HIGH-TEMPERATURE OXIDATION IN AIR OF 316L STAINLESS STEEL SURFACE:

CHEMICAL AND MORPHOLOGICAL STUDIES

Luis Porras1,2*, Aarn Muoz1**, Samuel Aquino1, Gema Gonzalez3, Hebert Molero4
(1)
Grupo de Instrumentacin y ptica, Departamento de Fsica, Facultad experimental de Ciencias y
Tecnologa, Universidad de Carabobo, Valencia, Venezuela.
(2)
Investigacin y Desarrollo, Instituto Geogrfico Militar (IGM), Quito 17-01-2435, Ecuador.
(3)
Centro Tecnolgico, Instituto Venezolano de Investigaciones Cientficas (IVIC), Caracas 1020A, Venezuela.
(4)
Prometeo, Secretaria Nacional de Ciencia, Tecnologa y Saberes Ancestrales (SENESCYT), Zonal 1 y 2.
Ibarra, Imbabura, Ecuador
*luis.porras@mail.igm.gob.ec ; **aamunoz@uc.edu.ve

ABSTRACT
Steel has become the backbone material of the modern world because of its many unique and irreplaceable
characteristics and properties and will remain the foundation for future industrial development and progress.
316L austenitic stainless steel has mechanical and chemical properties that made it idoneus to be used as bone
implants. The aim of the present study was studied and characterized the modification of the 316L austenitic
stainless steel surface to understand furthermore the role of the surfaces topology when it is coating with
bioactive ceramics. All samples were mechanical polished with a silicon carbide grinding paper from 120grit to
2000grit taken them to a mirror like quality and some of them were ground at 240 grit. The samples were
thermally treated at 900C for one hour in air. The morphological characterization was made using scanning
electron microscopy, optical microscopy and roughness measurements, while the structural characterization
was done with X-ray diffraction. The oxidation at 900C in air of the samples with an initial mirror like quality
and mechanical polished at 240 grit were rationalized resulting that the samples with a 240 grit initial finishing
had uniform oxide film and the samples to a mirror like quality had an irregular stratified surface with poor
adhesion to the substrate. The scales formed on the later samples with an initial mirror like quality after thermal
oxidation comprises hematite and magnetite, with much less wustite and the oxide film found after the heat
treatment was rich in different structures.
Keywords: Stainless Steel, Oxidation, Roughness, Heat Treatment, Morphological Characterization .

RESUMEN
El acero inoxidable se ha convertido en la columna vertebral del mundo moderno debido a sus muchas
caractersticas y propiedades nicas e irremplazables y seguir siendo la base para el futuro del desarrollo
industrial y el progreso. El acero inoxidable austentico 316L tiene propiedades mecnicas y qumicas que lo
hacen idneo para ser utilizado en implantes seos. El objetivo de este trabajo fue estudiar y caracterizar la
modificacin de la superficie del acero inoxidable 316L para entender la funcin de la topologa de la
superficie cuando es recubierto con cermicas bioactivas. Todas las muestras fueron tratadas
metalogrficamente con papel de carburo de silicio de 120grit a 2000grit y posteriormente algunas de las
muestras fueron pulidas a calidad espejo. Las muestras fueron tratadas trmicamente a 900C durante una hora
en aire. La caracterizacin morfolgica se realiz mediante microscopa electrnica de barrido, difraccin de
rayos X, microscopa ptica y mediciones de rugosidad. Se analiz y estudi el desprendimiento de la capa de
xido en las muestras a un espejo de calidad y la formacin de una capa de xido uniforme sobre la muestra a
240grit. Las capas de xido formadas despus del tratamiento trmico comprende hematita y magnetita, con
una proporcin menor de wstita y, adems, morfolgicamente la pelcula de xido encontrada luego del
tratamiento trmico era rica y diversa en estructuras.
Palabras Claves: Acero Inoxidable, Oxidacin, Rugosidad, Tratamiento Trmico, Caracterizacin
Morfolgica.
pg. 1
1. INTRODUCTION
Stainless steels consists primarily of iron, carbon, chromium, nickel and other alloying elements at varying
concentrations, depending on the desired applications. Each of the alloying elements has a specific effect on the
properties of the stainless steel. The combined effect of all the alloying elements, and to some extent the
impurities determines the property profile of different stainless steel grades [1]. Chromium, molybdenum and
nitrogen are the alloying elements that increase the resistance of stainless steels to both pitting and crevice
corrosion.
Its higher levels of chromium yield better oxidation resistance and the presence of nickel-molybdenum is the
responsible for its excellent resistant to stress corrosion cracking and good properties in sulphur-containing
environments at high temperatures [1,2]. Although originally developed for industrial purposes, these materials
have been tried for biomaterial uses due to their relatively high corrosion resistance and excellent mechanical
properties. However, when used as biomaterials, these materials pose several problems due to the presence of
nickel. These problems include toxicity of corrosion products and fretting debris to the human body, fracture
due to corrosion fatigue and fretting corrosion fatigue, lack of biocompatibility, and inadequate affinity for cells
and tissues. In particular, the toxicity problem brought about other problems such as allergy reaction, tumor
formation, teratogenicity, and inflammation [3,4]. The release of nickel trace elements which cause toxicity has
prompted the development of nitrogen-containing nickel-free austenitic stainless steels [5].
Type 316 is an austenitic chromium nickel stainless steel containing molybdenum, and has a density of
7.99g/cm3 [6]. The addition of molybdenum increases its general corrosion resistance, improves its resistance to
pitting from chloride ion solutions, and provides increased strength at elevated temperatures [7,8,9]. The
passivity phenomenon is extremely important since it is the basic mechanism in the corrosion resistance of
stainless steels, and involves the formation in fine barrier layer on alloy surface of the order of 1.0nm to 2.0nm
thick, which reduces the corrosion rate to negligible levels [10].
The passive films of stainless steels are very thin, being 1-5nm thick, and are generally described as hydrous
oxides, which are mostly enriched primarily with chromium, silicon, and molybdenum and are naturally free of
pores [11,12]. The nature of passive film formed on stainless steels depends on the underlying metal, and will
have different properties in areas where the surface is homogeneous.
The effect of exposure of a material to media can be a very complex subject. Elevated temperatures tend to
increase corrosive action, heat transfer may affect corrosivity, thermal cycling can increase metal wastage
through spalling of protective scale on the metal surface, and metal temperature probably will not be the same
as the environment to which it is exposed [13]. Generally, if oxidation or other forms of scaling are expected to
be severe, a greater cross-sectional area beyond that indicated by mechanical property requirements is
usually specified.
The strengthening of stainless steels by cold working or heat treatment can be beneficial in the temperature
range where the steels behave in an elastic manner (up to about 900F (482C)). With time at temperature,
changes in metallurgical structure can be expected for almost any steel or alloy. In stainless steels, the changes
can be softening, carbide precipitation, or embrittlement. Softening occurs in the martensitic stainless steels
when exposed to temperatures approaching the original temperature. Cold-worked austenitic stainless steels
may also soften at elevated temperature. Carbide precipitation may occur in certain austenitic stainless steels in
a temperature range of 800-1650 F (427-899C). This causes a loss of toughness and except for the low-
carbon L grades and the stabilized types may make the steel subject to intergranular corrosion in certain
environments. Embrittlement usually means the loss of room temperature toughness. Embrittled equipment
must be handled carefully to avoid the impact when it is cooled down for maintenance.
Carbon is the most important alloying element in carbon steels and its level in steels depends on the required
mechanical properties. Manganese is another important element in carbon steels; however, very little attention
has been focused on the effect of manganese on steel oxidation. Most of the experimental steels used in the
early studies also contained relatively high levels of silicon (at about 0.2%), because it was used as a
deoxidizing agent during steelmaking.

pg. 2
For this study was used the type 316L austenitic stainless steels, with samples mechanical polished at grit 240
and to mirror like quality to form and characterize morphological and chemical changes caused by heat
treatment at 900C for one hour in air. The idea is to form a resistant surface and with sufficient affinity to
serve as support for a film of hydroxyapatite (HA) for use, in the future, as interface to the bone-implant
system. The HA has a composition similar to that of the bone reducing the possibility of rejection by the human
body structure.
In this work, is characterized in detail the morphology and chemical changes on the 316L austenitic stainless
steels surface to a mirror like finishing and to grit 240 subjected to heating in air at 900C. The detachment of
the oxide scale on the samples of a mirror finished and the formation of a uniform oxide layer on the sample to
mechanical polished at 240grit is rationalized.

2. EXPERIMENTAL PROCEDURES

2.1. Substrate preparation

The 316L austenitic stainless steel was a rod of 12.5mm in diameter with a chemical composition (at.%) as
follows: 17.29% Cr, 9.75% Ni, 1.81% Mn, 1.24% Mo, 0.03%S, 1.04% Si, 68.86% Fe. The samples were cut
into 3-mm-thick discs. The discs were rectified to obtain a sample with two parallel planes (see Figure 1a).
During cutting and grinding coolant was used to ensure that the samples were not warmed up. The samples
were mechanical polished with a silicon carbide grinding paper between grit 120 to 2000 [14] (Figure 1b).
Finally, the samples were polished to a mirror like finish with 1.0 m and 0.05m diamond powders (Figure
1c). In order to assure the uniformity and polished of the 316L stainless steel samples, the test of Hartmann was
used for to study and control of the preparation of substrates to a mirror like quality [15].
After each surface treatment, all the samples were ultrasonic cleaned for 20 min, firstly in acetone and distilled
water, secondly in 96% ethanol (in volume) before a final rinsing with distilled water and finally air dried [16].

2.2. Surface characterization

X-ray diffraction (XRD) measurements with Cu K radiation source were carried out to detect the phase changes
in the surface layers. The current and voltage of the X-ray tube were 20 mA and 40 keV respectively. The
samples were measured in the continuous registration mode (at a speed of 4/min) within the 2 -angle range
from 30 to 95.
The surface roughness were measured based on ISO Standard 97 using a Mitutoyo 178-923-2A, SJ-201
Surftest. Samples were randomly selected for recordings (five measurements per each one). The whole
measured length was lm=5 mm. Quantitative profilometry provides four definitions: 1) average roughness Ra;
2) peak-to-valley height Rz, defined as the difference between the maximum and minimum surface heights; 3)
root mean square roughness value Rq 4) and, finally, the highest difference between the maximum and the
average surface heights Ry. The pick-up had a skid type diamond stylus with a radius of 5m and a tip angle of
90.
The hardness machine used for this study was the Buehler Macromet 5100 Rockwell Type Hardness Tester,
manufactured by the Mitutoyo Corporation. To apply the load to the samples, a 1/16 in. diamond ball indenter
was used in the Macromet.
The morphological features of the substrates were studied by optical microscopy using an Intel Play QX3
Computer Microscope. Five areas on different samples were examined for each magnification (10X, 60X and
200X).
For to identify the microstructural features of phases present was used the etching following the norm ASTM E
407-70. This solution was formed by 100ml of distilled water, 20ml HNO 3 and 60ml of HCl and this were
studied with a Union MC-86267 Metallurgical Microscope with magnification of 100X, 200X, 400X and
1000X.
The micro-morphology of the surface was observed by the JEOL JSM-5300 Scanning Microscope and the
EDX analysis was performed in a Phillips XL30 attached with an EDX DX4 and backscattering system.

pg. 3
2.3. Thermal treatment
For the thermal treatment in air of the stainless steel samples the Small Benchtop Muffle Furnace FB1315M
120V was used. The samples with mechanical polished at 240grit and to mirror quality were put into a
preheated furnace and kept at 900C for a fixed time of 160 min. The isothermal oxidizing has been followed
by a slow cool down into the furnace to prevent the phase change of the material and the variation of his
mechanical properties. All samples were investigated at room temperature.

3. RESULTS

3.1. Characterization of the untreated sample

The mechanical polishing to a mirror like quality of the samples was controlled using the Hartmanns test [15].
The optical micrographs (see Figure 1) show the behavior of the surface during the process of metallographic
preparation.

Figure 1a Figure 1b Figure 1c

Figure 1. Optical micrograph of the metallographic process of the 316L stainless steel samples.
1a) rectified; 1b) ground to grit 240; 1c) to mirror like quality.

Average roughness parameter for the substrates is showed in the Figure 2. The values correspond at least to 10
measurements during the grinding of the samples between 120grit to 600grit. The values on the Figure 2 are
averages of the measurements taken in the parallel and perpendicular directions. Roughness measurements
higher to 600 grit cant be performed because the skid type diamond stylus produces a deformation on the
surface of the sample.

Roughness vs. Grit

210
180
Ra (nm)

150
120
90
60
30
0
100 150 200 250 300 350 400 450 500 550 600
Grit (grains/plg2)

Figure 2. Mean roughness parameter Ra versus grit 316L stainless steel surface.

The Hatmanns test [15] was performed to determine the final quality of the
mechanically polished to a mirror like quality samples. Basically, the Hartmanns test
consists of using a Hartmanns screen that produces a Hartmanns pattern that allows us
to determine the quality of the mirror like finishing of the samples. The test quantify the
difference in the intensity of the reflected light (the source is mostly a laser because of
pg. 4
its coherently and high intensity light) from the surface of the sample with the intensity
of the Hartmanns pattern obtained from the reflected light coming from a commercial
mirror, In Figure 3 is possible to few Hartmanngram of the reference mirror and mirror
like finishing samples. Our criteria in selecting the high quality mirror finishing was to
choose those samples with an average quadratic deviation of intensity less or equal to
10 % with respect to the commercial mirror.

Figure 3. Hartmanns patterns of the sample to mirror like quality. The Figure A correspond Hartmanns pattern of the
reference (commercial mirror).

In the analysis of the microstructural phases present of the untreated sample the austenite phase has been
identified without any evidence of martensite according to methods in the norm ASTM E 407-70 Practice for
Microetching Metals and Alloys [17] (Figure 3). The dark lines seen in the microstructure are the grain
boundaries. The spots seen are the inclusions and the carbides. Grain size can be measured using the optical
microscope on a transverse metallographic mount by counting the number of grains within a given area, by
determining the number of grains that intersect a given length of a random line, or by comparison with
standards references (ASTM-E112-96). The average grain size of this sample is about 6, that mean between 24
to 48 numbers of grains/in2(mm2) at 100X. The Rockwell D average hardness value was 36.8.

Figure 3. Optical image of etched as received 316L stainless steel microstructure verifying the austenite phase (200X was
used).

The X-Ray diffraction analysis of 316L stainless steel without thermal treatment confirmed the presence of
austenitic phase (Figure. 4). The substrate presents diffraction peaks at 43.7, 50.8, 74.7, 90.7 and 95.9 2
scattering angles which are consistent respectively with (111), (200), (220), (311), (222) reflections of
austenite. As expected, untreated 316L stainless steel presented characteristic diffraction spectra of face-
centered-cubic austenite. No peak other than diffraction peaks were detected.

pg. 5
 Figure 4. XRD pattern of as received 316L stainless steel show (111), (200), (220), (311), (222) reflections of
austenite.

3.2. Surface analysis of thermally treated sample.

The heat treatment applied to the samples not produce a phase change in the same, that is, the austenite phase is
maintained. Only an increase in grain size that happens to have between 12 to 24 grains per square inch at
100X magnification occurs thus has a grain size of 5. The Rockwell hardness test performed on the 316L
stainless steel samples showed a decrease in hardness after the heat treatment process at 900C. The Rockwell
D average hardness value was 26.3. This decrease of the hardness is rationalized as a consequence of the
decrease of the intergranular interface.
The scale formed after 60min of oxidation on 316L stainless steel initially finished to mirror like quality has
poor adherence of the substrate. Surface roughness measurements for the area between the center of the disc
and the edge had values between 1,44 + 0,01m to 1,58 + 0,01m; respectively, and for the center area of the
sample had an average value of 1,18 + 0,01m. Average value of roughness obtained as consequence of oxide
layer growth is non-uniform and non-adherent to the substrate.
Figure 5 shows SEM images of 316L stainless steel surface after the thermal treatment at 900C. The oxide
film found was rich and diverse in structures after the treatment, confirming the heterogeneity of the surface
and this occurs also microscopically. SEM micrograph reveals the formation of at least two stratified structures;
the outer has a series of spheroidal or granular particles with different sizes, which are seen in detail on the
Figure 5a, and Figure 5b. This layer has poor adhesion with the substrate and the dark color of this material is
different to the color of the substrate suggesting that its composition is different, indicating that a migration-
diffusion process is different for the various elements present in the steel [31]. Because of the expansion of the
detached areas as a result of the blister growth and coalescence, the scales formed after longtime oxidation
comprise hematite and magnetite, with much less wustite being present (Figure 8) [18-20].

Figure 5a Figure 5b
Figure 5. SEM images (Figure 5a and 5b) of 316L stainless steels to mirror like quality thermally treated. The micrograph
shows different structures on the substrate formed after the treatment.

The poor adhesion of this layer can be explained in several ways, which may occur simultaneously: First,
during the oxidation process increases the lattice constant of the crystals in the material causing an increase in
the volume on this increasing lateral pressure and causing a possible detachment abruptly layer formed.

pg. 6
Secondly, the loss of chemical affinity between the top layer and the substrate, that possibly occurs when a
layer thick enough has created their own identity very different of the substrate from which it was generated.
Finally, during steel oxidation, carbon from the steel substrate can be oxidized, causing decarburization of the
steel when the rate of carbon oxidation exceeds that of iron. Decarburization is normally observed above
700C, particularly for steels containing relatively high levels of carbon [21-24]. Simultaneous scaling and
decarburization has been studied [18,23,25, 23,25-27] and the general consensus is that during steel oxidation,
carbon reacts with the scale via the following reaction:
[C] + FeO = Fe + CO (1)
where [C] denotes carbon in solution in steel. Further reaction between CO and the scale may produce CO 2 via
the following reaction:
CO + FeO = Fe + CO2 (2)
The reactions can proceed only when CO and CO 2 can escape through the scale [28,29]. It was proposed that
these gases could escape through microchannels, such as microcracks or pores.
Moreover, the scale structures formed in air or oxygen on steel after oxidation for a short time are usually
similar to those formed on pure iron, comprising a thick inner wstite layer, a thin magnetite layer and a very
thin surface hematite layer.
Cross-sectional observations of the blistered area has revealed a thin scale layer comprising primarily hematite
and magnetite arching outward over a cavity between the scale and the substrate [20,35]. This is because at the
blistered area, iron supply is terminated as a result of scale detachment from the substrate, and the wstite
formed earlier is oxidized to higher oxides at the later stages. At those areas where the scales are still in contact
with the substrate, the scales comprise three layers, but the thickness ratios between the three layers tend to
vary at different locations. This proportion of oxide phases reflects the fact that diffusion coefficient of iron in
wstita is much greater than in magnetite and that the diffusion of oxygen and iron through the hematite layer is
extremely slow [20,36, 36-38].

Figure 6a Figure 6b
Figura 6. The inner scale of SEM images (Figure 6a and 6b) of 316L stainless steels to a mirror like quality and thermally
treated. A porous structure on the substrate was observed.

This fact is confirmed due to the presence of a porous structure on the substrate (see Figure 6a), which allows
the percolation of the gases from the interior of the sample, but these cannot go outside because the scale is
forming dense enough to prevent the escape of gases producing an abrupt detachment of the scale. The carbon-
bearing gases generated during steel oxidation can also be transported via the outward movement of voids
originated at the scalesteel interface [28,29, 29]. A large number of vacancies are left at regions at or near the
scalesteel interface with the continuous outward diffusion of iron through the scale. These vacancies may
condense to form voids at the interface, providing a space to store the CO and CO 2 gases produced by reactions
(1) and (2). Voids formed in the scale on steels or iron containing over 50 ppm carbon has been clearly
observed in previous studies [30-33].
While it is not possible to discern a unique process that can explain the morphology obtained after heat
treatment of the sample with an initial mirror like finishing; it can be concluded that the chemical composition
of the oxide film is different from the substrate,substrate; this is verified in the micrographs in backscattered
electron mode (see Figure 7).
pg. 7
 Figure 7a Figure 7b
Figure 7. Backscattered electron mode micrographs of 316L stainless steels to a mirror quality and heat treated. The
chemical composition of the scale is different from the substrate.

Figure 8. XRD pattern of the 316L stainless steel to mirror like quality thermally treated. The x-ray pattern reveals the
existence of a magnetite and hematite phases. The peaks corresponding to Cr2O3, CrO, NiO and CrO were observed.

The X-Ray diffraction pattern after oxidation for 60min at 900C reveals the existence of a surface Fe 3O4
(magnetite) phase (see Figure 8). The patterns recorded revealed the existence of the -Fe2O3 surface phase
(hematite). Comparison of the intensity of the diffraction lines corresponding to the three oxides and suggests
that the oxide film has a layered structure consisting of three layers, of which -Fe2O3 is the outermost and FeO
is next to the steel substrate [34]. The peaks corresponding to Cr 2O3, CrO, NiO and CrO were observed.
EDX results of the oxide films for the 316L stainless steel to mirror like finished formed at 900C in air showed
that the outer layer was rich in Fe, the ratio Cr/Fe is equal to 0,04; while the inner layer was richer in Cr and Fe
(Figure 9), ratio Cr/Fe is 0,94. The line scan analysis results are shown the outer layer of the oxide film
consisted mainly of Fe oxide. In the inner layer (Figure 9b) the content of Cr oxide increased sharply and that
of Fe oxide decreased. In addition, Ni enrichment was observed at the interface between the metal matrix and
inner layer.

Figure 9a Figure 9b
Figure 9. EDX analysis of 316L stainless steels to mirror like quality thermally treated. The outermost layer is composed
principally of an iron rich mixed oxide phase (Figure 9a) and the inner layer is composed of Cr oxide (Figure 9b).

pg. 8
EDX analysis (Figure 9) shows two domains. The outermost layer is composed of an iron rich mixed oxide
phase. The oxidation is controlled by the diffusion of Fe 2+ ions through of this oxide layer. Initially the diffusion
of Cr3+ ions determines the rate of reaction and formation of the scale. Then from a certain thickness of
chromium oxide, the diffusion of Fe3+ takes over, which limits the rate of formation of external oxide layer;
thereof, the outer oxide layer becoming rich in iron. There is thus a step of the growth mechanism of the oxide
which controls the speed of the reaction.
The effect of heat treatment of a 316L stainless steel sample with a finishing of 240 grit was the formation of a
uniform oxide layer all over the sample (see Figure 10).

Figure 10a Figure 10b

Figure 10. Optical micrograph of the 316L stainless steel samples ground to 240grit and thermally treated. The thermal
treatment formed a uniform oxide layer on the surface.

Average roughness parameter for the thermally treated substrates is higher respect to the substrate untreated.
The values measured were between 0,11 + 0,01m to 0,32 + 0,01m before and after the thermal treatment;
respectively, the surface uniformity is confirmed with the results of the others roughness parameters (see Table
2) and only a small disruption of this uniformity to the edges of the sample as shown in Figure 10b. In this area
a detachment of material was observed of the sample but this behavior is due to edge effects, which are not
representative of the sample surface; moreover, and also the extent of the material detachment is small.
Table 2. Average roughness parameters of the 316L stainless steel ground to 240 grit and thermally treated.
316L stainless steel ground to 240 grit
Measure1 Measure2 Measure3
(m) (m) (m)
Ra 0,32 0,32 0,32
Rq 2,41 2,44 2,33
Ry 1,51 1,75 1,56
Rz 0,41 0,42 0,42

The surface of these samples is quite uniform, Figure 11, shows a Hhigh magnification micrographs (see Figure
11) representative area of 240 grit finishing and thermally treated at 900 C for 1 hour samples; it is possible to
see theshowed marks of the mechanical work with certain irregularities produced by detachment of inclusions
or outcrop material grains. Backscattered electron mode micrographs (see Figure 12) showed in more detail
athe surface of the sample where darker small areas are visible; indication of a local enrichment of lighter
elements, probably iron. Furthermore, there is no problem to say that the surface is uniform because these dark
areas represent a small percentage of the surface of the sample.

pg. 9

Figure 11a Figure 11b
Figure 11. SEM images (Figure 11a and 11b) of 316L stainless steels ground to 240grit and thermally treated. The
micrograph shows that the surface is uniform.

Figure 12a Figure 12b

Figure 12. Backscattered electron mode micrographs of the 316L stainless steel ground to 240grit and thermally treated.
The darker small areas can indicate of a local enrichment of lighter elements.

The nature of this well adhered surface must be richer in chromium oxides as a part of a passivating layer
formed on the surface, it was confirmed with the EDS Cr/Fe ratio, which is equal to 0,32, see Figure 13.b,
which is higher to the tipical Cr/Fe of a passivated layer formed when the surface of the stainless steel is
exposed to the atmosphere at nomal conditions. In our case the EDS Cr/Fe ratio of the sample exposed to the
atmosphere is 0,26 and the presence of oxygen was out of the detection limit of the instrument, see Figure 13.a.
While, the amount of oxygen on the sample thermally treated was quite high, the ratio O/(Cr+Fe) is equal to
0,44. This is a clear indication of a thicker passivating layer as a concequence of the thermal treatment. The
initial oxidation rate is controlled by the transport of oxygen in the gas phase to the sample surface [20].

Figure 13.a. EDX analysis of 316L stainless steels exposed to the atmosphere

pg. 10
Figure 13.b. EDX analysis of 316L stainless steels to 240grit thermally treated

The high adhesion and uniformity can be explained basically in three different ways:
1. - The initial roughness and the structural changes resulting from use of carbide silicon paper during the
mechanical polished to 240 grit not allowed a buildup of the gas produced by the oxidation-reduction reaction
during the thermal treatment.
2. The increase of the surface area product of the mechanical polished to 240 grit helps to reduce the surface
tensions which may be increasing during the formation of oxide.
3.- And finally, the fact that the large population energetically favorable for the formation of stable oxides on
the surface sites increases due to an increase in the population of defects, which are more active than areas
where there is absence. This energy produces enough stable oxides favoring to form a passive layer which
prevents that the oxidation of the 316L stainless steel keeps going on.

Figure 13. EDX analysis of 316L stainless steels to 240grit thermally treated.

EDX analysis (see Figure 13) showed an enrichment of chromium on the sample surface to 240grit thermally
treated. The scale thickness on steel after the oxidation process was increased with the increase of the oxygen.
The initial oxidation rate is controlled by the transport of oxygen in the gas phase to the sample surface [20].
The proportion rate Fe/Cr was of 3,35 after the thermal treatment.

4. CONCLUSIONS
Results of the oxide films for the 316L stainless steel to mirror like finished formed at 900C in air showed that
the outer layer was rich in Fe, while the inner layer was rich in Cr and Fe. The oxide film macrostructure is

pg. 11
layered.
The surface morphology is important in 316L stainless steel oxidation process. That is, an initial polished to
mirror quality favors the formation of an oxide scale with poor adhesion to the bulk of the sample. A
mechanical polished to 240 grit favors the formation of a uniform passivating layer of mixed oxide passivated.
The expansion of the detached areas as a result of the blister growth, the scales formed after thermal oxidation
comprises hematite and magnetite, with much less wustite, iron supply is terminated as a result of scale
detachment from the substrate, and the wustite formed earlier is oxidized to higher oxides at the later stages.
Some later studies suggested that blisters could form during oxidation at high temperatures as a result of CO
generation. This proportion of oxide phases reflects the fact that diffusion coefficient of iron in wstita is much
greater than in magnetite and that the diffusion of oxygen and iron through the hematite layer is extremely
slow.
Importantly, the fact that the 316L stainless steel presented in this study is austenitic, due to the thermal
oxidation processes of about 900C is necessary retained their mechanical and thermochemical properties. The
heat treatment produced a migration-diffusion process for the various elements present in the steel.

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 Resumen Grfico (Graphical Abstract)

Para la versin online de la RLMM, se les pide a los autores que incorporen un Resumen Grfico (Graphical
Abstract) de su trabajo. Este resumen grfico debe ser: una figura original (no utilizada en su totalidad en la
escritura del manuscrito), a color, cuyo tamao horizontal est entre 300 a 350px (7.9 a 9.3cm), y con una
tamao vertical entre 200 a 250px (5.3 a 6.6cm). Se les invita a los autores a visitar los ltimos nmeros de la
RLMM, donde podrn observar diferentes tipos y modelos de resmenes grficos.

pg. 15