, TiO2, ZrO2, and the metal-organic complexes.

3.2. Corrosion resistance

3.2.1. Potentiodynamic polarization analysis
Potentiodynamic measurements were collected to evaluate the corrosion resistance of the substrate and
TZVCCs, obtained after various conversion treatment times in a 3.5% NaCl solution at pH 6.8. The specimen
polarization curves are shown in figure 5 and the corrosion potential (Ecorr) and corrosion current density (Icorr)
of different specimens, obtained by Tafel extrapolation [31], listed in table 2. The treatment generated significant
changes in both anodic and cathodic responses, compared to untreated specimens, especially at over 30 s of
treatment. The Ecorr values of TZVCC increased as conversion time extended from 10 to 50 s and decreased
slightly from 50 to 90 s, with the Icorr values showing opposing trends. The trends of Ecorr and Icorr for the TZVCCs

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Mater. Res. Express 7 (2020) 086402 W Zhu et al

Figure 2. SEM images of bare AZ91D magnesium alloy (a) and TZVCCs obtained with different conversion treatment times10, 30, 50,
70, 90 s(b)–(f), respectively).

Figure 3. SEM-EDS results of white granules formed on TZVCC surfaces.

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Mater. Res. Express 7 (2020) 086402 W Zhu et al

Figure 4. XPS spectra of the TZVCC: overview XPS spectra (a); spectra of Mg 2p; Ti 2p; Zr 3d; V 2p; F1s; C 1s and O 1s (b)–(h),
respectively).

were closely related to coating morphology (figure 2). The Ecorr value of TZVCC obtained at 50 s was −1.47 V,
which shifted to ∼130 mV in the positive direction from that of the untreated AZ91D substrate at Ecorr =−1.60 V.
The Icorr of the substrate was 23.58 μA·cm−2 while that of the 50 s TZVCC specimen was 2.45 μA·cm−2, i.e., about
one order of magnitude lower. This significant decrease in Icorr value suggested that the alloy’s corrosion resistance
was markedly enhanced by TZVCC treatment.

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Mater. Res. Express 7 (2020) 086402 W Zhu et al

Figure 5. Polarization curves of substrate and TZVCCs obtained with different conversion times, at 10, 30, 50, 70 and 90 s.

Figure 6. Nyquist plots of bare AZ91D and with TZVCC from different conversion time, at 10, 30, 50, 70 and 90 s.

Table 2. Parameters of polarization curves for substrate and TZVCC in figure 5.

Substrate 10s 30s 50s 70s 90s

Icorr (μA·cm−2) 23.58 23.76 13.69 2.45 3.04 5.96

Ecorr(V) −1.60 −1.56 −1.49 −1.47 −1.52 −1.53

3.2.2. EIS analysis

The corrosion resistance indicators of TZVCCs and AZ91D magnesium alloy sheets were further investigated
via EIS. The corresponding Nyquist plots showed that the untreated AZ91D plot included a capacitive arc in the
high-frequency region, which was created by metal dissolution in the corrosion process. There was also an
inductive arc in the low-frequency region caused by weakening of the oxide film due to anodic dissolution of
metals (figure 6) [33].
The equivalent circuit for the substrate and TZVCC/substrate was fitted according to the known
characteristics of the corrosion process [34–36] using ZsimpWin software (figure 7(a)). Here Rs was the solution
resistance, Q the capacitance of the partial protective oxide/hydroxide layer formed on bare substrate in
3.5% NaCl solution, Rct the resistance of charge transfer between the alloy surface and corrosive medium, RWE
the diffusion or Warburg impedance, Rc the resistance of the oxidation coating formed on the AZ91D

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Mater. Res. Express 7 (2020) 086402 W Zhu et al

Figure 7. Equivalent electrical circuit models for the bare substrate (a) and TZVCCs (b) immersed in 3.5%NaCl solution system.

Table 3. Electrochemical parameters obtained from Nyquist plots shown in figure 6.

Parameters

Specimens RS/Ω·cm2 Q n Rc/Ω·cm2 L1/H·cm2 RWE/Ω·cm2 L2/ F·cm2 Rct/Ω·cm2

Substrate 10.50 5.56×10−5 0.94 60.5 2994 68.53 297.6 74.31

10 s 8.37 2.86×10−5 0.85 1179 2.5×105 — — 1464
30 s 7.93 3.40×10−5 0.83 1244 1.24×104 — — 1384
50 s 8.96 2.74×10−5 0.84 1962 1.67×104 — — 1778
70 s 9.85 4.71×10−5 0.81 1897 2.28×104 — — 1227
90 s 8.42 3.56×10−5 0.82 1195 4.99×104 — — 1870

magnesium alloy surface when exposed to air, and L1 and L2 the induction behavior at high and low-frequencies,
respectively. The EIS spectra of TZVCC produced by various conversion times were also fitted by an equivalent
circuit (figure 7(b)), where Rc corresponded to conversion coating resistance while other parameters were
denoted similarly as those used above.
The parameter values for untreated and treated specimens extracted from Nyquist plots are shown in table 3,
where higher Rc and Rct represent better corrosion resistance [37–39]. The Rc and Rct values of all TZVCC
specimens were much higher than those of untreated AZ91D alloy sheets. TZVCC produced by a 50 s treatment
showed the highest Rc and Rct, which indicated that anodic dissolution was less likely in this sample substrate
than others, with the TZVCC appearing to have prevented the corrosive medium from penetrating the substrate
surface. The impedance value trend for different treatment times were in accord with the potentiodynamic
measurements and SEM analytical results. Thus, TZVCC effectively inhibited anodic dissolution of the
substrate, prevented corrosive material from entering the substrate surface, and altogether enhanced the alloy’s
corrosion resistance.

4. Conclusion

A golden-yellow TZVCC layer was successfully applied on an AZ91D magnesium alloy sheet by a chemical
conversion treatment using MgO, Mg (OH)2, MgF2, TiO2, ZrO2, V2O5, V2O3 and metal-organic complexation.
SEM images showed that a conversion treatment time of 50 s produced a coating with a relatively uniform
surface and thickness of ∼1.5 um. XPS analysis indicated that this 50-s TZVCC layers consists of Mg, C, O, Ti,
Zr, V, and F. Electrochemical analyses including potentiodynamic and EIS measurements showed that the
corrosion resistance of the AZ91D magnesium alloy improved considerably after this conversion treatment. The
TZVCC reported here thus represented a promising conversion coating treatment for safe and effective
magnesium alloy fabrication.

Acknowledgments

This study is financially supported by the Natural Science Foundation of Guangdong Province (Grant No.
2018A030310024), the Guangdong Basic and Applied Basic Research Foundation (Grant Nos.
2019A1515110466 and 2019A1515110913), the Novel Light Alloy and its Process Technology Key Laboratory of
Dongguan City, the Guangdong Research Center of High Performance Light Alloys Forming Technology and
funds from the Dongguan University of Technology (Grant Nos. GC300502-45 and GC300501-087).

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Mater. Res. Express 7 (2020) 086402 W Zhu et al

ORCID iDs

Wenfang Li https://orcid.org/0000-0003-2086-3914

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