Effects of zinc bath temperature on the coatings of hot-dip galvanizing

Peng Bicao, Wang Jianhua, Su Xuping

, Li Zhi, Yin Fucheng

School of Mechanical Engineering, Xiangtan University, Xiangtan Hunan 411105, China
Key Laboratory of Materials Design and Preparation Technology of Hunan Province, Xiangtan University, Xiangtan, 411105, P.R. China
Received 25 April 2007; accepted in revised form 24 July 2007
Available online 2 August 2007
Abstract
The purpose of this work is to identify the influence of zinc bath temperature on the morphology and the thickness of hot-dip galvanizing coating.
Hot-dip galvanizing samples were prepared at temperatures in the range of 450530 Cin steps of 10 Cand at different immersing time. The samples
were characterized by using scanning electron microscopy/energy dispersive X-ray analysis. When the galvanizing temperature ranges from 450 to
470 C, the coating has a coherent and compact layer on the top of a layer. phase coexists with liquid zinc pocket around 480 C. It was found that
the coating thickness reaches maximum at 480 C. When the temperature is above 500 C, the coating changes to be primarily phase.
2007 Elsevier B.V. All rights reserved.
Keywords: Hot-dip galvanizing; Coating morphology; Coating thickness; Galvanizing temperature
1. Introduction
Hot-dip galvanizing is known as the major method used to
apply zinc-based coating on steel in order to provide sacrificial
protection against corrosion. According to the FeZn phase
diagram, when iron is immersed in molten zinc at the typical
galvanizing temperature (450490 C), Horstmann [1] proposed
that the following layers should form: zinc saturated -iron,
phase layer,
1
phase layer, phase layer, phase layer and
phase layer. However, the sequential nucleation of the FeZn
phases occurs at the interface beginning with (1) phase layer,
followed by (2) phase layer, then (3) the phase layer after some
incubation time [2]. Based on iron-loss experiments, the effect of
temperature on the kinetics of the reaction between liquid zinc and
pure iron [3] shows that the total layer growth kinetics for long
immersion times is parabolic (lower parabolic region) below
495 C. It is again parabolic above 520 C (upper parabolic).
Linear attack (linear region) occurs between these two regions, but
short time experiments up to 30 min also show parabolic attack in
the region [3]. This could be disputed, considering that it is only
true in some cases andiron-loss measurements give no information
on the relative rates of the growth of individual layers. Also it is
probable that some unalloyed iron is removed by acid during the
stripping process [4]. Verma compared the coatings formed in the
temperature range of 520550 C with that formed at 450 C. It
was found that the coating thickness reaches the maximum at
530 C when low carbon steel (0.042 wt.% C, 0.2 wt.% Mn) was
galvanized in zinc bath [5].
The main objective of this study is to identify the effect of the
temperature on the growth of hot-dip galvanizing coating, the
change of the morphology of FeZn phase in the coating at
different temperatures and to explain the reason about the fast
growth of the coating.
2. Experimental
The investigated material is a commercial pure iron of which
the composition is shown in Table 1. The thickness of the pure iron
sheet is 1.8 mm. The iron sheets were degreased for 15 min in an
alkaline cleaner, followed by pickling in 100200 g/l HCl for
5 min. Next the sheets were dipped in a flux bath consisting of
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Surface & Coatings Technology 202 (2008) 17851788
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E-mail address: sxping@xtu.edu.cn (S. Xuping).
Table 1
Composition of base steels
Element C S Mn Si P Cr Mo
Composition (wt.%) 0.0073 0.0077 0.128 b0.007 0.0143 0.0263 0.003
0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.07.044
500 g/l of 25/75 wt.% ZnCl
2
/NH
4
Cl salt solution which was kept
at 80C. The fluxedsheets were dried for 30min at 70 Cin drying
box. Then the sheets were dipped in the zinc bath saturated Fe for
1, 2, 3, 5 and 8 min at the temperatures in the range of 450530 C
in steps of 10 C. For the characterization of cross-sections,
samples were embedded in a room temperature setting resin,
polished to a mirror finish using Al
2
O
3
and etched with 4% nital.
The coatings were analyzed by using SEM/EDS (JSM-6360LV).
An accelerating voltage of 20 kVwas used for SEM/EDS analysis.
3. Results and discussions
The pure iron sheets were galvanized in the entire temperature
range of 450530 C with the immersion time of 1, 2, 3, 5 and
8 min respectively, then cross-sectioned and studied by using
SEM/EDS. The depth of the coating was measured ten times and
then averaged as the coating thickness. The measured results of the
coating thickness are shown in Fig. 1.
The thickness of the coatings varies noticeably in the
temperature range of 450530 C as shown in the figure. The
coating thickness reaches a maximum at 480 C in the case of the
same immersion time. Below 480 C, the thickness of the coating
increases with the temperature. Above 480 C, the coating
thickness decreases significantly first and then changes little in the
range of 500530 C. With the increase of the immersion time, the
coating becomes thicker at the same temperature.
According to the changes of the microstructure and the
morphology of the coating in the range of 450530 C, the entire
temperature range can be divided into three partial ranges which
represent different coating growth kinetics: (1) 450470 C; (2)
around 480 C and (3) 490530 C. The representative SEM
micrographs of the coating cross-section at different temperature
ranges are shown in Figs. 25. In all samples two phases were
detected, which are denoted with serial numbers in these figures.
Table 2 averages the results of the EDS analysis of these phases
corresponding to all figures.
Comparing the analysis results with the composition variation
range of FeZn phases listed in Table 3, it was found that #1, #3
and #5 correspond to the zeta () phase, #2, #4, #6, #7 and #8 to the
delta () phase respectively. The phase is too thin to be detected
exactly, and it is only seen when immersion time is relatively long
[7,8]. The micrographs and the EDS analysis results of the coating
showthat when the temperature is in the range of 450470 C, the
Fig. 1. Plot of coating thickness as a function of temperature.
Fig. 2. SEM micrograph of the coating galvanized at 460 C and immersed for
5 min.
Fig. 3. SEM micrograph of the coating galvanized at 480 C and immersed for
5 min.
Fig. 4. SEM micrograph of the coating galvanized at 490 C and immersed for
5 min.
1786 P. Bicao et al. / Surface & Coatings Technology 202 (2008) 17851788
morphology of the crystallites is coherent and columnar, and the
phase is relative compact in which there are fewer cracks. The
morphology and the grain size of the phase change significantly
with the variation of hot-dip temperature. The morphology of the
phase changes to granular at 480 C. Compact layer can no
longer exist in the coating, and a lot of cracks appear in the layer,
as shown in Fig. 3. But galvanized at 490 C, the phase appears in
the form of columnar crystallites again as shown in Fig. 4. The
structure of the coating at 490 C is similar to the structure at
460 C, but it is coarser at 490 Cthan that at 460 Cbecause of the
effect of temperature on nucleation and growth. The depth of
phase layer decreases with the increase of temperature until the
phase no longer appears in the coating, even though the phase
diagram shows that it is stable up to 530 C [9]. When the
galvanizing temperature is above 500 C, the phase dominates
the coating primarily according to the analysis of the coating
presented in Fig. 5. The phase changes from compact to
fragmental and the cracks in phase become more noticeable with
the increase of the temperature, in which liquid zinc appears.
Horstmann [10] pointed out that the compositions in the steel
have considerable effects on hot-dip galvanizing. When the steel
immerses in liquid zinc, it will be eroded and dissolved by liquid
zinc. At the same time the alloying elements (C, Si, P, Mn etc.) in
the steel will also be dissolved. These alloying elements affect the
growth of the FeZn phase. C, Si and P can accelerate the growth
of the phase and restrain the formation of the phase [1113].
When the content of Mn is above 1.3%, it will accelerate the
growth of the coating [4].
While the commercial pure iron immerses in liquid zinc, the
phase forms firstly [2]. The solubility of zinc and iron in the phase
changes noticeably from 425 C to 530 C, based on the Zn-rich
region of the FeZn binary phase diagram shown in Fig. 6 [14]. It
can be concludedthat the ability of the phase to accommodate the
other alloying elements changes noticeably from425 Cto 530C,
too. Besides, Si is almost insoluble in the phase [15,16].
Moreover, it can be concluded that the diffusing flux of dissolved
Fig. 5. SEM micrographs of the galvanized coatings. (a) galvanized at 500 C
and immersed for 5 min, (b) galvanized at 520 C and immersed for 5 min.
Table 2
Average results of the EDS microanalysis of the cross-section of the galvanized
coatings
Phase number Fe (at.%) Zn (at.%) Phase
1 6.75 93.25
2 10.67 89.33
3 6.24 93.76
4 10.89 89.11
5 6.92 93.08
6 9.80 90.20
7 9.31 90.69
8 8.72 91.28
Table 3
Composition variation range of the phases in FeZn alloys [6]
Phase Fe (at.%) Zn (at.%)
Zeta () 5.97.1 94.192.9
Delta () 8.113.2 91.986.8
Gamma-1 (
1
) 18.924.0 81.176.0
Gamma () 18.031.0 82.069.0
Fig. 6. Zn-rich region of ZnFe system [11].
1787 P. Bicao et al. / Surface & Coatings Technology 202 (2008) 17851788
iron from iron sheet into the bath is determined by the galvanizing
temperature and increases with the temperature from Eq. (1) [17].
D
ZnL
Fe
2 10
7
exp
33600
RT

m
2
s
1

1
The dissolved iron and other alloying elements increase with
the increase of the diffusing flux of dissolved iron. With the
increase of the temperature, the solubility of alloying elements in
the phase decreases, so the alloyingelements will segregate in the
grain boundary of the phase when it forms, such as the
segregation of Al at the galvanized coating steel interface [18].
Liquid pocket will form in the grain boundary of the phase in
order to accommodate these alloying elements. Liquid pocket
appeared in the boundary of phase prevents the formation of
coherent and compact layer whichleads to the formation of liquid
paths. As a result, liquid zinc can contact with the phase directly.
Because it is impossible for the equilibrium between the phase
and liquid Zn below 480 C[15,19], the phase will be eroded by
liquid zinc and phase will form according to the peritectic
reaction between the phase and liquid zinc. Rapid interface
reaction accelerates the formation of the phase and makes the
coating growfaster at 480 C. The coexisting of phase and liquid
zinc pocket can relax the stress within the phase which makes the
phase fragmental and numerous cracks formed within the
phase. As the decrease of the thickness of the phase, the amount
of the alloying elements expelled from phase at 490 C is much
less than that galvanized at 480 C. So the amount of liquid zinc in
the boundaries of the phase is less, which results the appearance
of a coherent and compact layer again.
When the temperature is above 500 C, the phase begins to
disappear and the phase contacts with liquid zinc directly. It is
generally accepted that primary crystallization of phase at the
outer region of the coating helps to keep the phase under stress. In
the absence of phase, these stresses relax, partially at least, and
numerous cracks form in the phase [20]. So the cracked diffuse-
(+liquid zinc) forms. Because of the absence of the phase,
erosion of the phase accelerates at high temperature [4].
Althoughthe coating has a diffuse-layer, the depth of the coating
is thinner than that formed at 480 C.
4. Conclusions
The following conclusions may be drawn from the present
study:
The layer changes with the increase of temperature
significantly. The segregation of the alloying elements in the
boundary of the phase results in the formation of the liquid paths,
which prevent the formation of coherent and compact layer. As a
result, liquid zinc contacts the phase directly and erodes the
phase. Rapid interface reactions accelerate the formation of the
phase, which makes the coating grow faster. From the above
investigation it is concluded that the coating grows fastest at
480 C in hot-dip galvanizing at the same immersion time. It is
different from the conclusion drawn by Verma, in which the
coating thickness reaches the maximum at 530 C when low
carbon steel was galvanized in zinc bath. The phase formed at
480 C is incoherent and loosen, so in the galvanizing industry the
steels should not be galvanized at this temperature.
Acknowledgements
The authors acknowledge the financial support of the National
Natural Science Foundation of China (No. 50671088) and a
project supported by the Scientific Research Fund of Hunan
Provincial Education Department (05A004).
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