GALVANISING OF HOT ROLLED STRIP
L. Bordignon
CRM, Rue E. Solvay 11, B-4000 Liège
ABSTRACT
A systematic study of the various process
parameters has allowed to identify the
main parameter responsible for the poor
coating wettability: the carbon segregation
before hot dipping. Indeed, during the hot
rolling process, carbon segregation at the
steel/scale interface induces the formation
of pearlite. During reheating at low
temperature, that pearlite can reject carbon,
which diffuses at a short distance to form a
graphite structure on the steel surface and
inhibits the Al-Fe-Zn reactivity. An
increase of the annealing temperature
promotes decarburising and improves
significantly the zinc wettability. Other
possibilities have been found to suppress
the graphite type segregation like a re-
heating under pure hydrogen or a surface
pre-oxidation. The most easily way to
improve zinc wettability on industrial lines
is however the increase of the bath and/or
the strip temperature.
Finally, H2 blistering seems to be
associated mainly to the amount of H2 in
the reheating furnace.
1. INTRODUCTION
Today, the continued trend for the
production of galvanised strip rather than
for uncoated strip is also more and more
applied on hot rolled materials for heavier
applications.
Moreover, the improved quality of thinner
gauge hot rolled strip now means that for
an increasing range of end products cold
rolling is no longer necessary. That
practice often needs however to finish the
hot rolling in the ferritic structure, which
significantly modifies the scale thickness
and improves the mechanical properties of
the hot rolled strip. Consequently, there are
potentially large savings to make on
production costs providing, of course, the
finished hot rolled galvanised product is
fitted for purpose and reaches the same
quality as the cold rolled steel grades.
Nevertheless, with hot-dip galvanising of
hot rolled strip some problems can arise :
- Poor coating adhesion can be caused by
oxides staining after pickling or bad
surface preparation after reheating at
low temperature
- Atomic hydrogen can be introduced in
the steel during pickling and annealing.
The H diffusion and recombination at
the steel/coating interface can induce an
hydrogen blistering.
A systematic study of the influence of
various process parameters on galvanising
reaction and coating formation will lead to
better understand and overcome these
galvanising problems.
2. EXPERIMENTAL PROCEDURE
The different industrial hot rolled steel
grades, alloyed with increasing amounts of
C, Mn, Nb, Si and Cr (see table 1), were
pickled, reheated and galvanised in the
conditions below.
- pickling conditions : 150 g/l hydrochlo-
ric acid (at 37%) was used with 0.1%
inhibitor (Leuzolit), 60 g/l Fe2+ as FeCl2
and 5g/l Fe3+ as FeCl3. After pickling
for 60 seconds at 80°C the panels are
rinsed and brushed in demineralised
water at 80°C for 5 seconds. Cold water
is then sprayed on the panels before a
final dipping in methanol ;
- annealing conditions : the samples are
reheated in an infrared furnace at 25°C/s
up to the soaking temperature (typically
550°C) during 25 seconds in an
atmosphere containing 20%H2 and
0.038% H2O (Dew point - 30°C) ;
- galvanising conditions : after cooling at
5°C/s, the panels are hot dipped at a
temperature slightly higher (5°C) than
the bath temperature (typically 460°C)
during 5 seconds in a bath containing
0.22%Al (± 0.01)-Fe saturated

Table 1. Steel composition (wt% 10-3)

Rolling Steel C Mn Nb Cr Si P S N Al Cu Ni
A 35 243 1 26 6 13 11 4.1 44 10 20
B 50 247 3 20 6 10 12 2.7 55 13 28
C 39 249 3 25 6 16 11 3.2 44 21 32
D 71 335 2 29 9 14 12 5.2 45 15 29
Austenitic E 146 765 2 25 9 10 5 8.8 43 19 31
F 137 747 - 29 8 14 9 4.5 30 14 35
G1/G2 92 938 37 31 10 19 10 6.8 44 32 35
H 68 916 - 517 38 43 3 5.6 41 69 40
I 65 1270 18 27 470 13 5 9 30 12 34
Ferritic J 31 216 <1 14 5 10 7 - 42 7 25

3. RESULTS AND DISCUSSION carbides (pearlite). That segregation

The study was more focused on a classical could be explained by the impossible
steel grade (steel A) and on a high alloyed diffusion of carbon through a compact
steel (steel H) for the study of the different iron oxide layer to form carbon
process steps : monoxide on the surface.
- characterisation of the base materials
- surface characterisation after pickling 0.04 Fe 0.7

and annealing Cr
0.6
0.03
- zinc wettability and reactivity after
Fe intensity (V)
Intensity (V)

galvanising C 0.5
0.02
- H2 blistering. Steel H 0.4

0.01 O
0.3
Characterisation of the base materials Cu
The GDOS profiles (Fig.1) made on the raw 0.00 0.2
materials (steels A and H) clearly show 0 100 200 300 400 500

some segregation at the steel/scale TIME (s)

interface : Fe
Steel A
- less oxidisable elements than iron like 0.04 0.7
Cr x10
Cu (and also Ni). The presence of such Cu 0.6
0.03
element is explained by a back-diffusion
Fe intensity (V)
Intensity (V)

mechanism during the scale grows ; 0.02

0.5

- more oxidisable elements than iron like C 0.4

Cr are also found at that interface. Their 0.01
0.3
segregations is described by a selective O

oxidation mechanism made by the 0.00 0.2

0 100 200 300 400 500
reduction of the iron oxide ;
TIME (s)
- finally carbon segregation can be
observed in the same interface. That Fig.1. GDOS in depth profile on hot rolled
carbon is associated with iron to form steels A and H
 12500 C1s 3000 Fe-OH Fe-O
Fe2p3 Fe-metal O1s
10000 Fe-oxide 1750 C-C 2500 H2O
7500 600°C 2000 Sb Sb
1250
500°C 1500

c/s
c/s
5000
c/s

450°C 1000
2500 750
Pickled R-CH3 500
0 250 0
740 730 720 710 700 300 295 290 285 280 545 540 535 530 525
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Fig.2. Influence of re-heating temperature on surface chemistry of steel A (XPS analysis)

Characterisation of the pickled and to the XPS apparatus, is sufficient to

annealed strip
After pickling, a thin iron oxide layer
covers the surface as indicated by the XPS
analysis (Fig.2). For getting a clearer
lecture of the pictures, the backgrounds are
however adapted to avoid curves
overlapping.
Indeed, the detection of the metallic iron
peak (707eV), without any surface
sputtering, shows that the oxidised layer is
very thin (less than 5nm). That oxide is
formed after pickling by a classical surface
passivation.
Moreover, the detection of C-H (285.0 eV),
C-OH (286.3eV) and C-OOH (289.1eV)
peaks reveals the presence of a pollution
film over the oxidised surface, which is
rapidly removed by a sputtering of less than
1nm. All these results indicate that the
pickling operation was correctly done.
An annealing at low temperature (500°C),
performed in a chamber directly connected
20000 Fe2p3
16000
12000
c/s
completely remove the oxidised layer but
produces the segregation of a new carbon
pollution, which is essentially composed of
C-C bonds (284.4eV) like in the case of
graphite/soot compounds.
Other less oxidisable elements than iron
(like Sb, but also Ni, Cu As (not
represented) can also segregate to the top
surface to form less than one monolayer of
non oxidised elements around the weak
selective oxidation of Mn, Al, Cr. Indeed,
as the diffusion kinetic is very low in this
range of reheating temperature, the amount
of external selective oxidation is also very
weak. These considerations indicate that the
Gibbs segregations are possible because all
the elements such as Sb, As, Cu, Ni and C
are over-concentrated just under the
steel/scale interface as shown on figure 1.
To better illustrate that point, an annealing
was performed on a mechanically polished
hot rolled strip (Fig.3).
3500 C1s 7000 O1s
3000 6000
2500 5000 Sb3d5
Pickled (metal)
2000 4000

c/s

Polished
c/s

8000 1500 3000

4000 1000 2000
Pickled + 600°C
500 1000
0 Polished + 600°C
0 0
740 730 720 710 700
300 295 290 285 280 545 540 535 530 525

Binding energy (eV) Binding energy (eV) Binding energy (eV)

Fig.3. XPS analysis: Influence of surface preparation for steel A on surface chemistry

If the same pollution is observed on the the steel H (Fig.4) : pollution distillation
polished surface (thin iron oxide and weak and carbon segregation (C-C bonds). The
carbon pollution), no C and Sb segregation other Gibbs segregations Sb, Cu, Ni, As are
can be noticed on the top surface after not represented on this figure. In that case, a
reheating at 600°C. more important Cr selective oxidation is
formed over the residual Cr oxide of the
The same observations have been made for pickled strip.
 20000 3500 2500 Cr2p3

Fe2p3 R-CH3
3000 C1s
16000 2000
2500
12000 Pickled + 650°C 2000 1500

c/s
c/s
1500
c/s

8000 1000
Polished + 500°C
Pickled
1000 C-C
4000 500
Polished 500
0 0 0
740 730 720 710 700 300 295 290 285 280 605 595 585 575 565
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Fig.4. Influence of surface preparation and annealing on surface chemistry (steel H)

Zinc wettability and reactivity after hot The coating adhesion can also be strongly
dip galvanising deteriorated in the case of an incomplete
After hot-dipping, the coating layer, which pickling (Fig.6).
covers steel A, is very homogeneous and is
not affected by a wide variation of the Pickling: standard solution - 15s
annealing conditions. Indeed, the reheating
can vary between 500°C and 700°C, the H2
FeOx
amount between 5% and 60% and the dew
point between -50°C and -5°C, without Zn
influencing the coating reactivity or its
adhesion. That Fe-Zn reactivity is however
Fe
strongly influenced by the cooling rate after FeZn

hot dipping (Fig.5). a)

1.8 180

1.6 160
1.4
140
1.2
Fe and Al (g/m²)

120
C.W. (g/m²)

1
100
0.8
80
0.6

0.4 60

0.2 40
b)
0 20 1 mm
0 2 4 6 8
Cooling rate (°C/s)
Fe (g/m²) Al (g/m²) C.W. (g/m²)

Fig. 6. Influence of under pickling (steel A) on

Fig.5. Influence of cooling rate on the Fe-Zn Fe-Zn reactivity (cross section a) and on
reactivity (reheating : 600°C) coating adhesion after 180° bending (b)

Indeed, the lowering of the cooling rate The residual scale promotes the formation
gives more time for the destabilisation of of brittle Fe-Zn compounds instead of the
the inhibition layer and the formation of Fe- classical Fe2 Al5 inhibition layer, what
Zn crystals, like in the case of the lowers also the coating adhesion. We have
development of the galvannealing reaction. however to notice that the reheating at
The zinc wettability is however deteriorated 600°C reduces sufficiently the surface of
if the bath and strip dipping temperatures the residual iron oxide layer to allow a good
decrease down to 440°C. In that case, zinc wettability.
numerous bare spots are observed in the
coating. A thin iron oxide can however be admitted
before hot dipping. Indeed, if 100 ppm
oxygen are polluting the cooling gas, the
iron oxide, made between 600°C and
465°C, can be partially reduced by the
aluminium contained in the bath. SIMS
analysis (Fig.7) shows indeed the presence
of an important aluminium oxide over the
residual iron oxide at the steel/coating
interface. That aluminothermia reaction
however allows a sufficient iron oxide
reduction and the formation of the Fe2 Al5
inhibition layer, which lead to a good
coating wettability and adhesion.
1.2E+5 O 16
1.0E+5 FeAl 83
O, AlO (cts/s)
8.0E+4
6.0E+4
4.0E+4 Cooling without O2
2.0E+4
0.0E+0
500 1500
1.2E+5
1.0E+5
O 100 ppm O2
O, AlO (cts/s)
8.0E+4 AlOx
6.0E+4
4.0E+4
2.0E+4
0.0E+0
500 1500
Fig.7. Influence of oxygen pollution in the
cooling gas on reactivity of steel A (SIMS
analysis)
All the other steel grades (including steel I)
have also a good coating wettability and
adhesion, except steel H where some scarse
bare spots can be observed and steel G2
where some zinc flows can be observed
(Fig.8) in the wiping direction. Steel F has
the same kind of defect but only on one
face and at a lower amount. That bad
wettability is characterised in fact by the
presence of 2 different areas where very
different coating thicknesses are measured.
Indeed, instead of having a homogeneous
coating of 20µm, one kind of area is
covered with 1-2µm and the other one with
30-40µm. Moreover, a lot of micro-bare
spots (some tenth of millimeters) are
observed in the thin areas.
Entry Temp : 465°C Entry Temp : 480°C
3 cm
Fig.8. Suppression of zinc flows by dipping
AlO 43 7200
steel G2 at a higher temperature (bath : 460°C)
FeO 72 6000
FeO, FeAl (cts/s)
4800
3600
If that result can partially be explained by
2400 the presence of external selective oxidation,
1200 the main explanation has to be found in the
0 carbon segregation on the top surface
2500 3500 before hot dipping as it was reported above
t (s)
on figures 2-4.
Cooling with 7200
Figure 8 also indicates that the simplest
6000
way to improve wettability is to increase
the bath aggressiveness by increasing the
FeO, FeAl (cts/s)
FeOx 4800
strip/bath temperature. That result could be
3600
explained by a better zinc diffusion through
FeAl 2400
the graphite/soot layer and the development
1200
of Fe-Zn reactions at the steel coating
0 interface. Auger mapping (Fig.9), made
t (s) 2500 3500
after the sputtering of the coating in the
ultra high vacuum, clearly reveals the
presence of a continuous carbon layer
around the Fe2 Al5 inhibition layer in the
case of steel G2. The other steel grade G1
with the same composition, has no zinc
wettability problems and also has no carbon
segregation around the steel/zinc interface.
It means that it is not the steel composition
which is important, but the hot rolling
conditions, which promote different iron
oxide layers and carbon segregation at the
steel/scale interface.
The rolling conditions have been changed
in a wide range to determine the main
parameters influencing the carbon
segregation at the steel/scale interface and
the coating wettability.
 (a) To verify the influence of the pearlite
segregated at the steel/scale interface, steels
C Al
Al G2 and F have been mechanically polished
before reheating and galvanising. No
wettability problems were observed after
such preparation, which suppress the
carbon segregation after reheating (see
figs.3-4).

Fe Zn
Zn 20000 Fe2p3
Fe-met

Fe-ox
15000

c/s
10000 700°C
5000
515°C
0
740 730 720 710 700
Binding energy (eV)
(b)
R-CH3 C-C
4000 C1s
C Al 3000

c/s 2000
1000
0
300 295 290 285 280
Binding energy (eV)

Zn 1600 Mn2p3
Fe Mn ox
Mn met
1400
c/s

1200
1000
800
670 660 650 640 630
Binding energy (eV)

5µm Fig.10. Influence of the reheating temperature

Fig.9. Carbon segregation at the steel/zinc
interface (Auger mapping) :
(a) steel G2 with wettability problems -
(b) steel G1 without wettability problems
It appears that the cooling rate between the
end of rolling and the coiling, the change of
the temperature at the last stand including
austenitic and ferritic rolling has no
influence on the galvanising behaviour.
Only a decrease of the coiling temperature
down to 320°C or 100°C seems to induce
the formation of some scarse bare spots on
a microalloyed steel grade (same kind of
composition than steels G).
on surface chemistry (steel F)
To improve the coating wettability different
solutions were found. We have previously
discussed the benefic effect of a dipping at
higher temperature. The increase of the
reheating temperature also improves the
coating wettability even if the amount of
external selective oxidation increases. This
result is of course explained by a decrease
of the carbon amount on the top surface
(Fig.10), which is due to the strip
decarburising as illustrated on the GDOS
profiles (Fig.11).
 0.20 The injection of water vapour to increase
C intensity (a.u.)
the intensity of that reaction is however not
0.15
efficient at the reheating temperature
0.10 usually applied (550°C) probably because
600°C the reaction kinetic is too low in that range
0.05
700°C of temperature. Surprisingly, the annealing
0.00
800°C
at 550°C in an atmosphere containing
0 0.2 0.4 0.6 0.8 1 100%H2 significantly decreases the carbon
DEPTH (µm) amount on the top surface and improves the
0.20
galvanisation.
C intensity (a.u.)

0.15 Another way to prepare a surface without

0.10
600°C any carbon segregation is to preoxidise the
strip before the reheating treatment as
0.05 indicated on figure 12. That treatment has
0.00
700°C
800°C
also the advantage to significantly reduce
0 1 2 3 4 5 6 7 the external selective oxidation.
DEPTH (µm)
Finally, the use of an IF steel, will suppress
Fig.11. Influence of the reheating temperature
all carbon segregation, which allows to
on surface composition of steel F (GDOS obtain a perfect coating appearance.
analysis)
Fe-metal
4000 C-C 2200
17000 Fe2p3 Fe-oxide C1s Cr2p3
3000 1900
12000
c/s
c/s
c/s

2000 Reduction 500°C 1600

7000
2000 1000 Ox.450°C+Red 500°C 1300
Oxided 450°C
-3000 0 1000
740 730 720 710 700 300 295 290 285 280 600 590 580 570
Binding energy (eV) Binding energy (eV) Binding energy (eV)

Fig.12. Influence of a pre-oxidation in air during 5s at 450°C on surface chemistry (steel H)

H2 blistering on galvanised hot rolled bination is observed on top of the inhibition

strips layer.
A major problem encountered in the case of
galvanised hot rolled strips is the formation An important factor influencing the H2
of H2 blisters, which occur at the steel/ blister formation is the hydrogen amount in
coating interface after a few hours (Fig.13). the annealing furnace as illustrated on
figure 14. This figure, obtained by image
analysis, represents the number of blisters
per cm² having the indicating area.

It can also be noticed that the number of

blisters decrease when lead is added to the
bath but the blister size increases
Fig.13. Cross section on characteristic H2 significantly, keeping in fact constant the
blister. total area covered by the blisters. That
could be explained by the fact that some
More exactly, Auger and SIMS analyses zinc grains orientations preferentially give
have shown that the hydrogen recom- the H2 blistering problems. If the spangle
size increases, the amount of the H2 under
one sensitive orientation also increases, which significantly reduces the zinc
which can lead to increase the size of the wettability on the steel surface. An increase
blisters. of the annealing temperature promotes
decarburising and improves significantly
If the decrease of the reheating temperature the zinc wettability. Other possibilities have
also lowers the total amount of H2 absorbed been find to suppress the graphite type
by the steel strip and consequently the segregation like a re-heating under pure
intensity of the H2 blisters, the influence of hydrogen or a surface pre-oxidation. The
the pickling operation seems to play a most easily way to improve zinc wettability
minor role in the formation of the H2 on industrial lines is however the increase
blisters. Indeed, when the reheating is made of the bath and/or the strip dipping
in atmosphere containing 5% H2, quite no temperature. That practice increases
blisters are observed on the coated however the steel/bath reactivity and
products. induces the formation of brittle Fe-Zn
compounds at the strip/coating interface
Bath : 0.21 % Al with probably the formation of a higher
amount of drosses in the bath.
1000

100
These results indicate that the hot rolling
N/cm2

10
conditions are more important for the zinc
1
100 % H2 wettability than the steels. Indeed many
0 60 % H2
steel chemistries alloyed with Mn (up to 1
2-4

20 % H2
4-8

8-10

10-12

12-14

wt%) and Si (up to 0.4 wt%), have been

14-16

16-18

18-20

galvanised without any zinc wettability or

Surface (x10³) µm²
coating adhesion problems.

Bath : 0.21 % Al + 0.05 % Pb That result is mainly explained by the weak

1000 selective oxidation amount induced by the
100
low re-heating temperature (550°C). That
low temperature is however sufficient to
N/cm2

10
1
reduce completely the iron oxide left on the
100 % H2 surface after pickling. A thin iron oxide,
0 60 % H2
produced during cooling, can however be
2-4

20 % H2
4-8

8-10

10-12

12-14

14-16

16-18

admitted on the surface before hot dipping

18-20

Surface (x10³) µm²

without lowering the zinc wettability or the
coating adhesion.
Fig.14. Influence of H2 amount in the reheating
furnace and spangle size on H2 blistering Finally, H2 blistering is due to the zinc de-
cohesion at the Fe2Al5/zinc interface. The
CONCLUSIONS amount of H2 absorbed during annealing
A systematic study of the various process seems to be much more important than the
parameters has allowed to identify the main H2 pick-up during pickling. Therefore the
parameter responsible for the poor coating amount of H2 in the annealing atmosphere
wettability: the carbon segregation before plays a key role in the H2 blistering
hot dipping. Indeed, during the hot rolling problem.
process, carbon segregation at the
steel/scale interface induces the formation ACKNOWLEDGMENTS
of pearlite. During reheating at low The author would like to thank the
temperature, that pearlite can reject carbon European Community and Union Minière
to form an homogeneous graphite layer, for the sponsorship of this work.