Abstract

Austenitic stainless steel is used widely in almost all industries due to their excellent
properties. 304SS is one of these types used; however, its pitting resistance is low
because of the formation of the MnS inclusions that serve as initiation sites of the
pitting corrosion. One can increase the pitting resistance of this steel using some
method of reducing or eliminating the amount of MnS inclusions present in the
austenite phase. Laser surface melting can do this job. Laser surface melting is one of
the laser surface processes used to treat different type of materials to improve their
properties. Upon treatment by LSM, 304SS shows increase in pitting resistance due to
the formation of the delta-ferrite phase in the melting pool where the solubility of the
sulfur is much higher, hence hindering the formation of MnS inclusions. In this
experiment, different scanning speeds of LSM have been examined to study the effect
on the pitting resistance of the 304SS. The most notable conclusion is that as we
increase the scanning speed, the pitting resistance of the 304SS decreases.

Introduction
Austenitic stainless steels are widely used in different industries because of their
desirable mechanical and electrochemical properties. AISI 304 SS is widely used in
process industries because of the low cost and excellent corrosion resistance
properties. However, the pitting corrosion resistance is not high enough for durable
service in industries. This is due to the formation of the MnS inclusions in the
austenitic stainless steels which serve as initiation sites for pitting corrosion. The
pitting corrosion resistance can be increased by introducing the ferrite phase in the
austenitic stainless steels because sulfur has much higher solubility in ferrite phase
than that for austenite phase.

Laser surface modification processes have become widely used because of the low
cost and brilliant control of the processes. Laser Surface Melting is one of these
processes which involves rapid melting and rapid solidification of the austenitic
stainless steel producing fine-grained microstructure of delta-ferrite phase. This, as
discussed above, will modify the pitting corrosion resistance of the AISI 304 stainless
steel. One more advantage of using LSM for curing austenitic stainless steels is the
redistribution of the Cr atoms in the substrate yielding to better passive film
formation, hence, better pitting corrosion resistance [1].

Experiment:
The equipment used in the experiment is a Rofin-Sinar 2kW CO2 laser which is
coupled to an Aerotech CNC x-y table through a beam delivery system and laser
processing head as shown in figure1. After completion of the LSM process the
specimens then were sectioned, polished and electrochemically etched with oxalic
acid at 1A/cm2 for 15 seconds [2]. After that, the specimens were examined under the
optical microscope to note the difference between the specimens before and after
LSM treatment.

Table 1 summarizes the six different specimens were tested in the experiment. For the
single track experiment, different speeds of the laser beam were examined to study the
effects of scanning speed on the melting pool dimensions and the microstructure of
the specimens. Similar analysis was conducted for the overlap specimens with overlap
ratio of 50%. For the pitting corrosion resistance, two polarization curves for the two
different speeds were plotted and compared to the as-received specimen.
 Table 1: Laser operating parameters used in the experiment

Laser beam Scanning

Laser
Sample No. spot size, velocity, Remarks
Power, W
mm mm/s
1 60
2 90
S 3 1600 2 120 Single track
4 150
1 60
W 1600 2 Overlap
2 120

Results:
Figures 2 through 5 show the microstructure of the single track specimens examined
under the optical microscope. The melting pool dimensions are summarized in table 2
below. Figure 6 shows the melting pool dimensions as a function of scanning speed.
From the table 2 and figure 6 we notice that as we increase the scanning speed; while
keeping the spot size and the power constant, the melting pool dimensions decrease in
both the depth and the width. This can be interpreted as the melting of the surface of
the stainless steel at lower speed is higher because the surface is under effect of the
laser beam for a longer time. Notably, the melt width for the specimen at 60 mm/s
speed is much higher than that of the remaining specimens. If we exclude the
experimental and human errors, it can be inferred that there is a critical speed at which
the melting pool dimensions decreased dramatically with scanning speed. More tests
should be conducted to reveal the right conclusion as our conclusion depends on one
test only.

Table 2: Melting pool dimension of the single track specimens

Scanning Speed
Specimen Melt Depth, mm Melt Width, mm
mm/s
S1 60 0.22 2.16
S2 90 0.17 1.66
S3 120 0.09 1.64
S4 150 0.05 1.62

The as-received 304SS specimen when examined under the optical microscope is
shown in figure 7. From this figure, we can obviously figure out the austenitic
structure of the 304SS as the bulky globular grains. After laser treatment using LSM
method, one can notice the difference between the microstructure of the bulk material
and the microstructure of the deposit caused by the laser treatment. The bulk stainless
steel material is the same as the as-received specimen, austenitic. However, the
deposit microstructure, figure 8, is columnar and dendritic grains. Columnar grains
forms for the rapid cooling while the dendritic ones form under slow cooling of the
melt pool. The phase in the melt pool is δ-ferrite as it is the first phase to form after
solidification of the austenitic stainless steel [1]. This delta-ferrite phase is what gives
LSM-treated 304SS its desirable and better pitting corrosion resistance as discussed
above. The tiny bars observed in the austenite are the undesirable inclusions; MnS
among others, that formed in longitudinal bars along the rolling direction of the steel
[1]
. Final conclusion of this test is that as we increase the scanning speed, the ferrite
phase presence decreases also.
 To cover large surface area, the laser beam has to pass multiple times over the surface
of the stainless steel. Therefore, overlap technique is used. Indeed, to get nice constant
depth of the protective layer of the melted surface, overlapping to about 50% is used.
This ratio is what was used in our experiment. Figures 9 and 10 show the
microstructure of the overlap technique under the optical and scanning electron
microscopes respectively. From figure 10, we can see small transformation of the δ-
ferrite back to austenite in the reheated zone. This is because the increase in
temperature promotes the transformation of ferrite to austenite.

Finally, the electrochemical properties; the pitting resistance in this experiment,

increased as a result of the LSM treatment of the AISI 304SS. This is again due to the
formation of the ferrite phase in the austenitic matrix of the stainless steel. MnS
inclusions are believed to be the initiation sites of the pitting corrosion of the stainless
steels. Introducing the ferrite phase increases the solubility of the sulfur inside it and
prevents the formation of the MnS inclusions, hence increasing the pitting potential of
the stainless steel. Most importantly; as we increase the scanning speed, the pitting
potential decreases. This, as pointed above, due to the less amount of ferrite phase
formed for higher scanning speeds. The less amount of the ferrite phase means that
there are some sulfur not fully dissolved in the ferrite phase and might form the MnS
inclusions that would initiate the pitting corrosion of the stainless steel. Polarization
curves of the different 304SS specimens are shown in figure 11.

Safety Precautions:
The laser produces an intense, highly directional beam of light. The human body is
vulnerable to the output of certain lasers and, under certain circumstances; exposure
can result in damage to the eye and skin. The eye is almost always more vulnerable to
injury than skin. In addition, there are non-beam hazards and electrical hazards where
most lasers make use of high voltages that one should be aware of. Any use of the
laser equipment should rely under fully addressed standards such as IEC 60825 and
ANSI Z136. Report of all incidents during the use of the laser equipments should be
reported immediately to avoid further damage of human body and laboratory assets [3].

Conclusions:
 LSM is becoming more popular surface treatment of the austenitic stainless steels
because of the low cost and excellent results obtained
 LSM treatment of the AISI 304SS has increased its pitting resistance
 The LSM treatment produces duplex microstructure with austenite and ferrite
 MnS inclusions are no more present for the LSM-treated 304SS, because of the
high solubility of the sulfur in ferrite phase
 As the scanning speed of the LSM increases, the melt pool dimensions decrease
 Higher melt pool dimensions for 60mm/s scanning speed compared to the other
speeds
 Overlapping technique in LSM used to cover large surface areas transforms some
of the ferrite phase in the reheated zone to austenite increasing it is susceptibility
to pitting corrosion. However, enough amount of ferrite phase can dissolve all the
sulfur present
 Pitting potential of the stainless steel was increased after LSM treatment. However
higher scanning speed lowers the pitting potential; still above the as-received
pitting potential; due to the less amount of ferrite formed at higher speeds
References:
[1] Laser Surface Melting Of 304 Stainless Steel For Pitting Corrosion Resistance
Improvement; T.S. Seleka and S.L. Pityana; 8th International Corrosion Conference;
The Southern African Institute of Mining and Metallurgy

[2] Laser Surface Treatment of AISI 304 Stainless Steel; Ziu Liu; Corrosion and
Protection Centre; The University of Manchester, 2007

[3] Laser Safety; [http://www3.imperial.ac.uk/safety/training/presentations], accessed

28th December 2007

Appendix:
Figures cross-referenced in the report.

Laser beam
Focusing
mirror Laser

Workpiece

CNC unit
Workstation

Processing
head

Laser
beam

Nozzle
Travelling
direction

Melt pool

Workpiece

Figure 1: Schematic diagram of the set-up used [2]

Figure 2: Optical micrograph of single track specimen at scanning speed
of 60mm/s (S1) at 5x magnification

Figure 3: Optical micrograph of single track specimen at scanning speed

of 90mm/s (S2) at 5x magnification

Figure 4: Optical micrograph of single track specimen at scanning speed

of 120mm/s (S3) at 10x magnification

Figure 5: Optical micrograph of single track specimen at scanning speed

of 150mm/s (S4) at 5x magnification
 2.5

2
Melt Pool Dimension, mm

1.5

0.5

0
50 60 70 80 90 100 110 120 130 140 150 160
Scanning Speed, mm/s

Melt Width Melt Depth

Figure 6: Melting pool dimensions as a function of the scanning speed

Figure 7: Optical micrograph of as-received AISI 304SS [2]

Figure 8: Optical micrograph of LSM-treated AISI 304SS at 20x magnificaiton

 Figure 9: Optical micrograph of overlapping region

Figure10: SEM micrograph of overlapping region [2]

As-received
LSM
S2,atP=3
120kW,
mm/s
V = 8.3 mm/s
0.6 LSM at 60kW,
S4, p=3 mm/s
V = 16.7 mm/s
As-received SS 304L

0.4

0.2
E (V vs SCE)

0.0

-0.2

-0.4

-0.6
1E-10 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01
I (A/cm2)

Figure11: Polarisation curves of the 304SS before and after laser treatment [2]