Materials Science and Engineering A254 (1998) 305 – 310

Transformation of Fe–Al phase to Fe–Zn phase on pure iron

during galvanizing
Yoshitaka Adachi *, Masahiro Arai
Corporate Research and De6elopment Laboratories, Sumitomo Metal Industries, 1 -8 Fuso-cho, Amagasaki 660, Japan

Received 8 August 1997; received in revised form 17 September 1997

Abstract

Focussing on a nucleation site of Fe–Zn intermetallics, phase transformation of Fe – Al intermetallics to Fe – Zn intermetallics

in galvanized coatings are studied by combined ECP – SEM techniques. This study sheds new light on the effects of retained
Fe–Al intermetallics on the orientation relationship of Fe – Zn intermetallics with respect to substrates. Pure iron substrates are
galvanized using 0.20 mass%Al-bearing molten zinc bath. The parent high Al galvanized coatings are subsequently annealed using
a molten salt bath kept at 430°C, followed by water quenching. The Fe – Al phase formed during galvanizing shows no effect on
the orientation relationship between a FeZn13(z) phase formed during galvannealing and an underlying substrate. Based on this
result, and in conjunction with published reports by others, the nucleation mechanism of Fe – Zn intermetallics in high aluminum
coatings is discussed. © 1998 Elsevier Science S.A. All rights reserved.

Keywords: Fe – Zn intermetallics; Galvanization; Phase transformation

1. Introduction development of Fe–Zn intermetallics rather than sup-

The understanding of the phase transformation at the
iron (or steel)/molten zinc interface is of great impor-
tance to predict and control microstructures of both
galvanized and galvannealed coatings. Many experi-
mental and theoretical studies of the phase transforma-
tion have been made [1 – 8]. However, the precise
mechanism of the transformation is still under debate,
mainly since the reaction is complex and extremely
rapid, occurring in less than a second. It is well known
that aluminum in molten zinc tends to segregate at the
Fe/molten zinc interface with eventual precipitation of
the Fe–Al intermetallic phase that inhibits the develop-
ment of Fe–Zn intermetallics [4]. Particular attention
has been focused on the phase transformation of the
transient Fe–Al phase to the stable Fe – Zn phase at the
Fe/Zn interface during galvanizing [2 – 7]. The preferred
precipitation of the Fe – Al intermetallics relative to the
Fe–Zn intermetallics is known to arise from its thermo-
dynamic stability [5]. The predeposited Fe–Al in-
temmetallic phase acts as a diffusion barrier for zinc
diffusing toward substrates and eventually delays the
* Corresponding author.
pressing it completely. Many studies demonstrated the
limited lifetime of the inhibiting Fe–A1 intemmetallic
layer [6,7]. After a sufficiently long galvannealing pe-
riod, the inhibiting layer is destroyed and the diffu-
sional Fe/Zn reaction consequently takes place.
However, the exact nature of the Fe–Al/Fe–Zn phase
transformation still remains a matter of debate. Two
possible mechanisms currently available for the trans-
formation are as follows. A local Al-depletion in
molten zinc at a reaction front takes place due to the
formation of the Fe–Al phase on adjacent substrates
[2]. This Al-depletion would shift the equilibrium diffu-
sion path (Fig. 1A) downward (B, C), which destabi-
lizes Fe2Al5 and allows the formation of d1 and later z.
In particular, the Fe–A1 intermetallic is considered to
be formed favorably at Fe grain boundaries, which
depresses Al concentration in liquid at the Fe–Al(s)/
Zn(l) interface effectively enough to allow the forma-
tion of Fe–Zn intermetallics on the predeposited
Fe–Al phase, where (s) and (l) refer to solid and liquid
states, respectively. This mechanism seems to be able to
explain the so-called fast growing ‘out-burst reaction’ at
the intersection of Fe grain boundaries with substrate
surfaces. An alternative possible mechanism of the Fe–

0921-5093/98/ - see front matter © 1998 Elsevier Science S.A. All rights reserved.
PII S0921-5093(97)00840-X
306 Y. Adachi, M. Arai / Materials Science and Engineering A254 (1998) 305–310

Fig. 1. Diffusion path in the ternary Fe – Zn – AI system at 450°C, according to the Al-depletion model [2].

Fig. 2. Galvanizing and galvannealing processes.

Al/Fe–Zn transformation is that zinc would diffuse
through a preformed Fe – Al layer and reacts with sub-
strates with eventual formation of Fe – Zn intermetallics
at the Fe–Al/substrate interface [3]. Particularly zinc
would preferentially diffuse intergranularly along high
angle grain boundaries of the Fe – A1 phase formed at
the Fe grain boundary or between colonies of the
Fe–Al phase which have differing crystallographic ori-
entations each other. If this mechanism is valid, the
Fe–Zn intermetallic compounds may be also formed
preferentially at the intersection of Fe grain boundaries
with surfaces. This consideration may explain the out-
burst reaction as well. In addition with the active grain
boundary reaction, it has been extensively accepted that
the Fe/Zn reaction at the surface of Fe grains also plays
a significant role on the entire Fe/Zn reaction [8].
Further understanding of the Fe – Al/Fe – Zn phase
transformation is therefore required, by taking account
of the Fe/Zn reaction on Fe grains as well as that at the
intersection of Fe grain boundaries and substrate
surfaces.
The aim of the present study is to clarify the Fe–Al/
Fe–Zn phase transformation mechanism with particu-
lar attention to the effect of the preformed Fe–Al
phase on the crystallographic relationship between Fe–
Zn intermetallics and underlying substrates.
2. Experimental procedure
The substrates used here were 99.999% pure iron
with very large grain size(: 500 mm). To avoid the
substrate-orientation dependence of the Fe/Al as well
as the Fe/Zn reaction, the Fe grains with the orienta-
tion near {112} were used as substrates [8]. The sub-
strates were galvanized by immersion in a molten zinc
bath maintained at 460°C, after reduction. Further
details of the galvanizing process are shown in Fig. 2.
The zinc bath contains 0.20 wt.% aluminum. This con-
centration of aluminum is sufficient for the formation
of the Fe–Al phase more preferentially than that of
 Y. Adachi, M. Arai / Materials Science and Engineering A254 (1998) 305–310 307

Fig. 3. Morphology of interfacial layers and corresponding ECPs showing orientation of underlying a grains. (a) and (a%) As-galvanized (0.20%
Al); (b) and (b%) galvannealed for 180 s at 430°C (0.20% Al); (c) and (c%) as-galvanized (0.01% Al). The stereographic trace of the growing axis
of (b) the high aluminum (O.20% Al)-galvannealed z crystals by referring the corresponding ECP is in good consistency with that of (c) the 0.01%
Al-galvanized z crystals.

Fe–Zn intermetallics. To experimentally demonstrate
the zinc diffusion through the Fe – Al phase, the galva-
nized steels were annealed by dipping in the molten salt
bath kept at 430°C, followed by water quenching. To
examine the underlying alloys beneath the superposed
zinc layer, the remnant Zn layer was removed by
dipping the galvanized steels in 10 vol.% HCl solution.
An inhibitor (0.1 vol.%) was added to the solution to
prevent the underlying alloys from resolution in the
dilute hydrochloric acid. The interfacial alloys were
identified mainly using X-ray diffraction (XRD). Mi-
croscopy was carried out using a scanning electron
microscope (SEM).
3. Results
Fig. 3(a) and (a%) illustrate the microstructure of the
interfacial alloy formed on the {112} a grain during
galvanizing and the corresponding electron channeling
pattern (ECP) demonstrating the orientation of a
grains, respectively. The XRD pattern of the interfacial
alloy is in good agreement with that of the orthorhom-
bic Fe2Al5 phase, as presented in Fig. 4. The Fe2Al5
layer has two types of distinct morphology. One of
them looks to be fine and roughly equiaxed, as shown
by a single arrow. The other one seems to be coarser
and be constituted of parallelogrammic crystals, as
shown by a double arrow. The Fe2Al5 phase with the
coarser crystals appears to be well oriented, which
indicates that the Fe2Al5 crystals have a specific orien-
tation relationship with the underlying substrate. Fig. 5
shows a cross-sectional view of the Fe2Al5 layer. The
Fe2Al5 phase formed during galvanizing at 460°C for 3
s is : 250 nm thick. The grain boundary of the Fe2Al5
crystals is well observable. Fig. 3(b) depicts the change
in the microstructure of the interfacial phase by gal-
vannealing. The orientation of the substrate employed
here is also near {112} a as Fig. 3(b%) shows. The parent
galvanized specimen was fabricated by using the bath
with relatively high aluminum, namely 0.20%Al which
allows the primary Fe2Al5 phase to be formed, as
308 Y. Adachi, M. Arai / Materials Science and Engineering A254 (1998) 305–310
Fig. 4. XRD pattern obtained from an interfacial layer formed in 0.20% Al galvanized coatings. The pattern is in good consistency with that of
the Fe2Al5 phase.
mentioned above. In the galvannealed coatings, pillar-
like crystals are formed in place of the Fe2Al5 crystals.
The pillar-like crystal is apparently monoclinic
FeZn13(z) from the view of the morphology. For the
sake of brevity, the z phase will be termed to be high
aluminum-galvannealed z, hereafter. Fig. 3(b) demon-
strates that the high aluminum-galvannealed z crystals
are well oriented. This result implies unambiguously
that the high aluminum-galvannealed z crystals relates
to the substrate crystallographically, which is similar to
the z crystals formed in the galvanized coatings [8],
though the high aluminum-galvannealed z crystals look
thicker in width than the galvanized z crystals. As a
reference, the morphology of the z crystals formed in
the 0.01% Al-galvanized coating, which will be termed
as galvanized z, is shown in Fig. 3(c). The substrate has
the orientation near {112} a as well. The stereographic
trace of the growing axis of the high aluminum-gal-
vannealed z crystals by referring the corresponding
ECP is in good consistency with that of the galvanized
z crystals. This result probably indicates that the high
aluminum-galvannealed z crystals are formed in the
similar formation mechanism of galvanized z ones.
4. Discussion
4.1. Nucleation site of Fe– Zn crystals in high Al
gal6anized coatings
Two possible sites at which the Fe – Zn phases are
nucleated in liquid Zn – A1 on the underlying substrates
have been proposed, as Fig. 6 illustrates schematically.
Al depletion caused by the Fe2Al5 formation might
allow the formation of Fe – Zn crystals on the prede-
posited Fe–Al layer. Alternatively, Zn diffusion
through the Fe–A1 layer also permits the Fe – Zn phase
formation at the Fe – Al(s)/Fe interface. The present
study demonstrates that the high aluminum-gal-
vannealed z crystals relates to the underlying substrate
heteroepitaxially. This finding definitely bears out the
later consideration proposed by Guttmann [3], since the
strong orientation relationship between the high alu-
minum-galvannealed z and Fe can be brought only
when they are adjacent each other. Guttmann [3] has
verified that Zn atoms diffusing toward the substrates
can get across the predeposited Fe2Al5 layer 250 nm
thick in 3 s at 460°C. The galvannealing period in the
present investigation, namely 180 s at 430°C, is suffi-
cient for allowing Zn to achieve to substrates through
Fe2Al5 250 nm thick. There still remains the possibility
that the high aluminum-galvannealed z has a particular
orientation relationship with the underlying substrate
through the Fe2Al5 layer. If the Fe2Al5 crystals relate to
both the underlying substrates and the superposed z
crystallographically, the Fe2Al5 layer can act as a buffer
layer for them. However, the Fe2Al5 crystal has a
complex orthorhombic structure. It is, therefore, un-
likely that the high aluminum-galvannealed z crystals
still maintain the common orientation relationship with
the substrate, if the Fe2Al5 layer is retained on the
substrate. This consideration, therefore, invalidates the
Al depletion mechanism of the Fe2Al5 destabilization.
It might be interesting to mention that Guttmann has
recently claimed that the Al depletion due to the Fe2Al5
formation is much smaller than the necessary depres-
sion of it below the maximum solubility of Fe–Zn
intermetallics [3]. In addition, it has also evidenced
experimentally that the Al depletion is very quickly, for
less than 0.5 s, replenished again by Al diffusion in
liquid Zn [3]. These results also make the Al depletion
mechanism questionable. It has been shown that the
predeposited Fe2Al5 layer still remains at the z/Fe
interface [2]. It has also been demonstrated that the
galvanized z crystals formed on the Fe2Al5 layer are
oriented randomly [2]. Based on these findings, the Al
depletion mechanism is still supported by several re-
searchers [2,4]. However, there appears to be differing
explanations about the randomly oriented z crystals.
One possible mechanism is that the z crystals are
precipitated on the Fe2Al5 layer during cooling in the
galvanizing process rather than during the isothermal
hold at the galvanizing temperature. In that case, the
 Y. Adachi, M. Arai / Materials Science and Engineering A254 (1998) 305–310 309

Fig. 5. Cross section of the Fe2Al5 layer formed in 0.20% Al galvanized coatings. The layer is : 250 nm in thickness.

strong orientation relationship between z and Fe is for the preferential out-burst nucleation at Fe grain
hampered by the retained Fe2Al5 layer, though it has not boundaries. The coarser Fe2Al5 crystals have a particular
been fully proved. orientation relationship with the underlying substrate.
The Zn diffusion mechanism appears to be in conflict The grain boundary between the Fe2Al5 crystals formed
with the formation sequence of Fe – Zn intermetallics, on the different Fe grains is, therefore, regarded as a high
namely FeZn13(z) “FeZn7(d1) “Fe3Zn10(G), since the or random angle boundary. The high angle Fe2Al5
iron concentration of intermetallics formed at the Fe/Zn boundary allows high diffusivity of zinc atoms diffusing
interface decreases with increasing the galvanizing period toward substrates, which accelerates the development of
if zinc atoms preferentially diffuse into substrates. It the Fe–Zn intermetallics at Fe grain boundaries (see Fig.
might be worthy of note that the phase sequence depends 8).
on the magnitude of free energy change, if free energy
change of precipitates differs much from others. If free
energy change among precipitates is close to each other, 5. Conclusions
it is conceivable that the nucleation of a stable precipitate
phase can be very difficult because it has a similar With focusing on the precipitation site of the Fe–Zn
composition to that of the matrix, but a metastable phase
with a quite different composition can form (see Fig. 7)
[9]. In the Fe–Zn system, there is scarcely any difference
in free energy change among Fe – Zn intermetallics [10].
Therefore, at the start of precipitation, the z phase may
be favored since it differs much in composition even if
it can not be in stable equilibrium with the substrate.

4.2. Nature of out-burst mechanism

The consideration concerning the nucleation site of the

high aluminum-galvannealed z crystals can also account

Fig. 7. Demonstration of the effect of phase composition on the

Fig. 6. Possible nucleation sites of z in liquid Zn–Al on or above
underlying substrates. z nucleation (a) on Fe2Al5 and (b) at Fe2Al5/Fe
interface is proposed, based on Al-depletion model and Zn-diffusion
model, respectively.
driving force at the start of precipitation. If free energy change among
precipitates is close to each other, the nucleation of a stable precipi-
tate phase (a) can be very difficult because it has a similar composi-
tion to that of the matrix, but a metastable phase (b) with a quite
different composition can form.
310 Y. Adachi, M. Arai / Materials Science and Engineering A254 (1998) 305–310

Fig. 8. Possible mechanism for z nucleation in high aluminum coatings. Zinc diffusing towards the substrate through the Fe2Al5 layer consequently
reacts with substrates and z eventually precipitates at the retained Fe2Al5/substrate interface. In particular at Fe grain boundaries the high angle
grain boundaries in Fe2Al5 grains allow high diffusivity of zinc atoms as well as eventual out-burst precipitation.

phase, the breakage of the predeposited Fe2Al5 phase to References

the Fe–Zn phase during galvanizing was studied. The
Fe2Al5 crystals retained on substrates show no influence
on the strong orientation relationship between z and
Fe. Accordingly, the z crystals are very likely formed at
the retained Fe2Al5/Fe interface during galvanizing as
well as galvannealing. In relation with that, the Fe2Al5
layer is destabilized mechanically by Zn diffusing
through it with eventual precipitation of the high alu-
minumgalvannealed z crystals at the Fe2Al5/Fe
interface.
Acknowledgements
Acknowledgements are made to Professor H.Saka and
Professor K.Kuroda, Nagoya University, for continuing
encouragement during this work.
[1] C.S. Lin, M. Meshii, Metall. Mater. Trans. B 25 (1994) 721.
[2] J. Inagaki, Y. Sakurai, A. Nishimoto, Tetsu to Hagane 79 (1993)
1273.
[3] M. Guttmann, Y. Lepretre, A. Aubry, M.J. Roch, T. Moreau, P.
Dillet, J.M. Mataigne, H. Baudin, Proc. Galvatech 1995,
Chicago, 1995, p. 295.
[4] H. Bablik, F. Gotzl, R. Kukaczka, Werkst. U. Korro. 2 (1951)
1961.
[5] P. Perrot, J.C. Tissier, J.Y. Dauphin, Z. Metall. 83 (1992) 786.
[6] M.A. Haughton, Proc. 2nd Int.. Conf. on Hot Dip Galvanizing,
Oxford, 1953, p. 59.
[7] D. Horstmann, Arch. Eisenhuttenwes 27 (1956) 297.
[8] Y. Adachi, K. Kamei, T. Nakamori, J. Jpn. Inst. Met. 56 (1992)
1235.
[9] M. Hillert, in: H.I. Aaronson (Ed.), Lectures on the Theory of
Phase Transformations, The Metallurgical Society of AIME,
New York, p. 1.
[10] P.J. Gellings, D. Koster, J. Kuit, T. Fransen, Z. Metall. 70
(1979) 315.