Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 681685

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Infrared nanosecond pulsed laser irradiation of stainless steel: Micro

iron-oxide zones generation
M. Ortiz-Morales a,b,, C. Frausto-Reyes b, J.J. Soto-Bernal a, S.E. Acosta-Ortiz c, R. Gonzalez-Mota a,
I. Rosales-Candelas a
a
Instituto Tecnolgico de Aguascalientes, Lab. de Optoelectronica, Av. A. Lopez Mateos 1801 Ote. Fracc Bonagens, Aguascalientes 20256, Mexico
b
Centro de Investigaciones en ptica, A.C. Prol. Constitucin 607, Fracc. Reserva Loma Bonita, Aguascalientes 20200, Mexico
c
Lasertech, S.A. de C.V. Blvd. Olivares Santana 113, Fracc. El Dorado, Aguascalientes 20235, Mexico

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Periodic patterns of different oxides

zones were generated by IR laser
irradiation.
 The lms generated were attached to
the metal by laser irradiation.
 After laser irradiation an elemental
redistribution for each oxide zone
was observed.

a r t i c l e i n f o a b s t r a c t

Article history: Nanosecond-pulsed, infrared (1064 nm) laser irradiation was used to create periodic metal oxide coatings
Received 8 November 2013 on the surface of two samples of commercial stainless steel at ambient conditions. A pattern of four dif-
Received in revised form 26 February 2014 ferent metal oxide zones was created using a galvanometer scanning head and a focused laser beam over
Accepted 27 February 2014
each sample. This pattern is related to traverse direction of the laser beam scanning. Energy-dispersive X-
Available online 15 March 2014
ray spectroscopy (EDS) was used to nd the elemental composition and Raman spectroscopy to charac-
terize each oxide zone. Pulsed laser irradiation modied the composition of the stainless steel samples,
Keywords:
affecting the concentration of the main components within each heat affected zone. The Raman spectra of
Iron oxides
Laser irradiation
the generated oxides have different intensity proles, which suggest different oxide phases such as mag-
Stainless steel netite and maghemite. In addition, these oxides are not sensible to the laser power of the Raman system,
Raman spectroscopy as are the iron oxide powders reported in the literature. These experiments show that it is possible to
generate periodic patterns of various iron oxide zones by laser irradiation, of stainless steel at ambient
conditions, and that Raman spectroscopy is a useful punctual technique for the analysis and inspection
of small oxide areas.
2014 Elsevier B.V. All rights reserved.

Introduction
Nowadays, iron oxides play an important role in several disci-
plines such as chemistry, corrosion science, geology, soil science,
Corresponding author at: Centro de Investigaciones en ptica, A.C. Prol.
Constitucin 607, Fracc. Reserva Loma Bonita, Aguascalientes 20200, Mexico. Tel.:
+52 (449) 4428124; fax: +52 (449) 4428127.
E-mail address: maortiz@cio.mx (M. Ortiz-Morales).
biology and medicine. Their applications are growing with the
development of synthesis methods that allow creating iron oxides
with specic characteristics; they are used as catalysts for other
processes or as transport agents in medicine [1]. All iron oxides
consist mainly of Fe and O but differ in composition and crystal
structure. Iron oxides are of great interest for a variety of applica-
tions including opto-electronics, medicine, environmental remedi-
ation, pigments, corrosion protection, and gas sensing, among
others [25].

http://dx.doi.org/10.1016/j.saa.2014.02.201
1386-1425/ 2014 Elsevier B.V. All rights reserved.
682 M. Ortiz-Morales et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 681685
Laser thermal oxidation is a promising method for oxidation re-
search and for obtaining new results about laser metal interaction
and non-traditional methods such as laser synthesis from the
mixture of various elements [616]. It has been shown that the
synthesis of materials and their modication by laser radiation of-
fer several advantages [8,14,17]. For example, Li et al. showed that
UV lasers produce different colors on the surface of stainless steel
that are related to the type of oxide generated [18], Adams et al.
showed that it was also possible to create oxide coatings with
Nd:YAG (1064 nm) and to determine the relation of these oxides
to different colors [19] and Cui et al. showed that laser surface
melting affects the surface morphology of the oxides formed in
the heat affected zones [2022]. Amulevicius et al. describes the
synthesis of FeC compounds using laser irradiation on powder
samples [23]. Despite numerous published papers on laser thermal
oxidation of iron, to our knowledge there is still plenty of work to
be done about the mechanisms and parameters that can be con-
trolled in a laser based setup for materials synthesis and surface
modication, such as atmosphere, laser wavelength, laser power,
pulse width and frequency, scan speed and number of passes, to
name only the most important. In addition, a focused laser spot
has the advantage of generating, with the use of galvanometers,
very localized oxide micro-zones, with particular forms or pat-
terns. These complex forms and patterns can be used as small
detectors or small zones for catalytic processes or in any other
application that can be developed at microscale.
Raman spectroscopy has been recognized as a useful technique
for the analysis of solid and powder materials, oxide lms and
oxide layers on metal surfaces [2427]. In addition, this technique
has the advantage that the sample to be analyzed can be as small
as the laser focused spot size of the Raman system. As Raman spec-
troscopy uses a focused laser over the sample, the temperature of
the analyzing zone may increase to such a degree that it could in-
duce material alterations or even the destruction of the sample due
to local laser heating [8,28]. Raman spectroscopy has been used to
study different kinds of oxides, including iron, chromium, zinc, and
TiO2, among others, nding that it is possible to identify certain
types of oxides by comparing their spectra and the position of their
Raman bands [6,9,11,26,29,30].
Most of the works related to laser iron oxide generation, reported
the analysis taking the average of the oxide zone in the heat affected
zone and the color effect for appearance purposes, others are related
to the generation and deposition of thin lms over other substrates
but taking into account the average oxide zone generated by the
inuence of laser heat. Considering the above, in this work, the main
objective is to show that it is possible to generate different iron-
oxide micro-zones on the surface of commercial stainless steel
samples at ambient conditions using nanosecond pulsed, focused
infrared laser irradiation, controlling the size and the shape of the
generated patterns with a galvanometer scanning head. The oxide
micro-zones generated can be precisely analyzed by Raman
spectroscopy and Energy-dispersive X-ray spectroscopy; the results
are compared to those reported in the literature.
Experimental
Two samples of commercial stainless steel plates AISI304 and
AISI430 (1.5 mm in thickness) were used in this experiment; they
were cut to 10 mm  10 mm and cleaned with deionized water
and alcohol, and dried in air.
For irradiation, the samples were mounted on a table at a dis-
tance equal to the focal length of the F-theta lens of an Ytterbium
pulsed ber laser (IPG Photonics i-series marker model YLP-1-100-
30-30-HC) with an average power output of about 30 W and a
wavelength of 1064. The laser pulse width and repetition rate used
for irradiation were about 120 ns and 70 KHz, respectively. The
diameter of the focused laser beam was about 55 lm, the spacing
between laser scan lines was 0.2 mm, the scanning speed was
80 mm/s and three scanning cycles were performed.
The selection and identication of oxide zones to be analyzed
was made with an optical microscope (Axioscope, Zeiss) with
10 and 40 objectives. The images of the selected zones were ob-
tained using the Imagebase software and a M-PS-20 CCD camera
from kappa.
The Raman spectra were measured using a micro-Raman sys-
tem (Renishaw, 1000B with a backscattering geometry) with a
600 lines/mm grating, a CCD camera (Rem Cam 1024  256 pix-
els); and a laser diode at 830 nm wavelength as excitation source.
The laser beam was focused onto the sample (spot-size of about
2 lm) using the 50 objective of a Leica (DMLM) microscope
[29]. The calibration of the instrument was done using the
520 cm 1 Raman line of a silicon wafer. Grams software was used
for data acquisition. Measurements were made at several points in
each selected oxide zone and along several lines, although only a
representative spectrum is shown. The shown Raman spectra have
not been smoothed and were normalized to the most intense peak,
and do not have a base line.
The elemental composition of the samples was determined with
Energy-dispersive X-ray spectroscopy (EDS), which is used in a
scanning electron microscope system (SEM, model JEOL JSM-
5900LV). Also with this SEM equipment, the width of the oxide
zones was measured. All the measurements were made at the sam-
ple surface in the selected oxide zones.
Results and discussion
Samples before irradiation
The Raman spectra of the surface of the two steel samples with-
out laser irradiation (not shown), did not presented any Raman
bands, and only the noise generated by the Raman system is ob-
served. So far, it could be said that there was no oxide layer on
the surface of the samples, or at least the oxide layer could not
be detected under the measurement conditions.
Although the stainless steel type is mentioned in the experi-
mental section, Energy-dispersive X-ray spectroscopy analysis
was done to know the elemental composition of the samples.
Table 1 shows the weight percent of the components with the
highest concentration for samples (denoted as S1 for SE304 and
S2 for SE430). The lack of oxygen is evident in both samples, which
allowed us to corroborate the assumption that there was no oxide
present before laser irradiation.
By analyzing the data shown in Table 1, it could be found that
the ratio of CrFe for S1 is 0.218 and for S2 is 0.204. This analysis
allows us to observe and conclude that the samples were not of the
same type of stainless steel.
Irradiated samples
Figs. 1 and 2 show the microscope images of the laser irradiated
samples using the 10 and 40 objectives respectively. We
identied a periodic pattern of three well dened zones, denoted
as (bd), on both sides of each marked line (zone a); these zones
Table 1
Energy-dispersive X-ray spectroscopy analysis for elemental composition of samples
S1and S2 before laser irradiation (elements with the highest wt.%).
Sample Elements
Cr (wt.%) Fe (wt.%)
1 16.46 75.42
2 14.95 73.00
 M. Ortiz-Morales et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 681685 683

Scan direction

Scan direction
Sample S1 Sample S2

Fig. 1. Amplied images of samples S1 and S2 (10), showing the four zones generated by laser irradiation and scanning direction.

Table 2
Scan direction Energy-dispersive X-ray spectroscopy results for elemental analysis of zones (ad) for
sample S1.

Oxide zone S1 Element

a/2
O (wt.%) Cr (wt.%) Fe (wt.%)
a 10.71 17.33 66.33
b 25.99 26.23 44.62
c 20.85 22.56 50.52
d 19.82 20.89 56.07

Table 3
Energy-dispersive X-ray spectroscopy results for elemental analysis of zones (ad) for
sample S2.

Oxide zone S2 Element

O (wt.%) Cr (wt.%) Fe (wt.%)
a 9.54 16.57 69.31
b 15.17 29.83 53.26
Fig. 2. Amplied image of sample S2 with a microscope objective of 40, showing c 11.25 25.53 57.52
the four oxide zones (ad). d 10.18 17.32 69.47

were generated by the focused spot laser. They were caused by the
temperature gradient created by the heat of the laser and the dif-
fusion of heat perpendicular to the laser scan direction. With the
laser beam moving, the temperature in the region may be high
enough to make material evaporate and the highest temperature
region would be at the edge of the laser spot over the sample,
creating distinct morphologies that appear as periodical parallel
ripples or periodic surface structures depending on the laser
marking parameters, such as pulse frequency, scanning speed
and laser power.
The zone that separates each scan line is also noticeable (zone
d), and the other zones are dened by slightly different shades of
gray and color.
Using the measuring tool of the SEM system, we computed the
average distance from the center of zone (a) to the center of each
selected zones (bd); the distance from zone (a) to zones (bd)
are 37.5 lm, 75 lm and 97 lm respectively. The average width
for each zone is as follows: (a) = 75 lm, (b) = 33 lm, (c) = 18 lm
and (d) = 24 lm.
Tables 2 and 3 show the main components with the highest con-
centration after laser irradiation determined by EDS analysis of the
four selected zones in samples S1 and S2, respectively. It can be ob-
served that the percentage composition of the main components
shown in Table 1 changed in every zone, and that oxygen is present
now, indicating the presence of an oxide. The CrFe ratio changed for
each zone in comparison to the nonirradiated samples. For example,
the CrFe ratio for zone (b) and zone (c) of sample S1 are 0.58 and
0.45 respectively; the same occurs for the sample S2, with ratios of
0.56 and 0.44 for zone (b) and zone (c) respectively. In addition, it
can be seen that zone (b) has the higher percentage of oxygen in
sample S1, but in sample S2 zone (b) has the higher percentage of
chromium. Despite these differences, the elemental distribution
over the oxide zones analyzed is quite similar in both samples.
Raman spectroscopy
We used Raman spectroscopy, as a punctual technique, to iden-
tify the kind of oxide present in the selected zones and to establish
their relation with the Energy-dispersive X-ray spectroscopy re-
sults. Fig. 3 shows the Raman spectra for samples S1 and S2 for
zones ad. It can be noticed that in the spectra of zone a there is
a sharp main band at 675 cm 1 and a shoulder at 633 cm 1,
which are present in both samples; these spectra are similar to
the one reported by McCarty [31], which corresponds to a spinel
structure solid solution of Fe1.8Cr1.2O4. In addition to this, there is
no signicant difference between the intensity prole of the S1
and S2 spectra of zone a, only a small difference in the intensity ra-
tio of the Raman bands at about 426 cm 1 and 489 cm 1, which
are possibly related to Cr2O5 [32].
In the Raman spectra of zone (b); two main Raman bands can be
observed in both samples, one at 483 cm 1 and another sharp
684 M. Ortiz-Morales et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 681685
Fig. 3. Normalized Raman spectra of the oxide zones (ad) generated on the surface
of samples S1 and S2.
band at 673 cm 1, related to the FeO vibration of Fe3O4 [3336].
In sample S2, there is a weak band at around 405 cm 1 that is not
present in S1 and a shoulder at 625 cm 1, which may indicate the
presence of Fe2O3 [37]. Also, taking the band at 483 cm 1 as refer-
ence, a shift of the band located at 673 cm 1 to 675 cm 1 can be
observed for the sample S2, which could be related to the differ-
ence in the percentage of elemental composition [31] (see Tables
2 and 3). This elemental difference for this zone (sample S1 con-
tains more oxygen than S2) is reected in the intensity ratios of
the main bands at 483 cm 1 and 675 cm 1, the values of which
are 2.1 and 11.6 for S1 and S2, respectively.
In the Raman spectra of zone (c) for both samples; it can be ob-
served that the prole intensities of these spectra are not so similar
to those of zones (a) and (b), although , they present two Raman
bands at 566 cm 1 and 673 cm 1, which are related to Fe3O4
[31]. In single-crystal studies, group theory predicts another three
Raman bands at 420 cm 1, 320 cm 1 and 298 cm 1, which are not
clearly observed in the spectra of this zone, possibly due to that the
oxide is not a single crystal structure [31]. In addition, there is a Ra-
man band around 714 cm 1 for S1 that is related to maghemite (c-
Fe2O3) [38]. The spectra shown for zone d are similar to the spectra
for zone c but are broader and less solved possibly because the
structure is more amorphous than crystalline [39].
Table 4 resumes the Raman bands found in this work. In gen-
eral, it can be observed that the Raman band at 673 cm 1, which
is related to magnetite, is clearly present, at least in zones (ac)
[3942]. The prole intensities of some Raman bands at low fre-
quencies are different from those reported in the literature, possi-
bly because of the way in which the oxides were generated in this
work. The lms generated were attached to the metal by laser irra-
diation, while in some reported works the analyzed oxides (pow-
ders and lms) were generated in a different way and, in the
Table 4
Raman bands for the oxide zones generated on the stainless steel samples.
Sample Zone
a b c d
Raman bands (cm 1)
1 489, 633, 675 483, 625, 673 566, 673, 714 566, 714
2 426, 633, 675 405, 483, 625, 675 566, 673 557, 686
analysis, showed to be very sensitive to the laser power of the
Raman system, as reported by Amulevicius et al. and de Faria
et al. [8,38] respectively. It is also worth noting, as reported by
McCarty [31], that the difference in the CrFe ratio inuences the
shift of the band at 673 cm 1.
4. Conclusions
Periodic patterns of four different oxides zones were generated
by IR laser irradiation in commercial stainless steel at ambient con-
ditions. These zones were characterized by Energy-dispersive
X-ray spectroscopy and Raman spectroscopy techniques. An ele-
mental redistribution was observed after laser irradiation, with
particular variations for each oxide zone. These variations were
corroborated by the changes in the prole intensities of the Raman
spectra, which suggest the presence of magnetite and maghemite.
In addition, it was observed that the prole of the spectrum was
related to the initial elemental composition of the commercial
stainless steel samples. Furthermore, it was noticed that, in the
Raman analysis, using high laser power, there were no new phase
changes in the oxides micro-zones due to the heating effects of
the excitation wavelength of the Raman system, probably because
the oxides are adhered to the metal surface. Our work may be
extended to other alloys with several applications taking into
account that laser thermal interaction could generate periodic pat-
terns of different oxides phases in small zones.
Acknowledgements
Authors would like to acknowledge to Centro de Investigaci-
ones en Optica, A.C. and Laser Tech, S.A. de C.V. for the opportunity
to make this work and the opportunity to continue working on this
eld.
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