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Abstract
The generation of zinc and zinc alloy coatings on steel is one of the commercially most
important processing techniques used to protect steel components exposed to corrosive
environments. From a technological standpoint, the principles of galvanizing have remained
unchanged since this coating came into use over 200 years ago. However, because of new
applications in the automotive and construction industry, a considerable amount of research
has recently occurred on all aspects of the galvanizing process and on new types of Zn coatings.
This review will discuss the metallurgy of zinc-coated steel from a scienti®c standpoint to
develop relationships to practical applications. Hot-dip zinc coating methods, i.e. batch and
continuous processes, will ®rst be reviewed along with Fe±Zn phase equilibria and kinetics.
Commercially, the addition of aluminum to the zinc bath results in three important types of
coatings, galvanized, galfan and galvalume, and produces complex reactions at the coating/
substrate interface. Fe±Zn±Al equilibrium will be reviewed in the light of recent studies of
solubility and inhibition layer formation and breakdown. The eect of steel substrate
composition on these reactions will also be critically analyzed. The overlay coating formation,
or the coating alloy, is speci®cally chosen for its desired properties. The morphology of the
galvanize, galfan and galvalume coating overlays will be reviewed, as well as the eect of heat
treatment to produce a galvanneal coating. Finally, the eect of the microstructures of these
coatings on the important properties of corrosion, formability, weldability and paintability will
be discussed. # 2000 Elsevier Science Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
1
Tel.: +1-610-758-4197; fax: +1-610-758-4244; e-mail: arm@lehigh.edu
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 193
1. Introduction
Zinc coatings are predominantly used to improve the aqueous corrosion of steel
by two methods, barrier protection and galvanic protection. In barrier protection,
the zinc coating, which separates the steel from the corrosion environment, will
®rst corrode before the corrosive environment reaches the steel. In galvanic
protection, zinc is less noble or anodic to iron at ambient conditions, and will
sacri®cially corrode to protect the substrate steel, even if some of the steel is
exposed as cut edges or scratches in the coating. Typical processing methods used
in producing zinc coatings include hot-dip galvanizing, thermal spraying and
electrodeposition. This review will be limited to hot-dip galvanizing, i.e. the
immersion of a steel article in a liquid bath of zinc or a zinc alloy, by batch or
continuous processing. The continuous process is more advantageous for coiled
products such as sheet, wire and tube, whereas the batch process is normally used
for bulk products.
In general, prior to immersion in the liquid zinc bath, the steel article to be
galvanized is ®rst cleaned to eliminate any surface oxide that may react in the zinc
bath. After hot-dipping, in which the steel reacts with the bath forming the
coating, the article is withdrawn, cooled and sometimes subsequently heat treated.
The anatomy of a zinc coated steel part consists of (1) the overlay or coating
alloy, (2) an interfacial layer between the overlay and the substrate steel
containing a series of intermetallic compounds, and (3) the substrate steel. Each of
these regions can be aected by the bath time and temperature, as well as the
chemistry of both the bath and the substrate steel.
It is the purpose of the present review to supplement and update the excellent
reviews of the 1970 s [1, 2]. In recent decades there has been a dramatic increase in
zinc coatings research worldwide led by new applications in the automotive and
building industries and indicated by the number of international conference series,
particularly Galvatech [3±6] and the TMS [7±9]. The object of this review is to
provide metallurgists with fundamental knowledge of a complex coating process as
well as to aid those scientists and engineers who are directly involved in the
production and application of zinc coatings. After brie¯y providing a background of
the coating production processes, Fe±Zn phase equilibria will be discussed, followed
by a critical analysis of substrate/alloy bath interface reactions and overlay coating
formation. The post coating heat treatment process will next be reviewed along with
a description of the various commercial coating types and their properties.
. To clean the surface of the article and the molten zinc so that the zinc and steel
can react.
. To reduce the danger of splattering when wet articles are dipped.
. To wipe the article during withdrawal, producing thinner coatings.
. To reduce oxidation of the surface of the molten zinc and thus reduce ash
formation.
. To prevent burning or overheating when immersing large objects or during
``double dipping''.
. To reduce distortion by preheating thin articles.
The ¯ux blanket can be made of ammonium chloride with additions of cryolite,
a sodium aluminum ¯uoride for higher Al contents, or zinc ammonium chloride.
The ¯ux blanket must ¯ow freely over the bath and remain in contact with the
article as it is immersed. The activity of the ¯ux blanket depends initially on the
ammonium chloride content and with time will become more viscous due to the
formation of high melting point Zn compounds. However, the ¯uidity of the
¯ux can be maintained for some time by periodic additions of ammonium
chloride.
In the dry process after cleaning, the article is pre¯uxed in an aqueous solution,
dried and then dipped in the molten zinc bath. The ¯ux used is aqueous zinc
ammonium chloride with a small quantity of wetting agent added. The solution
can be mixed in several ways, including special proprietary ¯uxes that are used for
the higher aluminum content zinc coatings. The temperature of the pre¯ux
solution may range from room temperature up to 808C. It is essential that the
article be thoroughly dried before immersion in the molten bath. The optimum
condition for drying is about 1208C for up to 5 min and should not exceed 1508C,
when decomposition of the ¯ux occurs. Wet patches on the piece can cause spatter
and splashing that can result in splash marks and bare patches on the ®nished
part. The explosion hazard is also more acute in dry galvanizing than in wet
galvanizing. Articles that have been pre¯uxed and dried should be galvanized
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 195
immediately, as the ¯ux coating picks up moisture from the air and also tends to
oxidize [10].
In both processes, the molten zinc galvanizing bath is maintained at
temperatures between 445 and 4558C and immersion times are in the range of 3±
6 min depending upon the thickness of the workpiece. The predominant coating
made by the batch process is galvanized, although some small quantities of galfan
(5% Al) and galvalume (55% Zn) are also made. The time of immersion can be
varied to control the thickness of the coating that consists of iron±zinc alloy
phases at the interface along with a top coat of pure zinc. Good cooling control is
also necessary since the zinc can continue to react with the substrate to produce
further alloying and detrimentally aect the properties of the coating.
The oxides do not form a continuous layer on the surface but are present as
islands. The nonuniform distribution is to be expected since the amount available
for the diusion of the elements is so limited that easy diusion paths, such as
grain and subgrain boundaries, must clearly be favored sites for oxidation of the
Fig. 2. Total surface coverage of the oxides versus the sum of the bulk composition from [12].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 197
Fig. 3. Equilibrium partial pressure of water pH2O for reactions of the type:
x/y M + H2O \ y ÿ 1MxOy + H2 from Ref. [12].
x=y M H2 O () y ÿ1 Mx Oy H2 1
where M is the cation forming element. The shaded area in the ®gure represents
the range of temperatures and dew points investigated [12]. From these results it
can be seen that Fe3O4 will be reduced above 1508C at a dew point of ÿ20 to
ÿ308C, while the other alloy elements will be oxidized over the entire temperature
range. It should be noted that the equilibrium curves for oxidation of Ti, Si and
Al are beneath the bottom of the ®gure.
After cleaning, the sheet enters the heating and holding zones of the furnace
where it is annealed above the recrystallization temperature in excess of 7008C.
The speci®c recrystallization temperature used will depend on the type of steel
being coated. For example, Fig. 4 shows that for a given set of cold rolling,
coiling and annealing temperature (6508C) conditions, the kinetics of
recrystallization for an Al killed steel is faster than steels containing solute
additions of Ti, Ti/Nb or Nb [13]. At faster line speeds the annealing temperatures
would have to be higher to produce the same amount of recrystallization. As a
result of this step in the process the sheet is suciently heated to enter the bath
without aecting the bath temperature.
Fig. 5. Schematic of the pot region in a typical continuous hot-dip galvanizing line.
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 199
On exiting the furnace, the strip passes through a gas jet section capable of
cooling the strip temperature at 508C/s to 4608C prior to coating by immersion in
the zinc molten bath. As the strip exits the bath, Fig. 5, the thickness of the
molten metal ®lm is controlled by gas wiping dies that remove excess coating
metal. After coating, the sheet is either cooled by forced air or subjected to an in-
line heat treatment, called galvannealing, before being rewound into coil or
sheared into cut lengths at the exit of the line.
The bath temperature will depend upon the composition of the coating the bath
alloy melting point and the strip temperature prior to dipping. A galvanized Zn
(<0.3% Al) bath is kept between 445 and 4558C. Because the galfan (Zn±5% Al)
composition is a eutectic, a lower bath temperature of 4258C is usually used and
for a galvalume (Zn±55% Al) bath, the temperature of the bath is near 6008C.
Bath temperature and dipping time, a result of line speed, are speci®c operating
parameters that can be optimized to control ecient surface cleaning, strip
heating and minimization of alloy layer growth during the immersion step.
Typical dipping times range between 4±8 seconds for line speeds in excess of
175 m/min.
Dross in the Zn pot can be classi®ed as oxide types (Zn and/or Al) and
intermetallic compound types (Zn±Fe and Fe±Al). The latter type tends to cause
dross problems and form in the Zn pot when Al and Fe are present in the bath in
concentrations above the solubility limits [14]. Speci®cally, the problematic
intermetallic compounds have been identi®ed as Fe2Al5Znx ``top'' or ``¯oating''
dross and aluminum saturated d (FeZn7) phase ``bottom'' dross [15]. Even if
perfect Zn bath chemistry management is maintained, dross crystallization is
unavoidable due to the Al additions to the bath, Fe dissolution from the steel
strip and the insucient temperature uniformity and chemical homogeneity
obtained with conventional galvanizing technology. However, speci®c bath
management techniques utilizing computer software to measure eective Al have
been suggested to minimize dross formation [16]. Recently, the thermochemistry of
dross formation in the continuous galvanizing process has been reviewed [17].
On exiting from the liquid metal pot, the excess liquid is forced back into the
bath by gas wiping dies that blow either air or nitrogen onto the surface of the
steel, Fig. 2. This step is designed to precisely control and maintain a uniform
coating thickness and is usually monitored by on-line X-ray coating thickness
measuring equipment. As the sheet moves further up the cooling tower, Fig. 1, the
coating can be additionally cooled at this point or, on some lines, nucleation can
be induced by impingement of Zn particles. In the galvanneal process, the cooling
tower is transformed into an annealing furnace either by introducing an induction
furnace above the gas wiping jets and using a good part of the tower height as a
holding furnace, or introducing a gas heating furnace above the gas knives as
depicted schematically in Fig. 1. In either case, producing an optimized galvanneal
product is dependent upon controlling processing parameters such as heating rate,
peak or hold temperature, and cooling rate, as they all aect the amount of
alloying that will occur in the coating prior to reaching the tower roll. At this
point, all of the coating must be solidi®ed to avoid sticking on the tower roll.
200 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Subsequent processing and ®nishing steps such as roller leveling, temper rolling,
chromating and/or oiling, cutting and slitting, complete the manufacturing
process.
When the substrate steel is immersed in the liquid zinc bath, a number of
reactions occur depending upon the bath composition and the solutes found in the
steel. Before discussing compositional eects, it will be helpful to develop an
understanding of the reactions between iron and zinc.
The Fe±Zn system has been the subject of a number of review papers, e.g. [1, 2].
The phase diagram has been modi®ed several times, especially the zinc-rich
section, since it was presented in 1938 [18±23]. The most widely accepted iron±zinc
Fig. 6. Fe±Zn phase diagram From Massalski TB. Binary Alloy Phase Diagram. ASM International
1986. # 1986 ASM International. [24].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 201
equilibrium phase diagram (Fig. 6) is that of Kubachewski [23]; the zinc portion
of the diagram is seen in Fig. 7. The phases found in the current diagram are
outlined in Table 1. The primary phases formed during long-time immersion
galvanizing (or post-dip annealing) are zeta (z), delta (d), gamma1 (G1) and
gamma (G). Although not represented in the equilibrium diagram (Figs. 6 and 7),
eta (Z) phase is a solid solution of Fe in Zn with an iron solubility of 0.03 wt%.
Although older iron±zinc equilibrium phase diagrams show the existence of both a
delta (d) phase and a delta1 (d1) phase, the X-ray analysis of Bastin et al. [21]
indicates that only one delta phase exists up to 6708C.
Table 1
Fe±Zn phase characteristics.
Phases Formula Crystal structure VHN (25 mg) [20] VHN (25 g) [27]
that the following layers should form: zinc saturated a-iron, gamma (G) phase
layer, gamma1 (G1) phase layer, delta (d) phase layer, zeta (z) phase layer and an
eta (Z) phase layer. However, the sequential nucleation of the Fe±Zn phases
occurs at the interface beginning with (1) the zeta (z) phase layer, followed by (2)
the delta (d) phase layer, and after some incubation time, (3) the gamma (G) phase
layer, e.g. Fig. 8. In light optical microscopy, the gamma (G) phase layer is so
small that the layer is considered to contain both the G and G1 phases. The Fe±Zn
phase layer development is also shown schematically in Fig. 9, where the reaction
sequence is represented chronologically. Zero time is represented by t0, and the
phase development occurs according to time so that t0 < t1 < t2 < t3 < t4. In
studies on iron substrates (0.003 wt% C, 0.258 wt% Mn), it was found that zeta
(z) phase nucleation is immediately followed by delta (d) phase formation (t2) at
the a-iron/zeta (z) interface [27]. There was no apparent delay in the formation of
zeta (z) or delta (d) phases, as both were found to form a continuous layer after a
5 s immersion time. On the other hand, the gamma (G) phase was found to form
(t3) after an incubation time of 30 s.
A typical morphology found for a pure Zn hot-dipped coating is shown in
Fig. 8. Each of these phases have been con®rmed by EPMA measurements of the
iron content [27]. The gamma (G + G1) phases appear as a thin layer with a
planar interface between the steel substrate and the delta (d) phase layer. The
delta (d) phase has a columnar morphology as a result of a preferred growth
perpendicular to the interface in a direction along the (0001) basal plan of the
Fig. 8. Microstructure of Zn coating formed after 300 s immersion in a 4508C, 0.00 wt% Al bath on a
ULC steel substrate. (1) gamma (G) phase, (2) delta (d) phase (3) zeta (z) phase.
204 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 9. A schematic representation of Fe±Zn phase layer formation in a 0.00 wt% Al±Zn galvanizing
bath. t0 corresponds to zero time, and development occurs according to time such that t1 < t2 < t3 < t4
from Ref. [27].
hexagonal structure [30]. After time, cracks form along this basal plane of the
delta (d) phase layer, that can extend into the zeta (z) phase layer above and the
gamma (G + G1) phase layer below. The zeta (z) phase has two layers depending
upon the supersaturation of Fe in the melt. Adjacent to the delta (d) phase layer,
the zeta (z) phase grows in a columnar morphology that is supersaturated in Fe.
Continued growth of these crystals occurs rather than the formation of new zeta
(z) phase crystals. However, if the zinc melt is supersaturated with iron, and there
is sucient nucleation of new crystals, numerous tiny zeta (z) crystals can form in
the melt, that are separated from each other by the solidi®ed zinc Z phase [29],
Fig. 8.
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 205
Each phase layer in the zinc coating exhibits dierent growth kinetics,
depending upon the immersion temperature, that together aect the total layer
kinetics. For example, in short time immersions up to 300 s at 4508C, Fig. 10, the
zeta (z) phase layer grows rapidly at ®rst, then slows down, while the delta (d)
phase layer grows slowly and after time its thickness increases more rapidly. The
gamma (G + G1) phase layer forms only after long periods of time and seems to
reach a maximum thickness of about 1 mm [27]. Similar eects were reported at
4578C for times up to 6 h [2]. Horstmann [1, 29] reported that there is an overall
inward movement of the gamma (G + G1) phase layer towards the iron, whereas
the zeta (z) phase layer is displaced towards the zinc melt. The delta (d) phase
layer expands in both directions, but generally towards the zinc melt. Thus, as the
gamma (G + G1) phase layer grows into the iron, it is also consumed by the
growing delta (d) phase layer. Similarly, the delta (d) phase layer expands into the
growing zeta (z) phase layer that is advancing into the zinc melt. All of these
transformations are governed by the diusion of Zn into the iron substrate based
on inert marker experiments in both liquid zinc [31] and solid-state diusion
studies [32]. However, Fe probably also diuses outward through the alloy phases
into the zinc melt, but at a much slower rate [31].
To evaluate the kinetics of Fe±Zn alloy layer growth, a power-law growth
equation is generally used to interpret the growth rate data [1], as follows:
Y Kt n
2
where: Y = growth layer thickness, K = growth rate constant, t = reaction time,
and n = growth-rate time constant.
The growth-rate time constant, n, is an indication of the type of kinetics
controlling the growth of the layer under study. An n value of 0.5 is indicative of
parabolic diusion controlled growth, while an n value of 1.0 is representative of
Fig. 10. Individual Fe±Zn gamma (G) phase, delta (d) phase, and zeta (z) phase layer growth for a
ULC steel substrate hot dipped at 4508C in a 0.00 wt% Al±Zn bath. From Ref. [27].
206 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Table 2
Values of n for growth of alloy layers in the lower parabolic range [2]
Table 3
Individual phase layer growth at 4508C
up to 300 s on a iron substrate (0.003
wt% C) in a pure zinc iron saturated
(0.03 wt% Fe) bath [27]
(linear region) occurs between these two regions, but short time experiments up
to 30 min also show parabolic attack in this region [34]. With increasing
temperature, the zeta (z) phase layer decreases until 4958C, when it is no longer
possible to form a continuous zeta (z) phase layer. At about 5008C, the
nucleation of the zeta (z) phase layer is so slow that this compound no longer
appears in the iron-zinc coating, even though the phase diagram, Figs. 6 and 7,
shows that it is stable up to 5308C [29]. In the lower parabolic range, the delta
(d) phase layer continues to increase parabolically with temperature, until the
range of linear attack, where the delta (d) phase layer only grows to a certain
thickness as the outer portion continues to break away [34] up to the
temperature at which the delta (d) phase layer is no longer stable, 6658C.
Breakaway attack is commonly indicative of linear kinetics. According to the
phase diagram, Figs. 6 and 7, the double layer gamma (G + G1) phase can form
at the interface between the iron substrate and the delta (d) phase layer.
Between 550 and 6658C, only the gamma (G) phase layer is stable along with
the constant thickness delta (d) phase layer. Above 6658C, the delta (d) phase
layer is no longer stable and only a gamma (G) phase layer forms. Since there is
no evidence for ¯aking of the gamma (G) phase layer, this layer probably grows
parabolically in the linear region just as it grows in both the lower parabolic and
upper parabolic regions [29].
Substrate solute additions have been reported to aect the rate of attack of zinc
on steel during galvanizing [2]. However, most of the research has been conducted
on steel substrates containing a multiplicity of solute additions that can confound
the determination of any systematic solute eect. Few studies have been concerned
with pure Zn baths without the addition of Al. In general, small additions of
carbon are found to segregate to grain boundaries, impeding the reaction rate [35],
whereas Mn additions of up to 1±2 wt% have very little eect on weight loss and
coating microstructure [36]. Interstitial-free (IF) steel [37], produced by the
addition of titanium and/or niobium to an extra low-carbon grade to precipitate
interstitial carbon and nitrogen atoms, is being utilized as a galvanized coated
sheet product [38]. Phosphorous additions are also sometimes added to these steels
to improve mechanical properties. The eect these solute additions on the
formation and kinetics of galvanizing has recently been studied in Al containing
Zn baths [39±41].
The eect of Fe±Zn alloy formation in interstitial-free steels galvanized in a
pure Zn (Al free) bath has been investigated [27]. Table 4 shows the total alloy
layer growth-rate time constant, n, for a series of IF steels hot-dip galvanized at
4508C for up to 300 s and Table 5 shows the growth-rate time constant, n, for
the individual Fe±Zn phases formed. It was reported [27] that phosphorous
solute additions retard the kinetics of gamma (G) phase layer growth, but did
not aect the growth kinetics of any other Fe±Zn phases. On the other hand,
titanium and titanium + niobium solute additions had no eect on the growth
kinetics on any of the Fe±Zn phase layers found in the coating. As in the 0.003
wt% C substrate, the IF substrates exhibited a parabolic growth-rate time
constant, n = 0.5, for the delta (d) phase layer, indicative of bulk diusion and
208 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Table 4
Total Fe±Zn alloy layer growth-rate time-constant, n,
values for steels hot-dip galvanized in a 0.00 wt% Al±
Zn bath [27]
the zeta (z) phase layer had a value of n = 0.33, that may be related to the
solid±liquid reaction at the interface. The gamma (G) phase layer for the 0.003
wt% C substrate and the other IF steels (except for the phosphorous containing
alloys) had a growth-rate time constant of n = 0.25, indicative of grain
boundary diusion controlled growth. The phosphorous added alloys reduced
the gamma (G) phase layer n to 0.035 2 0.13, most likely by blocking Zn
diusion down solute grain boundaries and preventing gamma (G) phase
formation [42].
Table 5
Individual Fe±Zn phase layer growth-rate time-constant, n, values for steels hot-dip galvanized in a
0.00 wt% Al±Zn bath [27]
Gamma-phase layer
ULC 0.24 20.06
ULC±P 0.10 20.08
Ti IF 0.22 20.11
Ti±P IF 0.03520.080
Ti±Nb IF 0.23 20.05
Ti±Nb±P IF 0.13 20.28
Delta-phase layer
ULC 0.51 20.11
ULC±P 0.44 20.12
Ti IF 0.34 20.12
TI±P IF 0.37 20.13
Ti±Nb IF 0.44 20.15
Ti±Nb±P IF 0.39 20.15
Zeta-phase layer
ULC 0.32 20.03
ULC±P 0.32 20.03
Ti IF 0.28 20.05
Ti±P IF 0.29 20.03
Ti±Nb IF 0.33 20.05
Ti±Nb±P IF 0.33 20.03
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 209
4. Interface reactions
. Several reactions are occurring at the same time, including (1) wetting of the
solid substrate by liquid zinc, (2) dissolution of the steel by the zinc, (3)
isothermal solidi®cation of Fe±Al±Zn intermetallic compounds, (4) solid state
diusional phase transformations, and (5) solidi®cation of the liquid Zn alloy.
. The speed of the reactions are very fast and in some cases take place in less
than a second.
. The transformation front often becomes unstable and therefore is not governed
by simple equilibrium thermodynamics.
The ®rst systematic investigation covering the entire Fe±Zn±Al system was
conducted by KoÈster and GoÈdecke [44] by means of metallography observations
and thermal- and X-ray analysis on alloys. Urednicek and Kirkaldy [45] con®rmed
these ®ndings in a study at 4508C by means of microprobe analysis and
metallographic observations on alloys and solid±liquid diusion couples,
Fig. 11 [46]. As a result of the increased attention to galvanized steel, more recent
results have focused on the zinc-rich corner of the ternary diagram; in particular,
the solubility of (1) Zn in the various Fe±Al intermetallic compound, and (2) Fe
in molten Zn.
Perrot et al. [47] studied the metastable equilibrium conditions that arise during
short time (<30 min) immersion in Zn(Al) baths. They found that for these
relatively short times, an Fe±Al±Zn ternary isotherm at 4508C generated from
EPMA data, Fig. 12, showed extended solubility ranges when compared to the
previously accepted ternary equilibrium diagram of Urednicek and Kirkaldy [45].
For comparison, a long-term equilibrium phase diagram is also included in Fig. 12.
In particular, Fe2Al5 was found to have a solubility for Zn of up to 22.87 wt%
and 13.92 wt% Zn in FeAl3. Similarly, Chen [48] found extended solubility for Zn
in Fe2Al5 to be 21.0 wt%. Long-term equilibrium immersion studies reported that
the Zn solubility in Fe2Al5 was 18.71 wt% [47] or 14 wt% [45]. Perrot et al. [47]
also observed a transient phase for dipping times less than 2 min that had an
average composition of ZnFeAl3, that afterwards formed Fe2Al5 crystals saturated
in Zn. The phase corresponded to a previously reported transient phase [49], that
210
A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 11. Isothermal section of the Fe±Al±Zn phase diagram at 4508C, (a) overall section, (b) zinc rich corner. From Ref. [46].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 12. Evolution of Fe±Zn±Al phase diagram with time at 4508C, (a) metastable: <30 min, (b) equilibrium: >1000 h. From Ref. [47].
211
212 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
was observed during the ®rst step of galvanizing steel in Zn±Al baths. Chen's [48]
short term immersion results (30 min) also showed that the maximum solubility of
Zn in alpha iron was 2.0 wt% in a Zn bath containing 0 wt% Al. Perrot et al. [47],
also found that the delta (d) phase exhibited an extended solubility range of 3.71
wt% Al and an extended Fe solubility range of up to 16 wt% in a Zn bath
containing 0 wt% Al (normally 11.5 wt%. Fe). Similarly, the eta (Z) phase was
also found to be oversaturated in Fe for short-term immersions.
The determination of bath iron saturation has been studied by a number of
investigators in Zn±Al baths [45, 47, 50, 51]. However, in a more recent critical
analysis, an improved zinc rich Zn±Fe±Al ternary equilibrium phase diagram was
developed [52, 53]. Additional studies by Tang et al. [54, 55], on the iron solubility
limits in molten zinc as a function of aluminum content, were conducted and the
intermetallic compounds in thermal equilibrium with the liquid were identi®ed. It
was previously established [23, 56] that the iron solubility limit ([Fe] in wt%) in
pure zinc is a function of temperature ([T] in Kelvin):
lnFe 17:78 ÿ 15388=T
3
For Zn±Al melts, the following was established at 4608C for the zinc corner of the
Zn±Fe±Al ternary equilibrium phase diagram, Fig. 13 [53, 54]:
. When the bath aluminum content is less than 0.10 wt%, the phase in
equilibrium with the liquid is the zeta (z) phase.
. When the bath aluminum content is between 0.10 and 0.14 wt%, the phase in
equilibrium with the liquid is the delta (d) phase.
. When the bath aluminum content is greater than 0.14 wt%, the phase in
equilibrium with the liquid is the Fe2Al5Znx (Z) phase.
These results con®rm previous data [45, 47, 50, 51], that the solubility limit of Fe
decreases continuously with increasing Al content at a given temperature
isotherm. The eect of temperature on the solubility product, [Fe]2[Al]3 in wt%, in
the Fe2Al5Znx (Z) phase dominant region satis®es the following equation:
Fig. 13. Zinc-rich corner of the 4508C isothermal section of the Fe±Zn±Al phase diagram. From
Ref. [54].
agitation, (5) increasing the presence of Si in the steel, and (6) decreasing surface
roughness [2]. The complex solidi®cation and solid state diusional reactions
during galvanizing has been reviewed recently [57].
Fig. 14. Mechanism of formation of the inhibiting layers. From Ref. [58].
Table 6
Summary of coating microstructure in continous galvanizing [59]
Al content Equilibrium Intermetallics Alloy layer Nucleation rate (s) Growth rate (mm/s)
(wt%) compound in coating characteristics
the amount of dissolved Fe in the bath, since supersaturated Fe can combine with
Zn and Al to form Al-containing zeta (z), delta (d), and Fe2Al5Znx (Z) particles,
further reducing the amount of Al in the liquid Zn. Avoiding the entrapment of
intermetallic particles in bath samples can be very dicult, thus determining the
eective aluminum from the bath assay is problematic [57]. Based on the revised
Zn±Fe±Al ternary equilibrium phase diagram [53, 54], Fig. 13, new technologies
for determining eective bath Al, such as the DEALTM computer program along
with Al sensors [59, 60] have been developed. The program calculates the eective
Al content from bath assays of total Al and Fe in Zn. The program also
calculates the dissolved Fe content and predicts the types and amounts of
intermetallic dross particles entrapped in the bath assay sample [54].
The rate of Al uptake in Zn coatings was found to be dependent on strip-entry
temperature and to change rapidly with time [61, 62]. Isobe [61] showed that in the
time required for steel to pass through a bath on a continuous galvanizing line
(<3 s), a signi®cant amount of the total Al uptake occurs, Fig. 15. The amount of
Al in the Al±Fe alloy layer increased continuously with Al bath content [63],
Fig. 16. Thus, the incubation period (i.e. the time for Fe±Zn phases to form)
increases with an increase in Al content in the bath and decreasing bath
temperature [64], Fig. 17. Faderl et al. [62] found that for a bath containing 0.18
wt% Al, the Al content in the interface increased approximately linearly with the
dierence between the strip-entry temperature and the bath temperature.
However, long immersion time studies [65, 66], resulted in the growth kinetics of
the inhibition layer following a parabolic time law and that bath Fe contents
in¯uenced the overall growth kinetics. Tang [55] showed that the formation of the
Fig. 15. Growth kinetics of Fe2Al5 layers at 4708C for various bath Al contents. From Isobe M. Initial
alloying behavior in galvannealing process. CAMP-ISIJ 1992;5:1629. # 1992 The Iron and Steel
Institute of Japan. [61].
216 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 16. Eect of bath aluminum content on amount of aluminum reaction (bath temperatureÐ4608C;
immersion timeÐ1 s) from. Ref. [63].
inhibition layer is a two-stage process. The ®rst stage, associated with a high rate
of Al uptake at the coating/substrate interface, is controlled by continuous
nucleation of Fe2Al5, followed by a second stage diusion-controlled growth
process. He proposed a model in that Al uptake was shown to increase with
increasing strip-entry temperature and thickness, since both work to increase the
eective temperature for nucleation and growth processes. Al enrichment was
Fig. 17. Eects of bath aluminum content and alloying temperature on incubation period. From
Yamaguchi H, Hisamatsu Y. Reaction mechanism of the sheet galvanizing. Trans ISIJ 1979:19;649. #
1979 The Iron and Steel Institute of Japan. [64].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 217
100z jj 101a
010z jj 121a
As the aluminum content is increased to between 0.12 and 0.14 wt%, Fe±Al±Zn
ternary phases begin to appear along with zeta (z) phase and/or delta (d)
phase [69±71]. The Fe2Al5 layer had a ®ne granular structure, whereas the
morphology for the zeta (z) phase was ``pillar-like'' and the delta (d) phase was
columnar. In most studies, it is unclear whether the Zn±Fe phases are nucleated
on top of the Fe2Al5 phase or if the Fe2Al5 phase and Zn±Fe crystals nucleated
Fig. 18. Microstructure of hot-dip galvanized DQSK steel in a 0.10 wt% Al±Zn bath # 1993 Elsevier
Science Ltd. [67].
218 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
side-by-side at the steel interface surface. In more recent results, an in-situ HVEM
study showed the existence of both z phase and d phase at the interface between
the Fe±Al inhibition layer and liquid zinc containing 0.2 wt% Al [72]. The relative
amounts of zeta (z), delta (d) and Fe2Al5 phases, are dependent upon the substrate
steel reactivity, bath temperature and immersion time.
Increasing the Al content or decreasing the bath temperature, increases the
stability of the Fe±Al inhibition layer. In baths containing in excess of 0.15 wt%
eective Al, a continuous Fe±Al inhibition layer forms upon immersion. The Fe±
Al layer was found to be essentially the orthorhombic Fe2Al5Znx (Z) containing
approximately 23 wt% Zn [43]. Guttmann et al. [43], found that the layer had an
overall thickness of 250 nm and was made up of two sublayers. The lower layer in
contact with the substrate was a compact layer of very small, roughly equiaxed,
closed packed crystals, having a diameter of the order of 60 nm. The crystals are
arranged in colonies of speci®c crystallographic orientation whose boundaries
delineate the underlying steel grain boundary. Several variants can exist within the
area of one substrate grain. The orientation relationship between the substrate
steel and the Fe2Al5 layer is reported to be [57]:
or
Tang and Adams [52] found that the Fe2Al5Znx compound had a growth
direction of [100]. The thicker upper layer on the coating side of coarser,
pancaked shaped crystals, approximately 300±600 nm in diameter and
approximately 200 nm in thickness, exhibits random crystalline orientations and
morphologies. These ®ndings can help to explain the two-stage growth kinetics
observed previously by Isobe [61], Fig. 15 and Al uptake by Tang [55].
. During the initial growth period (<1 second), the lower layer colonies grow to
meet each other forming a compact layer. This very rapid interface controlled
reaction probably exhibits linear kinetics.
. The second growth period (>2 seconds) corresponds to the formation of the
upper, coarse crystal layer. The slower kinetics may re¯ect control by solid state
diusion of Fe through the already formed lower layer.
Fig. 19. Typical outburst formation in a 0.20 wt% Al±Zn bath immersed at 4508C for 3600 s. From
Ref. [73].
Fig. 20. Schematic diagram showing the Fe±Zn outburst growth behavior. From Hisamatsu Y. Science
and technology of zinc and zinc-alloy coated sheet steel. GALVATECH '89. Tokyo: The Iron and Steel
Institute of Japan. 1989. p. 3. # 1989 The Iron and Steel Institute of Japan. [74].
formation of more stable Fe±Zn phases [45, 66, 76]. Guttmann [57] also showed
by diusion path analysis that this model was unable to predict the Fe±Zn
phase growth rate and morphologies that would result from Al depletion.
Nishimoto et al. [76] proposed that rapid precipitation of Fe2Al5 at the
substrate grain boundaries would produce a greater Al depletion at the
boundaries than in front of the grain interiors, Fig. 21. Model measurements
show that Al depletion would be minimum and would be replenished by the
bath Al content [43]. The reduction of surface oxides by Al dissolved in the
bath has also been proposed as mechanism for Al depletion [77], however,
oxide reduction by Al was experimentally shown not to take place [43, 78].
3. Diusion of zinc through the inhibition layerÐZn atoms reach the substrate and
cause nucleation and growth of Fe±Zn intermetallic compounds at the Fe2Al5/
substrate interface. Guttmann [43, 57] has proposed that inhibition layer break
down occurs by Zn diusion down short circuit paths in the Fe2Al5 inhibition
layer, as original suggested by Hisamatsu [74]. In reported studies on thick
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 221
Fig. 21. Schematic diagram of the formation of Fe±Zn phase growth at substrate grain boundaries.
From Nishimoto A, Inagaki J, Nakaoka K. Trans ISIJ 1986;26:807. # 1986 The Iron and Steel
Institute of Japan. [76].
In a recent study [78] iron oxide was used as a simulation inhibition layer to test
the Guttmann hypothesis [43, 57]. In these experiments, a pure Zn bath (0.00 wt%
Al) was used in order to prevent the confounding eect of the formation of an
additional Fe2Al5 inhibiting layer. The iron oxide initially acted as a physical
222 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 22. Short circuit Zn diusion path through Fe2Al5. From Ref. [43].
barrier for Zn diusion, but eventually outbursts form beneath the oxide layer
broke through the layer, causing sections to break away and become incorporated
into the coating, Fig. 23. Increased immersion time for a constant oxide layer
thickness led to an increase in the number of outbursts. Cracks and other
microdefects in the oxide acted as fast diusion paths for Zn, simulating the short
circuit diusion mechanisms for Fe2Al5 inhibition layer break down in Al-
containing Zn baths [43, 57].
Fig. 23. Outburst formation in a 0.00 wt% Al bath with a simulated iron oxide inhibition layer. From
Ref. [78].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 223
Table 7
Total alloy layer and individual Fe±Zn phase layer growth rate time constant (n) values for the 15- and
85-mm grain size ULC steel galvanized in a 0.00 wt% Al±Zn bath [79]
Fig. 24. Incubation time for outburst formation as a function of substrate steel grain size (log scale).
Ref. [79].
bath, Table 7. In the 0.20 wt% Al baths, outburst formation readily occurred due
to the initial formation of the Fe2Al5 inhibition layer; however, increased grain
size signi®cantly retarded incubation time and promoted Fe2Al5 inhibition layer
stability, Fig. 24. An SEM analysis of an 85 mm grain size substrate with outbursts
at grain boundaries [79, 80], Fig. 25, showed that the Fe2Al5 inhibition layer was
faceted and cracked, con®rming the Zn short circuit diusion mechanism through
the Fe2Al5 inhibition layer [43, 57].
Fig. 25. Outbursts in an 85 mm grain size ULC steel immersed in a 0.20 wt% Al±Zn bath for 1800 s.
From Ref. [80].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 225
Fig. 26. Outbursts at the same grain boundary in a phosphorous ion-implanted (P) side and a
nonimplanted side (NP). From Ref. [86].
226 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
after extended reaction times on both the P ion implanted and nonimplanted
surfaces [86]. The Fe±Zn outbursts were found to directly correspond to the
location of a single grain boundary site, Fig. 26, and that a greater Fe±Zn
reaction occurred on the P-free side (NP), since there was no P segregation in
the grain boundary. It was shown that substrate grain boundary cleanliness is
the dominant steel substrate structural feature that controls the kinetics of Fe±
Zn alloy phase formation in aluminum containing zinc baths. Recently, these
results were con®rmed with a study of phosphorous additions in IF-P steels.
Outbursts were ®rst found after 100 h in the 0.105 P and was related to a
Sandelin eect [87].
. Interstitial free (IF) alloy additionsÐIF steels can contain additions of titanium
and/or niobium at extremely low carbon levels. It is well known that Ti±IF
steels are more sensitive to outburst formation than Al-killed or even Nb±Ti
steels [74]. Because these steels are more likely to form carbide, nitride, sul®de
and phosphide precipitates in the grains, preventing segregation to the grain
boundaries, the concept of excess titanium, Ti**, has been introduced [39].
Ti Total Ti ÿ 3:99C ÿ 1:49S ÿ 3:42N ÿ 1:55P
5
A positive Ti** indicates excess titanium and therefore a clean, carbide free and
reactive grain boundary. A negative value of Ti** would indicate that not all of
the solute carbon is tied up and zinc diusion down the boundaries would be
blocked.
Fig. 27. Comparison of iron losses for dierent immersion times and dierent Si contents in the steel.
From Ref. [89].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 227
Fig. 28. A schematic representation of Fe±Zn phase layer formation in a 0.20 wt% Al±Zn galvanizing
bath. t0 corresponds to zero time, and development occurs according to time such that t1 < t2 < t3 < t4.
From Ref. [90].
Al and Zn±6 wt% Al baths, respectively [91]. Ichiyama et al. [94] suggested that
the intermetallic layer was Fe2Al5 or a composite layer of Fe2Al5/FeZn7/FeZn13
and Makimattila [95] suggested that two separate Fe±Al±Zn phases exist. The
initial formation of intermetallic phases after inhibition layer breakdown at 4508C
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 229
Table 8
Individual Fe±Zn phase layer growth-rate time constant, n, values
for the steels hot-dip galvanized in a 0.20 wt% Al±Zn bath [90]
Gamma-phase layer
ULC 0.0502 0.049
ULC±P ÿ0.03220.003
Ti IF 0.162 0.01
Ti±P IF ÿ0.528*
Ti±Nb IF 0.192 0.05
Ti±Nb±P IF 0.0362 0.158
Delta-phase layer
ULC 0.382 0.02
ULC±P 0.382 0.05
Ti IF 0.532 0.07
Ti±P IF 0.502 0.07
Ti±Nb IF 0.572 0.07
Ti±Nb±P IF 0.622 0.09
Fig. 29. The eect of Ti** on the growth rate time constant, n. From Ref. [80].
adherent to the iron substrate. However, aluminum again diuses to the iron
substrate through liquid channels in the interfacial layers and the reaction
proceeds rapidly. In both cases the exothermic reaction produced by forming
Fe2Al5 and FeAl3 consumes the panel in less than 2 min. Ghuman and
Goldstein [49] found a similar eect in baths above 6008C containing 1±10 wt%
Al, which was related to the formation of an Fe2Al5Znx (Z) phase, hypothesized
to be an Brewer±Engle compound, which forms by a large heat of evolution.
Thus, in this case an inhibition layer never has an opportunity to form.
Silicon suppresses the exothermic reaction by forming a solid interfacial layer
that acts as a diusion barrier or inhibition layer for the reactive species, which is
probably Al [101]. Therefore, in order for a reaction between the bath and the
iron substrate to occur, the Al has to diuse through the solid phase(s) in the
interfacial layer, which is considerably slower than liquid state diusion. The
composition of the interfacial layer of commercial galvalume was reported to be
in one study a single-phase layer containing 55.8 wt% Al, 33.7 wt% Fe, 6.7 wt%
Si and 3.8 wt% Zn, and in another study a two-phase layer containing 53.1 wt%
Al, 25 wt% Fe, 8.9 wt% Si and 13 wt% Zn, and 56.6 wt% Al, 36.7 wt% Fe, 3
wt% Si and 3.7 wt% Zn [102]. Table 9 lists the types of phases that constitute the
interfacial layer [101] as a function of dipping time at 6108C. In the 1.7 wt% Si
bath, T5C is the ®rst phase formed at the interface at short times (<4 s).The T5C
phase has a composition of 57 wt% Al, 30 wt% Fe, 6 wt% Si and 7 wt% Zn.
Table 9
Phases present in the reaction zone of galvalume 55wt% Al coatings hot-dipped at 618C as a function of dipping time [101]
4 ? T5C ? ? T4
25 Fe2Al5 + ? ? ? ? Fe2Al5 + ?
100 Fe2Al5 + ? Fe2Al5 + ? Fe2Al5 + ? Fe2Al5 + ? Fe2Al5 + ?
256 Fe2Al5 + ? Fe2Al5 + T1 + ? Fe2Al5 + T1 + T5H Fe2Al5 + T1 + T5H Fe2Al5 + ?
400 Fe2Al5 + ? Fe2Al5 + T1 + ? Fe2Al5 + ? Fe2Al5 + ? Fe2Al5 + ?
900 Fe2Al5 + FeAl3 + T1 Fe2Al5 + T1 Fe2Al5 + ? Fe2Al5 + T1 + ? Fe2Al5 + T1
FeAl3 + T5C FeAl3 + T2 + T4
1800 ± Fe2Al5 + T + 1 Fe2Al5 + T1 ± Fe2Al5 + T1 + FeAl3 + T2 + T3 + T4
FeAl3 + T5C + T5H FeAl3 + T2 + T5H
2700 ± Fe2Al5 + T1 ± ± Fe2Al5 + T1 + FeAl3 + T2 + T3 + T4
FeAl3 + T5C + T5H
3600 ± Fe2Al5 + T1 ± ± Fe2Al5 + T1 + FeAl3 + T2 + T3 + T4
FeAl3 + T5C + T5H
A.R. Marder / Progress in Materials Science 45 (2000) 191±271
231
232 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
As Al diusion continues with longer dipping times, Fe2Al5 and FeAl3 phases
containing 2±3 wt% Si form and continue to slowly consume the entire coating.
Apparently, the T5C phase acts as the initial inhibition layer with the Fe2Al5 phase
containing Si forming next to the substrate interface. Others have reported that
the intial inhibiting phase was a cubic structure based on the hexagonal phase
Fe5Si2Al20 with small amounts of a transition metal [103] and that these layers
form in as little as 0.3 s at 6008C [104]. It was found that alloy growth increased
from an immersion temperature of 590 to 6058C. However, no further increase
alloy growth was observed when the temperature was increased to 6208C. This
eect was related to an accompanied change in the structure and composition of
the interfacial alloy from Fe2Al5/cubic phase to Fe2Al5/FeAl3. It was also reported
that signi®cant alloy growth occurs during cooling from 6008C at rates as high as
308C/s [104]. Air cooled specimens were shown to produce faceted crystals on the
alloy layer that were prevented by the addition of 0.026 wt% V to the bath.
Localized outbursts are observed only at immersion times greater than 1800 s [101].
This reaction produces Fe2Al5 and FeAl3 phases, both of which ¯ake o the
substrate and ¯oat into the bath. Si was not found in Fe2Al5 and FeAl3 phases
formed in the burst region, whereas the Fe2Al5 and FeAl3 layers that adhered to
the panel contained Si. This may indicate a buildup of stresses at the interface in
the absence of Si in the Fe2Al5 and FeAl3 phases [100].
Table 10
Correlation between cooling rate, solidi®cation period and undercooling [105]
2 Air 10 <1
4 5% H2/N2 5 <1
15 5% H2/N2 2 <2
a
Results obtained from two dierent bath compositions (Zn + 0.2 wt% Al + 0.0025 wt% Pb and
Zn + 0.2 wt% Al + 0.05 wt% Pb) did not vary signi®cantly; thus, an average value is given
zinc interface which oers preferred nucleation sites for zinc dendrites. It may be
assumed that similar Zn alloy coatings will behave in the same manner in that
nucleation of the overlay coating will occur at the zinc/substrate interface.
The importance of aluminum additions to the bath to control the type and
amount of inhibiting layer(s) has been reviewed above. Actually, the eect of
aluminum additions to interfacial layer control is a result of the addition of
aluminum to produce a speci®c as-cast microstructure in the overlay portion of
the coating in order to induce speci®c properties in the coating such as corrosion
resistance. As a result of the aluminum additions, interface reactions require a
knowledge of ternary and quaternary equilibrium and metastability for the
elements involved. On the other hand, binary and ternary equilibrium interactions
are sucient to explain the as-cast overlay structure. This section will ®rst review
the important Zn±Al equilibrium phase diagram that will be followed by a
discussion of the three commercially important coatings: galvanized (<1 wt% Al),
galfan (5 wt% Al±Zn) and galvalume (55 wt% Al±Zn).
Table 11
Phase transformations in the Al±Zn system
Phase transformation Composition wt% (at % Zn) Temperature (8C) Transformation type
these phases, Table 11, are a eutectic at 95.0 wt% Zn (88.7 at% Zn), a eutectoid
at 77.7 wt% Zn (59.0 at% Zn) and the existence of a miscibility gap with a
critical temperature of 351.58C at 61.3 wt% Zn (39.5 at% Zn).
. Regular spangle, where the coating solidi®es from the dipping temperature by
air cooling, producing the well-known spangle ®nish.
. Minimum spangle, where the coating is quenched using water, steam, chemical
solutions, or by zinc powder spraying.
. Extra-smooth temper roll ®nish carried out as an additional operation with
regular and minimum spangle material.
236 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Hot-dip galvanized coatings often show a strong (0001) basal plane texturing of
the spangles (zinc crystals) upon solidi®cation. The proportion of basal plane
orientation increases with decreasing coating grain size [112] (i.e. minimized
spangle and temper rolled coatings) and correlate well with improved paint
adherence [113]. With preferred nucleation sites at the liquid Zn/substrate
interface, growth of the Zn spangles occurs in the following manner [105]:
. The initial growth stage (0.1 s) involves sideways growth of Zn basal planes
(0001) parallel to the interface in the [1100] growth direction. The entire steel
surface is covered by a solid layer of zinc dendrites, whereas the surface remains
liquid.
. The second stage involves slow thickening of the solid zinc grain which is
dependent on grain orientation.
. The third stage, or continuous thickening of the zinc grain, causes solute
enrichment of the remaining liquid and ®nally Pb precipitation between Zn
dendrite arms.
Large spangles are generally associated with solute additions to the galvanizing
bath and Pb, at concentrations greater than 0.04 wt%, is the solute generally
added to molten Zn to produce spangles, Fig. 32 [114]. Al, Mg, Sn and Cd
additions do not in¯uence spangle growth [109, 115], but Sb and Bi additions
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 237
Fig. 32. Eect of lead content on spangle size. From Ref. [114].
produce spangles [116]. Fasoyino and Weinberg [109] found that alloy additions
such as Pb and Sb have lower surface tension and promote spangle formation.
Strutzenberger and Faderl [105] proposed that these same elements segregate
ahead of the growing dendrite, lowering surface tension and allowing the growth
velocity of the zinc dendrite to increase, resulting in larger grains or spangles.
238 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 33. Planar view of the lamellar microstructure of a galfan coating. From Ref. [111].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 239
Fig. 34. Planar view showing (a) nodules and (b) colonies of a galfan coating. From Ref. [111].
Fig. 35. Schematic of the solidi®cation of a galfan coating. From Ref. [111].
appearance has been enhanced by decreasing the Pb content in the bath alloy and
by an increase in skin-pass reduction [124].
Fig. 36. Mechanism for galfan formation and denting/cracking. From Ref. [124].
242 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 37. Microstructure of galvalume coating: (a) spangle ®nish; (b) dendrite arm spacing; (c) cross-
sectional view. From Ref. [111].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 243
Fig. 39. The eect of cooling rate on Si particles in the galvalume coating. From Ref. [126].
244 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 40. Schematic of the solidi®cation of galvalume, t1 < t2 < t3 < t4. From Ref. [111].
6. Heat treatmentÐgalvannealing
Galvanneal coatings are essentially diusion coatings that expose the zinc
galvanized steel to an annealing temperature around 5008C to produce a fully
alloyed coating containing Fe±Zn intermetallic phases. This is accomplished by
inserting heating and cooling capacity above the liquid zinc pot in order for the
galvannealing process to be continuous, Fig. 1. The variables involved in
producing the desired galvanneal microstructure and properties are complex.
Good process control requires that the eects of heating rate, hold temperature
and time, and cooling rate on the Fe±Zn reaction kinetics be well understood so
that the optimum coating for the desired properties can be obtained. Besides
processing variables, variations in bath chemistry and substrate composition all
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 245
Fig. 41. Precipitates in the interdendritic boundaries of galvalume. From Ref. [111].
The topography of the galvanneal coatings is also important. Van der Heiden et
al. [128] studied the surface of typical production galvanneal coatings by SEM
stereophotography and found the existence of ``craters''. Crater formation was
observed in-situ in a hot-stage environmental scanning electron microscope [129].
Craters, Fig. 43, were found to be inherent to the galvanneal coating layer,
causing major ¯uctuations in coating thickness [128] and appear to be associated
with outburst formation [129, 130]. A mechanism was proposed that can explain
the relationship between outburst formation and the appearance of craters [128].
246 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 42. Morphology of galvanneal coatings: (a) type 0, (b) type 1, and (c) type 2. From Ref. [127].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 247
Fig. 43. Crater formation in galvanneal coatings: (a) cross-section, (b) planar surface. From Ref. [129].
Fig. 44. Schematic of the phenomenological model of galvanneal morphology development. t0 corresponds to zero time of the as-galvanized structure, and
development occurs according to time such that t1 < t2 < t3 < t4 < t5. From Ref. [129].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 249
the processing parameters and composition of the bath and substrate steel,
however it was proposed that the time sequence was as follows:
Fig. 45. Sequence of outburst formation during simulated in-situ galvannealing. From Ref. [132].
250 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
iron in the liquid eta (Z) phase or upon cooling. An interfacial gamma (G) phase
forms at the coating/steel interface [127].
. t3ÐZn depletion occurs with longer temperature exposure resulting in the
complete consumption of eta (Z) phase at the coating surface. Fe concentration
increases in the coating as the delta (d) phase continues to form, pushing the
zeta (z) phase to the surface and maintaining a constant 1 mm thickness gamma
(G) phase [133]. This has led many to rely on an Fe concentration measurement
(approximately 10 wt%) as a requirement for the optimum galvanneal coating,
see e.g. [134]. This microstructure is referred to as Type 1 galvanneal [127].
. t4ÐWith longer times at temperature, delta (d) phase diusional growth
continues towards the surface of the coating consuming the zeta (z) phase, while
maintaining a constant 1 mm thickness gamma (G) phase [133].
. t5ÐOnce the delta (d) phase reaches the surface it serves as the Zn rich side of
the delta (d) phase Fe±Zn/steel diusion couple, allowing for the continued
growth of gamma (G) phase at the expense of the delta (d) phase. Cracking
occurs along delta (d) phase basal planes parallel to the coating/steel
substrate [135]. This microstructure is referred to as Type 2 galvanneal [127].
Fig. 46. Morphology development for the Ti±IF steel (0.10 wt% Al bath). From Ref. [136].
Fig. 47. Typical temperature pro®le of the cooling tower. From Ref. [138].
252 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
Fig. 48. The eect of heating rate on the type 0 to type 1 microstructure transition. From Ref. [139].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 253
Fig. 49. Summary plot of temperature/time morphology transition for DQSK steel with (a) 0.10 wt%
Al±Zn, and (b) 0.15±Zn wt% Al. From Ref. [127].
Fig. 50. Eect of bath aluminum content on the growth of G1 phase as a function of Fe content in the
coating. From Ref. [64].
onset of outbursts [132]. Con and Thompson [41] were able to show that 0.07
wt% P can shift the phase ®eld boundary stability to longer times.
7. Coating properties
Fig. 51. Service life (time to 5% rusting of steel surface) versus thickness of the coating for various
atmospheres. From Ref. [148].
Fig. 52. Corrosion loss of coating layer after atmospheric exposure test. From Uchima Y, Hasaka M,
Koga H. Eect of structure and mischmetal addition on the corrosion behavior of Zn-5 mass%Al
alloy. GALVATECH '89. Tokyo: The Iron and Steel Institute of Japan. 1989. p. 545. # 1989. The
Iron and Steel Institute of Japan. [155].
7.2. Formability
The deformation and fracture behavior of Zn-based coatings on sheet steel can
alter the performance of steels in stamping operations [160]. During deformation,
increased frictional conditions at the sheet/tool steel interface and the substrate
mechanical properties can change the formability response of the material.
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 259
Fig. 53. Corrosion losses of hot-dip coatings in the industrial environment of Bethlehem, PA. From
Ref. [148].
Fig. 54. Schematic model for the coating exfoliation process. From Ref. [162].
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 261
7.3. Weldability
Fig. 55. Increase of active face diameter with the number of welds. From Ref. [178].
zinc melting point (4198C) [178]. Zn alloys with the Cu of the Cu/Cr/Zr electrode
to produce brass. The mechanical properties of brass are lower than the electrode
alloy, leading to mushrooming of the active face of the electrode, Fig. 55. As the
active face increases, the current density decreases, lowering the nugget size.
Spot weldability of galvanneal coatings is improved over galvanized coating
since it is more dicult for these Fe±Zn phases to alloy with the copper electrode,
thus improving electrode life. White et al. [179] studied the weldability of
galvanneal coatings and found that electrode life was primarily controlled by
welding current. The improvement in electrode life is due to the special ability of
the coating to form a convex shape without cavities on the electrode
tips [180, 181].This phenomenon allows a high current density to be maintained,
enhancing electrode life. Electrode life is also a function of steel substrate
composition. Boron additions to the base steel have been found to improve the
life of galvanneal coated IF steels [182, 183]. Electrode life can vary by a factor of
2±3 between ULC and HSLA steel, con®rming the fact that the electrode life is
governed by the ability of the coating to form intermetallic phases on the
electrode tip. These phases do not stick or diuse into the weld surface and
remain on the electrode tip [184].
7.4. Paintability
Although zinc coatings are often used in the as-coated state, some applications
call for a painted surface and therefore paintability is an important design
property of the coating. It has been shown that large spangle material is dicult
to paint [113], therefore most painted products are either minimum spangle or
A.R. Marder / Progress in Materials Science 45 (2000) 191±271 263
Table 12
Eect of hot dip coatings on threshold voltages for cratering
of cathodic electrophoretic primer [148]
temper rolled. In most painted products, a complex coating composite is used for
corrosion protection. In addition to the Zn coated sheet steel, the composite
includes a zinc phosphate pretreatment or complex oxide thin coating, the primer
and various top coats [185]. Much work has been done on chemical
pretreatments [186] and a detailed discussion of painting technology of zinc
coatings is beyond the scope of this review, see e.g. [187]. In the automotive
industry, following the pretreatment, most automobile bodies are primed with an
electrophoretic paint (e-coat) and as a result, resistance to e-coat cratering is an
important property. At high e-coat voltages, sparking as a result of exceeding the
dielectric properties of the deposited paint ®lm, causes localized heat generation,
®lm disruption and premature curing of the paint [188]. After paint curing these
sparked areas form pin-point craters that result in a paint surface with a
detrimental appearance [113]. Therefore, resistance to e-coat cratering, expressed
in cratering threshold voltage, is an essential paintability property, Table 12 [148].
These results show that zinc±iron galvanneal have a greater tendency to produce
cratering defects than galvanized steels, although galvalume coatings are superior
to both. However, galvanneal coating paintability is better than galvanized
coatings because of the microscopically rough surface formed as a result of the
Fe±Zn alloy phases throughout the coating.
Acknowledgements
The author would like to acknowledge the numerous discussions and invaluable
help given by his colleagues A.O. Benscoter, M.R. Notis, J.N. DuPont, M.
Dubois, J. Wegria, J. Faderl and F. van Loo. The review of the manuscript and
the enlightening conversations of F.E. Goodwin is greatly appreciated. The
speci®c ®nancial support through the years by the International Lead Zinc
Research Organization, British Steel, Cockerill Sambre, Union-Miniere, Voest
Alpine, National Steel, LTV Steel, Dofasco, Rouge Steel and Noranda is greatly
acknowledged. Thanks to the Technion, Israel Institute of Technology, for the
ability to initiate this eort on my sabbatical visit. Most of all, gratitude is due to
all my former students, S. Bluni, C. Drewien, S. Hayes, R. Fraley, K. Goggins,
264 A.R. Marder / Progress in Materials Science 45 (2000) 191±271
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