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Galvanising of Hot Rolled Strip91 - 1
Galvanising of Hot Rolled Strip91 - 1
L. Bordignon
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
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
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)
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)
c/s
Polished
c/s
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)
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
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)
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 30-40µm. Moreover, a lot of micro-bare
iron oxide, made between 600°C and spots (some tenth of millimeters) are
465°C, can be partially reduced by the observed in the thin areas.
aluminium contained in the bath. SIMS
analysis (Fig.7) shows indeed the presence Entry Temp : 465°C Entry Temp : 480°C
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.
3 cm
Fig.8. Suppression of zinc flows by dipping
1.2E+5 O 16 AlO 43 7200
steel G2 at a higher temperature (bath : 460°C)
1.0E+5 FeAl 83 FeO 72 6000
FeO, FeAl (cts/s)
O, AlO (cts/s)
8.0E+4 4800
6.0E+4 3600
If that result can partially be explained by
4.0E+4 Cooling without O2 2400 the presence of external selective oxidation,
2.0E+4 1200 the main explanation has to be found in the
0.0E+0 0 carbon segregation on the top surface
500 1500 2500 3500 before hot dipping as it was reported above
t (s)
on figures 2-4.
1.2E+5 Cooling with 7200
Figure 8 also indicates that the simplest
1.0E+5
O 100 ppm O2
6000
way to improve wettability is to increase
the bath aggressiveness by increasing the
FeO, FeAl (cts/s)
O, AlO (cts/s)
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)
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
16-18
18-20
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