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Received 18 October 2005; received in revised form 16 February 2006; accepted 21 March 2006
Abstract
Autogenous welded specimens of austenitic (S30400 and S31603), duplex (S31803) and super duplex (S32760) stainless steels were fabricated
by laser penetration welding (LPW) with a CW Nd:YAG laser in an argon atmosphere. The microstructure and the phases present in the resolidified
zone of the laser-welded specimens were analyzed by optical microscopy and X-ray diffractometry, respectively. The pitting and galvanic corrosion
behavior of the stainless steels in the laser-welded and unwelded conditions in 3.5% NaCl solution at 23 C was studied by means of electrochemical
measurements. X-ray diffraction analysis showed that the phases present in the weld metal depended on the composition of the base metal. While
the laser weld for S31603 retained the original austenitic structure, the laser weld of S30400 contained austenite as the major phase and -ferrite
as the minor phase. On the other hand, a slight change of -ferrite to austenite ratio was found in both the laser welds of S31803 and S32760, with
austenite present at the -ferrite grain boundaries. The welds exhibited passivity but their pitting corrosion resistance was in general deteriorated
as evidenced by a lower pitting potential and a higher corrosion current density compared with those of the unwelded specimens. The decrease
in pitting corrosion resistance of the welds was attributed to microsegregation in the weld zone of S31603, and to the presence of -ferrite in
S30400. For the duplex grades S31803 and S32760, the disturbance of the ferrite/austenite phase balance in the weld zone could be the cause of
the decrease in corrosion resistance. The initial free corrosion potentials of the unwelded specimens were considerably higher than those of the
corresponding laser welds, indicating that the welds were more active and were expected to act as anodes in the weldment. The ranking of galvanic
current densities (IG ) of the couples formed between the laser-welds (LW) and the as-received (AR) specimens with area ratio 1:1, in ascending
order, is: AR S31603/LW S31603 < AR S31803/LW S31803 < AR S32760/LW S32760 < AR S30400/LW S30400. The recorded IG in all couples
was low (in the range of nA/cm2 ).
2006 Elsevier B.V. All rights reserved.
Keywords: Laser welding; Stainless steels; Pitting corrosion; Galvanic corrosion; -Ferrite
1. Introduction
Owing to their excellent mechanical properties and corrosion
resistance, stainless steels are extensively used in many industrial and medical applications. Commercial products such as
razors, cigarette lighters, watch springs, motor and transformer
lamination, hermetic seals, battery and pacemaker cans, and
hybrid circuit packages require delicate welds with high quality and precision. A kilowatt laser beam can melt and vaporize
the material, and the pressure of the vapor displaces the molten
material so that a narrow and deep keyhole is formed. The keyhole supports the transfer of the laser energy into the material
and guides the laser beam deep into the material. Laser pene-
Corresponding author. Tel.: +852 2766 5691; fax: +852 2333 7629.
E-mail address: apaftche@polyu.edu.hk (F.T. Cheng).
0924-0136/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2006.03.128
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
C = 1 +
= 1+
169
1
1
(1)
where I(h k l) and I(h k l) are the integrated intensities of a given crystallographic
plane (h k l) from the and phases, respectively, and the values of R(h k l)
and R(h k l) of and for various planes were obtained from Jatczak et al.
[10]. The chemical compositions of the resolidified microstructure after LPW
were analyzed by energy dispersion X-ray spectrometry (EDS). In addition,
Table 1
Nominal compositions (wt.%) of various stainless steels
S30400
S31603
S31803
S32760
a
Fe
Cr
Ni
Mo
Mn
Cu
Si
Creq /Nieq a
Balance
Balance
Balance
Balance
18.4
17.6
22.5
25.6
8.7
11.2
5.6
7.2
2.5
2.9
4.0
1.6
1.4
1.5
0.6
0.2
0.8
2.1
1.4
1.6
0.7
0.08
0.03
0.03
0.03
0.3
0.4
0.4
0.3
0.1
0.1
0.2
1.70
1.62
3.59
2.09
Creq = [Cr] + [Mo] + 1.5[Si] + 0.5[Cb]. Nieq = [Ni] + 0.5[Mn] + 30[C] + 30[N].
170
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
Fig. 2. XRD patterns of as-received stainless steels and laser welds: (a) S30400, (b) S31603, (c) S31803 and (d) S32760.
ferrite as the minor phase. On the other hand, both S31803 and
S32760 were mainly composed of -ferrite, with austenite as the
minor phase. The microstructures of the stainless steels before
and after laser welding are shown in Fig. 3. In LW S30400, the
skeletal network of residual -ferrite is present in the austenitic
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
matrix () as shown in Fig. 3(e). Austenitic dendrites in different orientations are observed in LW S31603 as shown in
Fig. 3(f). After laser welding, the grain size of LW S30400 and
LWS31603, which were predominantly austenitic, was refined
due to rapid solidification. On the contrary, the grain size in LW
171
Fig. 3. Microstructure of various stainless steels in unwelded (as-received, AR) condition: (a) AR S30400, (b) AR S31603, (c) AR S31803 and (d) AR S32760; and
in laser-welded (LW) condition: (e) LW S30400, (f) LW S31603, (g) LW S31803 and (h) LW S32760.
172
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
Fig. 3. (Continued ).
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
Table 2
Volume fraction of -ferrite and microhardness in as-received (AR) and laserwelded (LW) regions
Stainless
steels
C (AR)
(%)
C (LW)
(%)
Difference
in C (%)
Hv0.2
(AR)
Hv0.2
(LW)
S30400
S31603
S31803
S32760
0
0
60
54
14
0
62
50
+14
0
+2
4
176
179
268
290
301
194
316
314
173
Fig. 4. Hardness profiles of various laser-welded specimens: (a) along the depth of the cross-section and (b) across the cross-section.
174
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
Fig. 5. Ec vs. time of the as-received stainless steels and their corresponding weldments: (a) S30400, (b) S31603, (c) S31803 and (d) S32760 in 3.5% NaCl solution.
values in the welds were nearly constant and higher than those
of the base metals (hardness outside the welds) as shown in
Fig. 4(b). The hardness of the weld zone for S31603, S31803
and S32760 was higher by 818% as compared with that of the
base metals. The most significant change in hardness is observed
in LW S30400, with an increase of about 70%. The increase in
hardness could be attributed to the refinement of grains and also
to the presence of hard -ferrite.
3.2. Free corrosion potential
From measurements of the free corrosion potentials (Ec ) of
the base stainless steels and their corresponding laser welds
(Fig. 5), information about the dynamic behavior of the passive
oxide film might be obtained. The Ec of the unwelded specimens increased towards more noble values and became steady
at the end of the 2-h test. This reflects that the growth of passive
oxide was almost complete. The steady values of Ec after 2 h are
shown in Table 3. For unwelded S32760, the oxide film was the
most stable because it was highly alloyed with the elements Cr,
Mo and N, all of which could enhance passivity. It can be also
observed that the Ec of all unwelded stainless steels are considerably higher than those of their corresponding welds. For
instance, the Ec of as-received S32760 (3 mV SCE) is higher
than that of its laser weld (327 mV SCE).
Table 3
Corrosion parameters of unwelded (AR) and laser-welded (LW) stainless steels
in 3.5% NaCl solution at 23 C, open to air
Specimens
Ec (mV)
Epit (mV)
Eprot (mV)
icorr (A/cm2 )
AR S30400
LW S30400
AR S31603
LW S31603
AR S31803
LW S31803
AR S32760
LW S32760
270
310
256
343
301
348
3
327
330
85
423
195
1170
671
1040
1040
39
11
76
39
1179
111
980
954
0.416
3.475
0.252
6.456
0.405
9.429
0.138
0.518
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
175
Fig. 6. Potentiodynamic polarization curves of the as-received stainless steels and their corresponding weldments: (a) S30400, (b) S31603, (c) S31803 and (d)
S32760 in 3.5% NaCl solution.
In addition, the pitting corrosion resistance and the repassivation capability of the laser welds were lower than those of the
unwelded specimens as reflected by lower values in both Epit
and Eprot . The ranking of the pitting corrosion resistance of the
specimens is as follows:
ARS30400 < ARS31603 < ARS32760 < ARS31803
and
LWS30400 < LWS31603 < LWS31803 < LWS32760.
Decrease in Epit is observed in the laser welds for S30400
(from 330 mV to 85 mV SCE), S31603 (from 423 mV to 195 mV
SCE) and S31803 (from 1170 mV to 671 mV SCE). On the other
hand, there is no significant change in Epit in the laser weld for
S32760. In addition, the corrosion current densities of all welds
increased.
While the results in the present study indicate a decrease in
corrosion resistance for stainless steels due to laser welding,
laser cladding (LC) of stainless steel on mild steel followed
by laser remelting resulted in increase of corrosion resistance
as reported by Li et al. [18,19]. This is not unexpected as in
laser surfacing the processing condition is chosen to yield a
homogeneous surface layer while in welding the primary aim is
to achieve joining. Some improvement in pitting resistance of
176
C.T. Kwok et al. / Journal of Materials Processing Technology 176 (2006) 168178
Table 4
EDS composition analysis of different regions in laser welds
Specimen
Region
Cr (wt.%)
Ni (wt.%)
Mo (wt.%)
LW S30400
16.4
19.9
7.8
8.2
LW S31603
Dendrite core ()
Interdendritic ()
16.1
18.2
9.6
12.3
1.5
2.1
LW S31803
20
24
6.3
5.4
1.8
2.6
LW S32760
26.7
26.1
7.1
7.2
3.2
3.8
Fig. 7. Time dependence of (a) EG and (b) IG for various galvanic couples in
3.5% NaCl solution.
EG (mV)
IG (nA/cm2 )
AR S30400/LW S30400
AR S31603/LW S31603
AR S31803/LW S31803
AR S32760/LW S32760
311
330
304
347
78.6
26
8.6
35
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