Colloids and Surfaces A 546 (2018) 221–236

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Colloids and Surfaces A

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

Current status, opportunities and challenges in chemical conversion coatings T

for zinc
⁎
Zhiqiang Gaoa,b, Dawei Zhanga, , Xiaogang Lia, Sheming Jiangb, Qifu Zhangb
a
Corrosion and Protection Center, University of Science and Technology Beijing, Beijing, China
b
National Engineering Laboratory of Advanced Coating Technology for Metal Materials, Central Iron & Steel Research Institute, Beijing, China

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: The susceptibility of Zn-based materials to corrosion in an aggressive environment limits their broad applica-
Corrosion tions. Innovative conversion treatment is the most interesting approach for enhanced corrosion performance of
Conversion coating zinc. This review covers recent research that has led to advances in conversion coating technology for zinc;
Zinc including the application of contemporary methods for chemical conversion coating, the establishment of a
Molybdate
corrosion protection framework for zinc, the illumination of processing control effects, and the attempts at the
Silane
inhibition mechanisms of zinc by coatings. This review drawing from many sources provides an impartial focus
Degradability
on new achievements. The environmentally acceptable conversion coating is reviewed in detail. This review also
covers engineering application aspects, including cost-effectiveness technology and process productivity. Finally,
future prospects and present challenges in the field of conversion treatment are reviewed, identifying the demerit
of each technique, meanwhile attempting to also identify future developments and directions.

1. Introduction
There has been a significant amount of research undertaken in
chemical conversion coatings when various comprehensive reviews
were written in this area. Table 1 illustrates the reported works from
selected authors. Previous reviews examined the effectiveness of con-
version coatings for several metal substrates involving Zn, Al, Mg and
their alloys. From these reviews, large amounts of useful information
can be abstracted and be used to focus on the application of conversion
coatings for zinc-based materials. It is essential for zinc protection by
establishing the strategies for more efficient treatment in engineering
applications.
Zinc and zinc-based alloys have been widely applied for the corro-
sion protection of metal substrates [10,11]. However, zinc-based alloys
pose a serious, unique challenge for corrosion protection as they do not
form a spontaneously passivating oxide film for retarding corrosion in
an aggressive environment, unlike other active light metals such as Al
and Ti. Several studies have focused on the development of an effective
method to inhibit the initial corrosion of zinc; most of the reported
methods involve the preparation of a coating or some functional barrier
layer on the surface for isolating base materials from corrosive en-
vironments [5,12]. Fig. 1 summaries various surface treatment techni-
ques established for protection of zinc. Among these technologies,
chemical conversion coatings are highly promising because of their

⁎
Corresponding author at: University of Science and Technology Beijing, Corrosion and Protection Center, Beijing, China.
E-mail addresses: gq770130@126.com (Z. Gao), dzhang@ustb.edu.cn (D. Zhang).

https://doi.org/10.1016/j.colsurfa.2018.03.018
Received 2 January 2018; Received in revised form 23 February 2018; Accepted 6 March 2018
Available online 11 March 2018
0927-7757/ © 2018 Elsevier B.V. All rights reserved.
Z. Gao et al. Colloids and Surfaces A 546 (2018) 221–236

Table 1 protection efficiency of the coating is considerably enhanced when the

Reviews for conversion coatings written by named authors. corrosive medium cannot easily penetrate into the metal surface
through coating defects such as voids or cracks. In this case, one of the
Author Year Type Substrate Ref.
biggest challenges in the field of conversion coatings is to produce
A. Amirudin 1996 phosphate coating steel [1] defect-free coatings with uniform coverage [6]. There now exists much
J.E. Gray 2002 chromate coating Mg [2] more comprehensive information on these characteristics. In the fol-
phosphate coating
lowing relevant sections these information will be discussed in detail.
fluorozirconate coating
stannate coating Hence, this review highlights important contributions during the de-
rare earth coating velopment of conversion coatings for zinc; and then upgrades the
cobalt coating conversion coating technology.
W. J. van Ooij 2005 silane coating Zn, Al, Mg, Cu, Ni [3]
cold-rolled steel
hot-rolled steel 1.1. Chromate coatings
stainless steel

Zou Zhongli 2007 vanadate coating Al, Mg [4] Chromate coatings have been widely used for the corrosion pro-
D. E. Walker 2008 molybdate coating Zn [5] tection of reactive metals such as Zn, Mg, and Al [22,23]. Chromating
X. B. Chen 2011 chromate coating Mg [6] solutions are well known to contain hexavalent chromium Cr(VI),
phosphate coating
predominantly CrO42― ions formed in an acidic solution. The formation
fluoride coating
stannate coating of chromate coatings on zinc-based materials mainly involves the oxi-
rare earth coating dation of the zinc matrix in bath solutions with the simultaneous
hydrotalcite coating transition of the zinc ions to solution and evolution of hydrogen. The
ionic liquid coating formation process of chromate conversion coating is schematically in-
multi-elements coating
dicated in Fig. 2. The reactions taking place during the whole chro-
vanadate coating
organic coating mating process can be categorized into several groups. A universal re-
action is expressed in Eqs. (1) and (2), which is mostly accepted in the
S.H. Zaferani 2013 silane coating Zn, Al, Mg, Cu [7]
Bing Liu 2015 phosphate coating metallic [8] field.
biomaterial
Anil Mahapatro 2015 bio-functional nano- metallic [9]
2CrO42― + 16H+ + 3Zn → 2Cr3+ + 3Zn2+ + 8H2O (1)
coatings biomaterial
Cr3+ + 3OH― → Cr(OH)3↓ (2)

The microstructural characterization of chromate coatings

Fig. 1. Surface treatment techniques.

comparatively low cost and easy implementation, which has been

widely adopted for the corrosion protection of zinc in industrial settings
[13–18]. In addition, such coatings may form a good base for sub-
sequent organic top coatings [6,19–21].
Several studies have reported the conversion coating technologies.
The characteristics of conversion coatings have been extensively in-
vestigated including composition, structure, physical, and mechanical
properties, solubility in ambient systems, porosity, hardness, abrasion
resistance, adhesion to the base metal or top coating, dyestuff sorption
ability, and heat or low-temperature resistance, as well as corrosion
resistance and protective properties of zinc substrates. The protective
properties of coatings depend on the type of base metal and condition of
its surface as well as the thickness and integrity of the coating. The Fig. 2. Schematic representation for the formation of chromate conversion coatings.

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Z. Gao et al.
Fig. 3. AES depth profiles for a chromate coating on zinc with 60 s dipping (a) and high
resolution XPS spectra of Cr 2p3/2 with 30 s dipping (b). Precusor solution consisting of
200 g/L Na2Cr2O7, 10 g/L H2SO4, pH 1.1–1.3 [24].
performed using AES and XPS is shown in Fig. 3 [24]. The chromate
layers contain hexavalent and trivalent chromium oxides or hydroxides.
Fig. 4 gives the typical chromate conversion coated surfaces [24]. The
Fig. 4. Typical morphologies of chromate coatings obtained with different dipping time: a 5 s, b 10 s, c 30 s, d 60 s. Precusor solution consisting of 200 g/L Na2Cr2O7, 10 g/L H2SO4, pH
1.1–1.3 [24].
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Colloids and Surfaces A 546 (2018) 221–236
emergence of several microcracks is probably attributable to that the
tensile stress increases with the thickness of the coatings [5,25]. The
cracked surface of coatings leads to porosity and allowing corrosive
species to react directly with the substrate. Thus, coating thickness is
not always a reliable indicator of corrosion resistance.
The present investigation reveals that the plating additives critically
influence the microstructure of both the galvanized coatings and
chromate layer [26]. The corrosion resistance of the coatings can be
enhanced by suppressing the {100} crystallographic planes of zinc and
minimizing defects along the zinc/substrate interface, and by pro-
moting formation of an amorphous oxide layer in the chromate film.
The observation should enable development of enhanced corrosion
resistant coatings via micro/nanostructural tailoring and engineering.
The protection efficiency of chromate conversion coatings is related not
only to their ability to act as effective barriers but also to self-healing
properties at the damaged sites of the coatings [27–29].
Despite the toxicity of chromate coatings, these coatings are still one
of the best intermediates for surface treatment [30,31]. However, car-
cinogenic effects of chromate compounds have led to serious hazardous
environment and safety issues; hence, there is an immense interest in
the development of a Cr(VI)-free, effective replacement for chromate
conversion coatings [5,27]. Several papers are available in the litera-
ture dealing with Cr(III)-based conversion coatings for zinc [32–34].
Nevertheless, the self-healing ability of Cr(III) conversion coatings is
not comparable to chromate coatings. Meanwhile, several attempts
have been made to develop Cr-free, environmentally friendly alter-
natives instead of chromate coatings. Some of the possible alternatives
demonstrate considerable potential if certain improvement is made,
and the possible mechanisms involved are understood in detail [35].
1.2. Phosphate coatings
Several authors have clarified possible formation mechanisms for
phosphate conversion coatings on zinc surfaces. Table 2 summarizes the
typical formation mechanisms for phosphate conversion coatings on
zinc-based materials. The first type of phosphating solution is based on
Z. Gao et al.
Table 2
Type of the phosphate coatings classified by formation mechanisms.
Type Primary bath composition Typical reaction
1 Alkali metal phosphate 4Zn + 4NaH2PO4 + 2O2 → Zn3(PO4)2 + ZnO + 2Na2HPO4 + 3H2O
2 Me(H2PO4)2 4Me2+ + 3H2PO4− ⇄ MeHPO4 + Me3(PO4)2 + 5H+
(Me: Zn, Fe, or Mn) Zn + Me(H2PO4)2 → ZnMe(HPO4)2 + H2
primary alkali metal phosphate. As the coatings are produced on the
zinc surfaces with the direct participation of the basis metal in the
process, such phosphate coatings are known as actual conversion
coatings. The second type of phosphating solution is primarily based on
metal phosphates such as Me(H2PO4)2 (Me mainly represents Fe, Zn,
and Mn). Such coatings are formed by the contribution of the metal
cations present in the solution itself, which are known as pseudo-con-
version coatings. The second type of phosphate coatings as a prevailing
technology has attracted considerable attention for the development of
excellent protection coatings via the optimization of their composition
and crystalline structure, especially those formed at room temperature
[36].
A model for the formation of the second type of phosphate coating is
indicated schematically in Fig. 5. The formation of phosphate coatings
on zinc-based materials mainly involves the oxidation of zinc surfaces
in bath solutions with the simultaneous transition of zinc ions to solu-
tion, followed by the evolution of hydrogen. The change in pH alters the
dissociation equilibrium of which leads to the formation of HPO42― and
PO43−. The localized change in the concentration of the supersaturated
reacting ions with poor crystallinity, including Zn2+, Me2+, HPO42―,
and PO43−, leads to a precipitation of these reacting ions from the so-
lution interface on the zinc surface. Thus, the formation of phosphate
coatings apparently depends on sufficient concentrations of Zn2+,
Me2+, HPO42―, and PO43− ions built up at the interface during im-
mersion.
However, compared to phosphate coatings on steel, it is appropriate
to perform phosphating for zinc and its alloys in a slow phosphating
solution, whereby the zinc matrix dissolves only slightly because of the
low aggressiveness of the bath environment.
Previous studies have revealed that other metal species, mainly Fe,
Mn, Ca, Cu, Ni, Co, Mo, W, and rare earth (RE) metals, can function as
important accelerators for phosphating coating [37–39]. These che-
mical accelerators facilitate the decrease in not only the duration of
coating formation but also the working temperature to room tempera-
ture. To refine the porous structure of phosphate coatings, various at-
tempts have been made to develop new structure modifier such as
graphene oxide (GO), aiming at upgrading the traditional phosphating
industry. Fig. 6 shows the effects of GO on the microstructure and the
corrosion performance of phosphate coatings [40]. With the optimum
GO concentration of 1.2 g/L, the phosphate coating obtained the most
uniform and compact structure (Fig. 6a) and achieved the strongest
corrosion resistance (Fig. 6b). The specific mechanism of acceleration in
Fig. 5. Schematic representation for the deposition process of pseudo-phosphate conversion coatings on the zinc surface.
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Colloids and Surfaces A 546 (2018) 221–236
Characteristic
Conversion coating
Pseudo–conversion coating
phosphating by GO could be deduced that GO sheets are absorbed on
the substrate surface and then act as sedimentary beds at the initial
stage of phosphating process, capturing metal ions and favoring the
nucleation of phosphate crystals. However, in all cases the formation of
phosphate coatings by the growth and coalescence of zinc phosphate
crystals inevitably forms pores, which are detrimental to the corrosion
resistance of coatings [41,42]. More effective ways to seal the pore in
the coating layer as completely as possible are still highly needed in
subsequent post-treatments [43,44].
Nevertheless, due to prohibition on overusing of phosphorus che-
mical from current legislation, it is anticipated that, in the future, the
search for more advanced and P-free coatings for corrosion protection
will be instigated by legislative decision. Many alternatives have been
explored so far, including several “green” surface treatments and pre-
treatments, such as silane coatings, Zr/Ti coatings and hybrid coatings.
1.3. Molybdate coatings
As molybdate anions are environmentally acceptable corrosion in-
hibitors [45,46], molybdate passivation treatment is considered as a
possible alternative to chromate treatment [47–50].
With regard to the visual appearance of molybdate coatings, thin
coatings generally appear iridescent, while thick coatings exhibit a dark
brown or matt black finish [51,52]. Similar to chromate conversion
coating, molybdate coating exhibits a cracked “dried riverbed” mor-
phology, as shown in Fig. 7 [27].
The reported formation mechanisms of molybdate coatings are il-
lustrated in Table 3. As previously stated, there is debate as to the
species present on the surface of molybdate coatings. Table 4 sum-
marizes the data cited from literatures. The different mechanisms pro-
posed in previous studies have indicated that the role of molybdate is
not completely understood. However, generally, the majority of mo-
lybdate coatings possibly contain Mo(IV), Mo(V), or Mo(VI) species,
which suggests that molybdate coatings inhibit the corrosion of zinc
substrate by a mechanism involving electrochemical reductions.
Notably, the performance of molybdate coatings is lower, in certain
cases, than that of chromate coatings under neutral salt-spray condi-
tions. Several studies have been conducted to develop a hybrid mo-
lybdate conversion coating doped with other chemicals [48,49]. Lim-
ited and varied success has been made with the addition of synergistic
chemical species, particularly phosphate, silicate, silane and Mg(II) or
Al(III) compounds [48,50], which can promote thinner, more compact
Z. Gao et al. Colloids and Surfaces A 546 (2018) 221–236

Fig. 6. SEM images of phosphate coatings (a) respectively obtained for 1, 4, 12, 20 min of immersion time and potentiodynamic polarization curves of specimens (b) obtained for 20 min
of immersion time. Phosphating bath containing Zn(H2PO4)2 55 g/L, Zn(NO3)2 60 g/L, H3PO4 8 g/L, GO 0–3.6 g/L [40].

coatings.
Fig. 8 shows the polarization curves for the untreated electroplated
galvanized steel (EG), molybdate/phosphate/silicate coated EG (MPS-
EG), and molybdate/phosphate/silane/silicate coated EG (MPSS-EG)
with POLFIT program [50]. Corrosion current densities and Tafel slopes
for the three samples are summarized in Table 5 [50]. The values of the
protection efficiency P = (1 − icorr/iºcorr ) × 100, where iºcorr and icorr de-
note the current density of the untreated and treated samples, respec-
tively [55]. The corrosion current density of the treated samples was
decreased and the protection efficiency was increased due to the
treatment. For the specimen treated in the MPSS process, P was 95.6%
which suggests that most of the surface was covered by a more or less
pore-free coating layer. Therefore, the outlook for molybdate coatings
on the zinc substrate is a promising one; with synergistic additions
reinforcing protection efficacy in corrosive environments.
1.4. Rare earth coatings
The effectiveness of rare earth (RE) salts, especially Ce and La, as
corrosion inhibitors or in conversion coatings, has been considerably
investigated as possible chromate-free alternatives [56–71]. The RE
coating consists of a mixture of rare-earth oxides/hydroxides, which
hinders the corrosion reactions of the substrate by reducing the rate of
both the cathodic and the anodic reactions [56,72,73].

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Fig. 7. Typical morphologies of molybdate coatings obtained with different dipping time: a 2 min, b 30 min. Precusor solution consisting of 0.3 M Na2MoO4 · 2H2O, pH 5.0 adjusted by
phosphoric acid [27].

Table 3 Cerium nitrate has been successfully tested for zinc substrates either as
Typical coating formation mechanisms proposed. aqueous corrosion inhibitor or in conversion coatings [50–60]. Previous
studies have revealed that a hydrated or hydroxylated cerium-rich
Author Year Typical reaction Ref.
oxide layer is formed by the adsorption of hydrated or hydroxylated Ce
Wharton 2003 3Mo7O246− + 14Zn2+ + 32H+ + 42e− → [47] (III) ions on the hydroxylated zinc surface [Zn]OH, expressed by Re-
7Zn2Mo3O8 + 16H2O actions (3)–(5) [58]. Repeated reactions of elongation (Eq. (4)) and
Rout 2007 MoO42− + Zn2+ → ZnMoO4 [52] bridging (Eq. (5)) lead to the formation of cerium oxide frameworks on
HMoO4− + Zn2+ → ZnMoO4 + H+ zinc substrates. The corrosion inhibition properties of RE layers have
MoO42− + 4H+ + 2e− → MoO2 + 2H2O been explained by the marked suppression of the cathodic process with
Silva 2009 2Mo3O114− + 14H+ + 6e− → 3Mo2O5·2H2O + H2O [27] Ce(III), primarily related to the coverage of the surface with a protec-
Mo6O216− + 12H+ + 6e− → 3Mo2O5·2H2O tive layer of Ce2O3 [59,61].
Kartsonakis 2016 7MoO42− + 8H+ → Mo7O246− + 4H2O [53]
[Zn]OH + Ce(III)OH → [Zn]OCe(III)OH + H+ (3)

[Zn]OCe(III)OH + Ce(III)OH → [Zn]OCe(III)OCe(III)OH + H +

(4)
Table 4
Oxidation states of Mo present in molybdate conversion coatings on Zn surfaces produced 2[Zn]OCe(III)OH → [Zn]OCe(III)OCe(III)(OH)O[Zn] + H +
(5)
by the named investigators.
Although there is no direct replacement for chromate conversion
Author Year Mo species found Techniques used Ref. coatings using RE salts, limited success has been reported with the
Treacy 1999 Mo(V) and Mo(VI) XPS [54] addition of synergistic chemical species such as PO43― [64], Si2O52―
Konno 2002 Mo(V) and Mo(VI) XPS [48] [57,60,63], octylthiopropionate C8H17S(CH2)2COO― (OTP―) [58],
Wharton 2003 30–40% as Mo(IV) and EXAFS [47] bis-[triethoxysilylpropyl]tetrasulfide (CH3CH2O)3Si(CH2)3S4(CH2)3Si
Mo(VI) (OCH2CH3)3 (BTESPT), 1,2-bis(triethoxysilyl)ethane (C2H5O)3Si
Rout 2007 MoO3 Raman [52]
(CH2)2Si(OC2H5)3 (BTESE) [57,60,62], tetramethoxysilane Si(OCH3)4
Silva 2009 Mo2O5 XPS [27]
Cheng-Yang Tsai 2010 MoO2 and MoO42− XPS [41] (TMOS) [76], γ-methacryloxypropyltrimethoxysilane CH2C(CH3)(CO)O
Kartsonakis 2016 polymolybdate ions XRD, Raman and [53] (CH2)3Si(OCH3)3 (MAP) [76], and γ-glycidoxypropyltrimethoxysilane
FTIR (CH3)3Si(CH2)3OCH2CHOCH2 (GPTMS) [62].
Fig. 9 shows EIS spectra for the samples pre-treated with the
BTESPT silane solutions doped with Ce or La cations [62]. The addition
EG MPS-EG MPSS-EG of Ce or La to BTESPT silane solutions increases the total impedance of
300
the pre-treatment for about two orders of magnitude comparatively to
250 the non-doped BTESPT film. Cerium is more effective than lanthanum.
200 The synergistic inhibition effect of Na2Si2O5 has been demonstrated
by the formation of a passive film composed of Zn(OH)2, ZnSi2O5, and
150
Ce2(Si2O5)3 on the scratched surface. Fig. 10 shows the backscattered
100 electron microphotographs and line analysis of Zn, Cl, Si, and Ce across
the scratch after the surface was scratched and immersed in 0.5 M NaCl
50
solutions [60]. A protective layer composed of Zn(OH)2, ZnSi2O5 and
0 Ce3+–Si2O52− salt or complex, in which Si2O52− and Ce3+ migrated
-50 from the scratched film, was formed on the scratched surface and
preferential precipitation of the silicate compounds occurred at a defect
-35 -25 -15 -5 5 15 25 of the protective layer to prevent pitting corrosion at the scratch
[60,63]. A schematic representation of the coated zinc surface after
scratched and immersed in NaCl solutions is depicted in Fig. 11 [60].
Fig. 8. Polarization potentiodynamic curves for EG, MPS-EG and MPSS-EG samples ex-
Thus, the passive films doped Si2O52― and Ce3+ exhibit a strong self-
posed to 0.5 N NaCl for 24 h. MPS solution consisting of 60 g/L Na2MoO4 · 2H2O, 90 g/L
Na3PO4 · 12H2O, and 50 g/L Na2SiO3 · 9H2O; MPSS solution additionally containing 50 g/
healing activity and high protective efficiency for the scratched zinc
L glycidoxy propyltri methoxy silane and 10 ml/L HNO3 (adapted from Ref. [50]). surface [57,60].
Similarly, RE-based coatings doped with phosphate exhibit con-
siderable self-healing properties, as zinc phosphate is formed pre-
Table 6 summarizes rare earth conversion coating systems for
ferentially at the defects of the coatings on the base metal surface,
Zn–based materials. Typically, RE salts, namely tetravalent Ce(IV) and
thereby strongly decreasing the corrosion kinetics. With regard to the
trivalent Ce(III) species, are used for corrosion inhibition of zinc as
mechanism of corrosion protection for zinc by OTP―, a trace amount of
high-valence RE ions are characterized by strong oxidation properties.

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Table 5
Parameters calculated with POLFIT program [50].

Name Ecorr (mV) icorr (μA/cm2) ba (mV) bc (mV) B (mV) P (%)

EG −1097 6.8 35 74 10.3 –

MPS-EG −1051 2.7 25 145 8.1 60.5
MPSS-EG −1027 0.3 15 215 6.2 95.6

Table 6
Rare earth conversion coatings cited from literature.

Author Year System Substrate Ref.

Montemor 2001 Ce(NO3)3 Hot-dip galvanised [65]

steel
Aramaki 2001 Ce(NO3)3 Zn [59]
Aramaki 2001 CeCl3, LaCl3, Ce(SO4)2, Ce Zn [61]
(NH4)2(NO3)6 and AlCl3
Aramaki 2002 Ce(NO3)3, Na2Si2O5 and Zn [57]
BTESE
Aramaki 2002 Ce(NO3)3, Na2Si2O5 and Zn [60]
BTESE Fig. 9. EIS Bode plots obtained for untreated galvanized steel and for galvanized steel
Aramaki 2002 Ce(NO3)3 and Na3(PO4)3 Zn [64] pre-treated with: non-doped BTESPT solution and doped BTESPT solutions. Spectra were
Aramaki 2002 Ce(NO3)3 and Na2Si2O5 Zn [63] obtained after 1day of immersion in 0.005 M NaCl. BTESPT solutions consisting of 4% v/v
Aramaki 2002 CeCl3 and NaOTP Zn [58] BTESPT, 90.5% v/v methanol, and 5.5% v/v aqueous solutions; doped BTESPT solutions
Montemor 2002 Ce(NO3)3, La(NO3)3 and Y Hot-dip galvanised [56] prepared by additionally dissolving 1 × 10−3 M Ce(NO)3 or La(NO)3 in aqueous solution
(NO3)3 steel [62].
Ferreira 2004 Ce(NO3)3, La(NO3)3 and Hot-dip galvanised [35]
BTESPT steel
Garcia-Heras 2004 Ce(NO3)3, TMOS and MAP Hot-dip galvanised [76] metavanadate, potassium metavanadate, or a vanadate obtained by
steel dissolving vanadium pentoxide with an amine; the type of vanadium
Montemor 2006 Ce(NO3)3 and La(NO3)3 Hot-dip galvanised [62] salt is not particularly limited as long as it can perform the above-
steel
Ferreira Jr 2016 Ce(NO3)3 and 2-butyne Electrogalvanized [74]
mentioned functions. VCCs mainly consist of V(V), tetravalent vana-
1,4 diol propoxylate steel dium V(IV) and their hydrates [83,88,90,95]. The XPS results for the
Su 2016 Ce(NO3)3, TMOS and Hot-dip galvanised [75] VCCs on zinc (Fig. 12 [90]) verify the case of the reduction of V(V) to V
(GPTMS) steel (IV). One opinion is probably that V(V) species (predominantly VO2+
Kartsonakis 2016 Ce(NO3)3 Hot-dip galvanised [53]
species formed in an acidic solution, as shown in Fig. 13 [85]) can be
steel
reduced to V(IV) along with the oxidation of zinc substrates, as ex-
pressed by Reactions (7) and (8).
zinc chelate with OTP― can effectively prevent the initiation of pitting
Zn → Zn2+ + 2e (7)
corrosion at the defects within layers in NaCl solutions, as expressed by
―
Reaction (6) [58,77]. VO2 + 2H + e → VO
+ + 2+
+ H2O (8)
―
Zn 2+
+ 2OTP → [Zn(OTP)2] (6) During the baking process and the accompanying water evapora-
tion, V(IV) (predominantly HV2O5― species formed in the alkalescence,
Meanwhile, similar to Ce ions, La ions have been used as aqueous
as shown in Fig. 14 [96]) and V(V) species (predominantly VO(OH)52―
corrosion inhibitors for the corrosion protection of galvanized steel
species formed in the alkalescence, as shown in Fig. 13) adhere on the
[35,78]. Their corrosion mechanism is possibly related to the formation
substrate and dehydrate together, followed by the formation of V2O4
of layers composed of La2O3 and La(OH)3, accompanied by a small
and V2O5 species, more or less, respectively, as expressed in Reactions
amount of Zn(OH)2 and ZnO [61,72,73].
(9)–(11).
The above-mentioned attempts have been made to explain the
mechanism of the formation of RE-based coatings on zinc substrates. 2VO2+ + 3OH― = HV2O5― + 2H+ (9)
The reaction and products in a majority of cases are similar, albeit the
H2V2O5 = V2O4 + H2O (10)
course of the intermediate reactions as reported by several authors is
different. Generally, all films consist of a mixture of RE oxides or hy- 2H7VO6 = V2O5 + 7H2O (11)
droxides.
VCCs exhibit excellent corrosion protection property, which is
possibly related to the barrier coating and the leaching of the V(V)
1.5. Vanadate coatings
species from base coatings [88,90,95,97]. V(V) is characterized by a
higher standard electrode potential (E°(VO2+/VO2+) = 1.00 V SHE)
Vanadates have aroused an ongoing attention as suitable candidates
compared to E°(Zn2+/Zn) (―0.762 V SHE). Thus, the passivation of V
for chromate replacement as they exhibit similar chemical properties
(V) appears to play a major role in the corrosion protection of zinc
for corrosion protection [79–84]. Previous studies have widely reported
substrates. Fig. 15 shows the corrosion kinetics properties of VCCs [90].
that vanadates are promising corrosion inhibitors to the corrosion of
It indicates that VCCs exhibit more or at least equivalent efficiency to
zinc in aqueous solutions [85–90]. In addition, some appropriate
the chromate conversion coatings in terms of the corrosion protection
methods have been reported to functionalize soluble vanadates via the
for zinc in specific conditions.
formation of conversion coatings in a manner resembling that exhibited
As shown in Fig. 13, V(V) species exhibit an extremely complex
by chromate-based coatings[91–94].
aqueous chemistry [79,85,90]. Also, the corrosion inhibition by V(V)
The application of vanadate conversion coatings (VCCs) involves
depends on their speciation as the inhibition by decavanadate was not
the use of a chemical treatment solution containing a water-soluble
observed [79,81,85]. This complexity has made their applications very
vanadium salt, such as ammonium metavanadate, sodium

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Fig. 10. Backscattered electron microphotographs and line analysis of Zn, Cl, Si, and Ce between points A and B across a scratch for the zinc surface pretreated in 1 × 10−3 M Ce(NO3)3
solution and covered with BTESE polymer film containing Na2Si2O5 and Ce(NO3)3 after the surface was scratched and immersed in 0.5 M NaCl for (a) 4 h and (b) 24 h [60].

Fig. 11. Schematic representation of the surface pretreated in 1 × 10−3 M Ce(NO3)3

solution and covered with the polymer film containing Na2Si2O5 and Ce(NO3)3 after
scratched and immersed in 0.5 M NaCl for 24 h [60].

challenging in industrial conditions. However, the application of VCC

for the corrosion protection of zinc substrates appears to be technically
Fig. 12. High resolution XPS spectra of V2p and O1s for vanadate conversion coatings on
feasible when VCC is combined with other supporting compounds. And,
electrogalvanized steel sheets. The vanadate conversion bath consisting of 24 g/L NaVO3,
VCC as a promising replacement for environmentally friendly coatings
8 g/L NaH2PO4, and 13 g/L K3Fe(CN)6, pH 1.8 adjusted with H3PO4, 60 s immersion [90].
is expected to be developed in the future. (VeO: 530.56 eV, VeOH: 531.06 eV).

1.6. IV(B) metal coatings
Group IV(B) metal hydrofluoric acids and their salts, mainly fluor-
ozirconate, fluotitanate, and their ammonium salts, are also promising
alternatives for the corrosion protection of Zn-based materials as they
can form continuous three-dimensional polymers or metalloid-oxide
matrices in aqueous solutions [2]. Also, environmental friendliness,
cost-effectiveness, and commercial availability make IV(B) metals
popular in several applications [19,98,99].
Thick IV(B) metal conversion coatings appear iridescent because of
the interference effect; their thickest coatings have a dark brown colour
or matt black finish; and their thin coatings are grey. Adherent ir-
idescent coatings have been reported to impart outstanding corrosion
resistance compared to dark brown or grey coatings. Although the

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been shown to correlate with the humidity resistance of coated panels

V2O5 (c) V4O124 V2O74 [101].
-1 Notably, IV(B) metal ions undergo spontaneous hydrolysis in an

V10O27(OH)5
alkaline medium. IV(B) metal conversion coatings often require the use
V10O286
of a solution acidified by phosphoric acid for industrial applications.
V10O26(OH)24
-2
However, an alkalescent aqueous IV(B) metal-based solution, such as
VO43 colloidal titanium phosphate and ammonium zirconium carbonate, has
V3O93
-3 been also widely applied for the surface pre-treatment in industry. The
effect of curing temperature on the structure and corrosion resistance of
an ammonium zirconium carbonate (AZC) coating on galvanized steel
-4
was investigated by Sako [102]. The morphologies of AZC coatings
VO2+ VO2(OH)2 VO(OH)52 cured at 80 °C, 120 °C, 160 °C, and 200 °C are shown in Fig. 16 [102]. A
-5 significant number of fissures in the coating surfaces cured at 160 °C
VO(OH)3 (aq) and 200 °C were observed. The polarization curves of the AZC coating
cured at various temperatures are displayed in Fig. 17 [102]. The
-6
0 2 4 6 8 10 12 corrosion resistance of an AZC coating cured at 80 °C was excellent.
However, the corrosion resistance tended to decline as the curing
temperature increased, and it was significantly inferior at temperatures
Fig. 13. LogΣmv/pH diagram for the vanadium(V)-water system at 298.15 K [85]. over 160 °C. It is considered that the fissures were caused by volume
shrinkage as the result of dehydration at 155 °C. This dehydration is
condensation of the hydroxide groups involved in conversion of an ol-
(VOOH)22+ V4O92 bridge to an oxo-bridge. The fissures became coating defects and de-
graded coating corrosion resistance. These observations are important
-1 to figure out the mechanism of structure and corrosion resistance of
V2O4
AZC coating itself for future development of Cr-free coatings.
-2 Typically, fluorozirconate conversion coatings are composed of
oxide (ZrO2), hydroxyl fluoride, and a small amount of hydroxyl oxide
-3 [103,104]. With respect to the dioxide formed, ZrO2 was the only
chemical present in the fluorozirconate-based layers. Fluotitanate
-4 VO2+ HV2O5
conversion coatings are also similar.

-5
1.7. Silane coatings
-6
Silane-based coatings have attracted increasing interest because of
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 their exceptional ability to form strong bonds with metal substrates and
simultaneously form cross-linking polymers on the surface. Both these
characteristics impart excellent adhesion, thereby providing corrosion
Fig. 14. LogΣmv/pH diagram for the vanadium(IV)-water system at 298.15 K [96]. protection to base metals [105–109]. Silane coatings composed of a
self-assembled monolayer are particularly attractive for corrosion pro-
tection applications because of the combined advantages of organic
polymers (easy processing, mechanical properties, and new function-
ality by the incorporation of organic or inorganic moieties) and char-
acteristics of inorganic oxides (hardness, thermal and chemical stabi-
lity, and transparency) [7].
The accepted corrosion inhibition mechanisms involve that silane
materials trigger hydrolysis and condensation on substrates during the
formation of silane films, as expressed by Reactions (12)–(14).

ReSieOR´ + H2O → ReSieOH + R´eOH (12)

2ReSieOH → ReSieO – SieR + H2O (13)

MeOH + ReSieOH → MeOeSieR + H2O (14)

As shown in Eq. (14), the formation of chemically adsorbed

Fig. 15. Polarization curves obtained for untreated, V-treated and Cr-treated electro-
galvanized steel sheets. The vanadate conversion bath consisting of 24 g/L NaVO3, 8 g/L
NaH2PO4, and 13 g/L K3Fe(CN)6, pH 1.8 adjusted with H3PO4, 60 s immersion [90].
fluorozirconate-based layer and fluotitanate-based layer are both sig-
nificantly thinner than the organic coatings, they are of crucial im-
portance for the top coating adhesion as well as for the corrosion re-
sistance [100,101]. Also, the uniformity of fluotitanate-based layers has
[MeOeSi] bonds leads to the desirable adhesion of the resulting silane-
based layers to metal substrates and top-coated organic coatings if an
appropriate R group is selected [110,111]. In addition, as shown in Eq.
(13), the formation of highly dense [SieOeSi] bond structure renders
the resultant film excellent corrosion protection of the base metals
[112]. Fig. 18 clearly shows the mentioned processes [113].
Notably, dipodal silanes in several coatings exhibit activity, parti-
cularly in case of primer systems and aqueous immersion applications.
Their efficacy is considered to be related to the ability of forming six
bonds with the substrates compared to the formation of three bonds
with the use of conventional coupling agents (Fig. 19 [7]). Therefore,
the more the hydrolysable groups in their structure, the more the

229
Z. Gao et al.
Fig. 16. Morphologies of the ammonium zirconium carbonate coating on galvanized steel sheets cured at various temperatures. The ammonium zirconium carbonate coatings were
prepared using an aqueous solution of ammonium zirconium carbonate (5 wt% as Zr) [102].
Fig. 17. Effect of curing temperature on the polarization curve for galvanized steel sheets
pre-treated in an aqueous solution of ammonium zirconium carbonate (5 wt% as Zr)
[102].
generated silanol groups, and the more the hydrogen bonds formed in
the presence of hydroxyl-covered metallic surface. In addition, the ex-
cess of hydroxide silicon groups (eSi[OH]3), can react in the solution,
leading to the formation of siloxane [SieOeSi] networks. These results
contribute to the understanding of excellent barrier properties of di-
podal-silane-based coatings, related to the increased crosslinking den-
sity of both the interphase and network in layers.
With respect to the application methods of silane films for zinc, the
sol–gel procedure is attractive because of its relative simplicity and
economic consideration from the engineering viewpoint. However, a
new preparation method referred to electro-assisted deposition has
been developed to facilitate the formation of sol–gel silane films on
230
Colloids and Surfaces A 546 (2018) 221–236
conductive substrates. Such silane-based films prepared by cathodic
electrodeposition exhibit enhanced resistance against corrosion com-
pared to those obtained by conventional dip-coating methods [114].
The possible mechanism of this coating achieved by electrodeposition
involves that a considerable amount of [eOH] groups generated at the
vicinity of the interface at cathodic potentials catalyse condensation,
affording uniform silane films [115].
Similar to other conversion coating, silane coatings doped with
several corrosion inhibitor additives, primarily RE [35,75] and nano-
particles such as TiO2 [112], ZrO2 [116], Ce2O3 [117], CeO2 [116,117],
La2O3 [118], SiO2 [119], and ZnO [120], can improve their barrier
properties. Fig. 20 shows the effects of several silane coatings doped
SiO2 particles on water contact angles [119]. Their corrosion kinetics is
shown in Fig. 21 [119]. These SiO2-loaded silane coatings modified by
hexamethyldisiloxane (HMDS)–tetraethoxysilane (TEOS) with a molar
ratio of 2 exhibit the best superhydrophobic properties and the better
corrosion resistance than other coatings.
Silane-based films primarily function as a barrier coating, which is
essential for inhibiting the initial corrosion reaction by remarkably
decreasing the permeation rate of electrolyte [121,122]; in addition,
such a film is a highly efficient protective coating, exhibiting excellent
corrosion resistant properties, which depends on the passivation action
by the doped corrosion inhibitors. Because of the anticorrosive, high
adhesion, and barrier properties, as well as the environmentally
friendly nature of silane film technology, silane materials are con-
sidered as a highly suitable candidate for replacing chromates.
1.8. Thin organic coatings
Depending on the mechanisms of coating formation, organic-coated
materials for zinc substrates in the industrial production mainly include
organic coordination compounds and polymer resins. These organic
coordination compounds, such as tannic acid (C76H52O46) [123,124]
and phytic acid (C6H18O24P6) [125,126], are capable of chelation with
zinc ions, affording some stable complexes because of their structural
uniqueness. This type of conversion coating composed of complex
compounds is proposed as a potential replacement for chromate coat-
ings. For another type of thin organic coatings, thin polymer coatings
on zinc substrates have been widely applied in construction, home
appliance, and automotive industries [127,128]. Considering the
Z. Gao et al. Colloids and Surfaces A 546 (2018) 221–236

Fig. 18. Bonding of silane coupling agents to metal surface (adapted from Ref. [113]).

Fig. 19. Dipodal silane structure (adapted from Ref. [7]).

advantages of processing at a high curing speed, superior performance,

including scratch resistance, strain resistance, high gloss, and surface
appearance, and environmentally friendly properties, this technology
has received considerable attention on corrosion protection of zinc
substrates in the galvanized steel industry.
Fig. 22 lists the performance of thin polymer coated galvanized steel
sheets. Notably, the distinction in the final performance between thin
polymer coatings and conventional organic coatings, this thin polymer
coating with a thickness of approximately 2 μm exhibits more func-
tional properties besides corrosion protection, including self-lu-
bricating, self-cleaning, anti-fingerprint, and static-free properties Fig. 21. Polarization curves for samples with silane coatings prepared using 4 wt% N,N-
[129]. These desirable technologies permit the formation of polymer dimethylformamide (DMF) aqueous solutions after modification by HMDS–TEOS solu-
coating films containing an organic resin, whereas the inorganic tions with different HMDS/TEOS molar ratios: 0, 0.5, 1, 1.5, 2, 3 and 4, named as S0,
treatment permits a thin film (only less than or equal to 1 μm). In ad- S0.5, S1, S1.5, S2, S3, S4, respectively. The sample with HMDS modification only was
named as HS [119].
dition, aiming to enhance the corrosion resistance of organic coatings, a
new coating technology employing a waterborne polymer doped with
inorganic chemicals has been developed to obtain a hybrid polymer of thin polymer coatings, from galvanization to resin coating and
coating, significantly increasing the protection efficiency for galvanized curing, and then the productivity can be also significantly improved in
steel sheets. In particular, such hybrid polymer coatings have been industrial requirements.
widely adopted as this technology often enables the in-line production

Fig. 20. Wettability of Zn surfaces (a) without coatings and

with silane coatings prepared using 4 wt% N,N-di-
methylformamide (DMF) aqueous solutions after modifica-
tion by HMDS − TEOS solutions with different HMDS/TEOS
molar ratios: (b) S0, (c) S0.5, (d) S1, (e) S1.5, (f) S2, (g) S3,
(h) S4, (i) HS. The modified samples with HMDS/TEOS molar
ratios of 0, 0.5, 1, 1.5, 2, 3 and 4 were named as S0, S0.5, S1,
S1.5, S2, S3 and S4, respectively. The sample with HMDS
modification only was named as HS [119].

231
Z. Gao et al.
Fig. 22. Customer’s quality requirements for thin polymer coated galvanized steel sheets.
1.9. Functional coatings for zinc-based biomaterials
Zn-alloys have showed great potential as a base material for the next
generation of biodegradable implant devices since they can provide
good mechanical properties and produce nontoxic corrosion products in
physiological systems [130–133]. Nevertheless, the choice of a specific
biomaterial is determined by many factors involving corrosion re-
sistance, controlled degradability, biocompatibility, and many other
application specific criterions. Chemical conversion technology gives an
opportunity for substrate surface modification in response to the above
demands on the surface of metals for their biomedical applications
[134,135]. These functional coatings for corrosion protection of me-
tallic biomaterials must be biocompatible and free of cytotoxic and
genotoxic effects, and simultaneously constitute a very specific corro-
sion protective system.
Fig. 23 shows a representative example of the fixation device [135].
Fig. 24 shows the section images for four zinc-based wire samples in
vivo after implantation for 1.5, 3, 4.5, and 6 months [130]. The wires
that remained in the biological milieu for different duration showed
signs of gradual corrosion. Healthy arterial tissue adhered firmly to the
Fig. 23. Representative example of application of metallic biomaterials: bone fixation
device (adapted from Ref. [135]).
232
Colloids and Surfaces A 546 (2018) 221–236
wires, and a limited amount of micro-scale corrosion particulate was
firmly embedded in the arterial tissue surrounding the zinc core (where
the arrow pointed).
The chemical surface modification techniques are based mainly on
the chemical reactions happening at the interface between the metal
surface and the solution [136]. Conversion coating layer is a nanosized
coating that presents a flexible method of carrying out surface mod-
ification of biomaterials to tailor their surface properties for specific
end applications, such as decreasing the corrosion rate or controlling
the degradation of zinc substrate in vivo in an ordered and slow manner
[133,136]. Various chemical treatments have been used for modifying
metallic biomaterials, which can be classified as acid treatment, hy-
drogen peroxide treatment, alkali and heat treatments, organic nano-
coatings, sol–gel coatings, ceramic coatings, and anodic oxidation, as
well as biochemical and photochemical modification. Self-assembled
monolayer (SAM) is another technique of surface modification. This
functional coating involves the formation of typically long alkyl chain
surfactant molecules which have a specific affinity towards particular
substrates and are attached by chemisorption. SAMs are so attractive to
surface modification of metallic biomaterials for medicine application
mainly because of their ability to tune the properties of surface by
modifying the structure and relative ease of preparation. The reported
base materials used to prepare SAMs include silane [137–140] and al-
kanethiol [141]. Other functional coatings that show potential to pro-
tect zinc-based biomaterials are hydroxyapatite coatings [142–144] and
chitosan coatings [133].
Fig. 25 shows the surgery of zinc-based implant with chitosan
coatings and the micro-CT graphs of the implant after 2 and 12 weeks
[133]. The implant edges remained distinct until 12 weeks, which re-
vealed that the degradation of the implant was impeded by coating
layers. Also, the chitosan coating stimulated the new bone tissues,
which obviously deposited and then surrounded the degraded implant.
The design of such function coatings for biomaterials is a complex
task. Although numerous strategies have been reported, there are still
several problems to be solved because the corrosion rate is not properly
controlled [145].
2. Conclusion and outlook
Detailed information about the conversion coating procedures for
Z. Gao et al. Colloids and Surfaces A 546 (2018) 221–236

Fig. 24. Cross section morphologies of four zinc-based wire explants after 1.5, 3, 4.5 and 6 months of implanted duration in the abdominal aorta of a Sprague–Dawley rat [130].

Zn-based materials was extracted from the papers herein. This review
covered several aspects of this rapidly growing field, from any pre-
treatment, coating chemicals, coating process and ultimate corrosion
performance.
The advantage and demerit of each technique has been clarified in
several modern industries, while the expected effects of various coat-
ings are achieved respectively. Of the various conversion coatings
under development, chromate conversion coatings exhibit a superior
ability [59]. Unfortunately, the toxicity of chromium salts creates en-
vironmental and health-related concerns; hence, considerable efforts
have been focused towards the development of an environmentally
acceptable alternative to chromate conversion coating [12]. Modern
phosphate coating is a characteristic example of pseudo-conversion
coatings as bath solutions typically contain several heavy metal ions as
accelerators. However, compared to conventional phosphating for steel
materials, a slow-phosphating process may be suitable for phosphating

Fig. 25. Implanted Zn-Mg alloy biomaterials with chitosan coatings: (a) Surgery of the chitosan coated implant with a rabbit, (b) the bone fractures and the implant after surgery 2 weeks,
(c) the degraded implant and the new formed bone tissues after 12 weeks [133].

233
Z. Gao et al.
zinc substrates. Molybdate, RE, vanadate, and IV(B) metal conversion
coatings are all promising replacements for chromate coatings, and
under particular conditions, exhibit corrosion protection efficiency
comparable to chromate coatings within the design period. However,
molybdate, RE, vanadate, and IV(B) metal species typically play an
assistant role in forming protective coatings. Depending on the barrier
properties, high adhesion, and the environmentally friendly nature of
film technology, the novel silane coating is also a highly suitable can-
didate to replace the chromate coating [7]. However, silane coatings
are typically vulnerable because of the formation of pores and channels
throughout its structure with the simultaneous removal of alcohol and
water from wet films during curing. It is necessary for silane to form
composites with other corrosion inhibitors to gain enhanced barrier
properties of coatings and to retain their functionality. The majority of
the new development related to conversion coating technologies are
based on thin organic polymer coatings, especially hybrid polymer
coatings [12,127–129]. This technology has been widely expanding
into new markets as hybrid-polymer-coated galvanized steels are ex-
tremely efficient to make up for the thickness reduction of zinc coatings
and afford more expected functions. However, to cope with customer’s
various requirements for extremely significant effects on corrosion
protection and new functions as well as excellent surface appearance of
coatings, the cost-effective technology, high process productivity,
comprehensive coating performance, and eco-friendly property are all
essential. Presently, there is a strong emphasis on the development of
advanced functional and smart coatings for corrosion protection in
different technological applications. Thus, bio-functional nano-coatings
on zinc-based biomaterials are driving newer demands and require-
ments for better performance of medicine materials. These nano-coat-
ings can serve primary functions such as corrosion protection and
controlling degradation along with many other secondary chemical
functions such as biocompatibility and controlling drug delivery. De-
spite many advances in this field, there are several challenges to
overcome, aiming at developing highly effective functional coatings for
zinc-based biomaterials.
Overall, the most frequent and reliable strategy for reinforcing the
corrosion protection afforded by versatile conversion treatments is
tailoring coating characteristics, such as thickness, homogeneous cov-
erage, postulated phase and structure in the coating, adhesion to base
metals, functional and smart features for specific requirements, and
corrosion inhibition mechanisms. In regards to the protection strate-
gies, it is essential to note that environment, service demand to design
and the surface property of base material itself are all the key aspects to
take into consideration for any corrosion protection scheme.
Acknowledgment
This work is funded by the National Engineering Laboratory of
Advanced Coating Technology for Metal Materials, Central Iron & Steel
Research Institute, Beijing, China.
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