Oxidation behavior of AISI 321, AISI 316, and AISI 409 stainless

steels: Kinetic, thermodynamic, and diffusion studies

Abdolvahid Movahedi-Rad
School of Metallurgical and Materials Engineering, College of Engineering, University of Tehran, Tehran 11365, Iran
Seyedeh Sogol Pelaseyed and Mitra Attariana)
Department of Materials Science and Engineering, Sharif University of Technology, Tehran 11365, Iran; and Razi
Metallurgical Research Center (RMRC), Tehran 37515, Iran
Reza Shokrallahzadeh
Iran Power Plant Project Management MAPNA, Tehran, Iran

(Received 3 September 2015; accepted 17 March 2016)

The oxidation behavior of three types of stainless steels, namely AISI 321, AISI 316, and AISI
409, was compared. In all stainless steels, oxide layers were formed and their masses and
thicknesses increased with oxidation time. Among them, AISI 409 ferritic stainless steel
demonstrated higher oxidation rate. According to the kinetical oxidation behavior of them at
elevated temperatures, the oxidation mechanism was determined. Among them, the AISI 409
ferritic stainless steel showed the lowest and AISI 321 austenitic stainless steel demonstrated
the highest oxidation resistance. Based on the experimental results, it was suggested that the
kinetic of oxide growth in stainless steels was followed by a parabolic relationship. In all cases,
a well-known Cr-rich internal oxidation zone (IOZ) was observed. The formation of IOZ was
suggested by the Gibbs free energy expression and confirmed by following up the formed
oxide layers at different holding times. Furthermore, the formation of thicker oxide layers in
ferritic stainless steel was explained by using solid-state diffusion relations and supported by
quasi-steady-state approximation of Fick’s first law.

I. INTRODUCTION excessive metal temperature during the operation. It is

Undoubtedly, steels are dominating industrial materi-
als. Among them, stainless steels with notable mechan-
ical properties and corrosion resistance are completely
essential for using in tools, structural, and energy
applications. These are due to the presence of alloying
elements such as chromium and nickel, which make
stainless steels quite distinct and superior from other
grades of steels, especially at the harsh atmosphere and
elevated temperature.1,2 Among the different grades of
stainless steels, austenitic stainless steels such as AISI
321 and AISI 316 with high contents of Cr and Ni are
wildly used in the industries at intermediate temperature
(923–1073 K).3 Recently, ferritic stainless steels like
AISI 409 by offering lower costs than austenitic grades,
due the absence of nickel element and offering lower
expansion coefficient than austenitic steels, as a great
advantage when temperature cycling resistance is needed,
have been developed.4–6
The presence of heavy oxidation at the elevated
temperature can cause degradation of the materials and
Contributing Editor: Edson Roberto Leite
a)
Address all correspondence to this author.
e-mail: m_attarian@razi-center.net
DOI: 10.1557/jmr.2016.141
because of the lower thermal conductivity of oxides in
comparison to the steels and may cause creep damage
and structural degradation.2,7 In addition to the temper-
ature, there are some other factors, which are effective on
the oxidation behavior of steels. For example, chemical
composition of material and gas, the rate of gas flow,
surface preparation, and pretreatment, which are effective
on the oxidation behavior of steels.8 Therefore, attempts
have been made to identify the oxide behavior at different
conditions. In Fe–Cr alloys, oxide layers of Cr2O3 and
Cr2O3/Fe2O3 are formed, which are the main protective
factor.9 There are researches in the literature, which
studied the high-temperature oxidation behavior of the
stainless steels.6,8,9 High-temperature oxidation in air of
Fe–13Cr–xAl alloys containing up to 4.5Al has been
studied in the temperature range 953–1253 K studied by
Kvernes et al.9 They showed that additions of Al modify
the oxidation behavior and at sufficiently high Al
concentrations, protective scales of Al2O3 are found. Re-
cently, the oxidation behavior of the stainless steel 441 was
investigated at a temperature range of 873–1223 K.10 It was
observed that the initial kinetic oxidation process of stain-
less steel 441 in pure oxygen atmosphere could be divided
into a quick linear oxidation stage, followed by a diffusion-
controlled stage at 873–1073 K and an interface reaction

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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies

controlled stage at 1173–1223 K. The influence of the determine the evolution of oxide formation at different
oxidation environment on oxidation behavior has been holding times by means of SEM and EDS.
considered as objective in some papers.11–13 Sabioni
et al.11 reported a comparative study of high-temperature
III. RESULTS AND DISCUSSION
oxidation behavior in AISI 304 and AISI 439 stainless
steels performed between 1123 and 1223 K, in oxygen and A. Kinetic of oxidation (oxidation resistance)
Ar–H2–H2O atmospheres. Based on their experiments it To study the kinetic of oxidation of stainless steels, at
was shown that oxidation resistance of the AISI 439 does first, the actual chemical composition of two austenitic
not depend on the atmosphere, however, the oxidation stainless steels (AISI 321 and AISI 316) and a ferritic
behavior of AISI 304 is temperature dependent and at stainless steel (AISI 409) is determined by spectroscopy
temperatures higher than 1223 K, the oxidation rate method and summarized in Table I. As can be seen, the
dramatically increases in oxygen atmosphere, in comparison Cr content is higher in austenitic stainless steels and AISI
to that observed in Ar–H2–H2O atmosphere. In the other 321 has the highest Cr content. In addition, the Ni content
studies by Huntz et al.6 and Carvalho et al.,13 the kinetics is also very much higher in two austenitic stainless steels
and oxide morphology of ferritic and austenitic stainless in comparison to the ferritic one.
steels in a temperature range of 1123 K and 1223 °C, in two As a next step, all samples were placed in the furnace
atmospheres of oxygen and Ar were investigated. for 72, 342, 1022, and 1202 h at the temperature of 873 K
To the best knowledge of the author, the comparative in air atmosphere. According to SEM observation, oxide
study of AISI 321, AISI 316, and AISI 409 at high layers were formed with different thicknesses, depending
temperatures during prolongated periods has not yet been on the alloy type and oxidation time. Figure 1 shows the
reported. Therefore, the aim of this work is to study the SEM micrographs of oxide layer of three stainless steels
high-temperature oxidation behavior of two austenitic after 72 and 1202 h holding under oxidation conditions. It
stainless steels of AISI 304 and AISI 304, and one AISI is seen that the oxide thickness is thicker in AISI 409
409 ferritic stainless steel at 873 K by measuring the ferritic stainless steel in comparison with two other
variation of mass and thickness of oxides during the austenitic stainless steels at both 72 and 1202 h oxidation
oxidation for kinetic studies. In addition, the formation of times. In addition, the presence of cracks is evident in
oxide layers is explained from thermodynamical perspec- oxide layers of austenitic stainless steels, which can be
tives. Furthermore, scanning electron microscope (SEM) related to their low thermal shock resistivity. On contrary,
and corresponding energy dispersive x-ray spectroscopy due to the lower coefficient of thermal expansion in
(EDS) are used to evaluate the thickness and chemical ferritic stainless no significant crack is observed.6
composition of oxide layers. At the ends, the diffusion As already explained, the weight of oxide layers was
reaction of oxides is also studied to justify the difference measured. Figure 2 shows the variation of weight loss
in the thickness of oxide layers. against cleaning time for all alloys. As can be seen, the
curves reach steady state and become straight, which
II. EXPERIMENTAL shows that there is no oxide layer on the surface of
samples. However, in the case of ferritic stainless steel,
To compare the oxidation behavior of three commonly the data present a slope which becomes lower with the
used stainless steels (AISI 321, AISI 316, and AISI 409), increase of the time, and at the end a small slope is
at first, their actual chemical compositions were deter- observed. SEM observation after the clearing process
mined by using spectroscopy method. After that, three
steel samples with the dimensions of 7.5 mm
10 mm

1 mm were prepared. Then, the samples were cleaned by TABLE I. Chemical composition of AISI 321, AISI 316, and AISI
409 stainless steels.
acetone, weighted, and placed in the furnace for 72, 342,
1022, and 1202 h and then left out. The temperature of Elements
furnace was 873 K and remained constant during the tests Alloys C Si Mn P S Cr Mo Ni
at air atmosphere. Subsequently, to measure the oxide
weight, the samples were cleaned with 10% chloride acid AISI 321 0.032 0.570 1.190 0.021 0.002 17.80 0.090 9.00
AISI 316 0.030 0.450 1.240 0.034 0.002 16.80 2.220 10.20
solution until their weight did not change significantly. In AISI 409 0.015 0.510 0.250 0.021 0.002 11.60 0.020 0.23
this case, to prevent possible corrosion of steels, hexam-
ine was used as an inhibitor. Some samples were pre- Elements
pared for oxidation characterization by polishing Alloys Al Co Cu Nb Ti V W Fe
technique. To do so, samples were sectioned and
AISI 321 0.031 0.005 0.070 0.019 0.350 0.130 ,0.02 Base
mounted by epoxy resin. Afterward, they were subjected
AISI 316 0.008 0.150 0.290 0.022 0.002 0.093 0.05 Base
to a fine abrasive lap grinding and subsequent 1 lm AISI 409 0.003 ,0.002 0.200 ,0.003 0.300 ,0.002 ,0.02 Base
diamond paste polishing. To observe the oxide layers and

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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies

FIG. 1. SEM micrographs of oxide layer after 72 and 1202 h holding under oxidation conditions, (a and b) AISI 321, (c and d) AISI 316, and
(e and f) AISI 409 stainless steels.

FIG. 2. The variations of weight loss per surface area against cleaning time at different holding times of (a) 72, (b) 342, (c) 1022, and (d) 1202 h in
three stainless steels.

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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies
shows that there are some very thin (1 lm) oxide
layers, which are distributed sparsely in intrusion parts of
surface. It is suggested that this small slope in ferritic
stainless steel can be attributed to very gradual cleaning
of this part of oxide layers. However, it is thought that
weight of such thin oxide layers is negligible.
Based on the SEM observations and weight measure-
ments, the variation of oxide mass and thickness for three
alloys at four holding times are illustrated in the three-
dimensional plots in Figs. 3(a) and 3(b), respectively. In
all samples, with increasing holding time, the thicker and
heavier oxide layers are formed. It is seen, there is a huge
difference in the thickness and mass of oxide layers
between austenitic stainless steels and ferritic stainless
steel. In this case, the thicker and heavier oxide layers are
related to the ferritic stainless steel after 1202 h.
Therefore, it is clear that the oxidation resistance of
ferritic stainless steel is much lower than austenitic ones.
These results are further used to determine the kinetic
behavior of oxide layers in stainless steels.
In this research, to find the oxidation mechanism, the
best fit of the experimental data has been found in
quadratic coordinates. Figures 4(a) and 4(b) show the
square variation of mass per surface area (Dm/s)2 versus
oxidation time (t) for ferritic and austenitic stainless
steels. It is seen that there is a linear relationship between
(Dm/s)2 and (t) in all cases. This demonstrates that the
FIG. 3. Three-dimensional plots of (a) oxide mass variations and (b) oxide
thickness variations at different oxidation times in three stainless steels.
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kinetic of oxidation for three stainless steels follows
a parabolic relationship based on the Eq. (1):

2
Dm
¼ kp t ; ð1Þ
s
where kp is parabolic oxidation constant. The kp can be
obtained by using of least squares method as a procedure
to determine the best fit line to experimental data.
Accordingly, the kp values for AISI 321, AISI 316, and
AISI 409, are 1.51
1012, 2.05
1012, and 1.26

1010 (mg2/cm4 s), respectively. So, AISI 409 shows
the highest and AISI 321 shows the lowest kp values. The
parabolic oxidation rate law suggests that the oxidation
behavior of three alloys is ionic diffusion-controlled
oxidation as a non-steady-state diffusion-controlled re-
action. This behavior corresponds to ohmic related mech-
anism in which ions diffuse thorough the point defects and
the thickness of the formed oxide layer is directly pro-
portional to oxidation time. Similarly, Huntz et al.6
reported that AISI 439 ferritic stainless steel obeyed
parabolic relationship from 1123 to 1223 K. However,
Carvalho et al.,13 reported a linear relationship for both
AISI 304 austenitic stainless steel and AISI 430 ferritic
stainless steel in the temperature range of 1373–1473 K.
FIG. 4. The square variation of mass per surface area (Dm/s)2 versus
oxidation time (t) in (a) AISI 409 ferritic stainless steel and (b) AISI
316 and AISI 321 austenitic stainless steels.
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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies

B. Characterization of oxide layers and Si is detected in the internal oxide layers. The
The EDS analysis of oxide layers in samples after 72 h formation of oxide layer with similar chemical composi-
of being under oxidation condition are listed in Table II. tion has been reported in the literature.6,9,14 According to
It is clear that the oxidation films are mainly composed of the EDS results, iron oxide (Fe2O3) is proposed for
iron oxide. However, a little Cr in three alloys and Ni in external oxide layer of stainless steels. By comparing
two austenitic stainless steels are also detected. Regard- the chemical composition of oxide layers at 72 and 342 h,
ing the chemical composition of oxide films, it should be it can be concluded that the chromium oxide in the
noted that quantitative EDS results may be over estimated internal oxide layer has been formed during the oxidation
for the Fe, Cr, and Ni elements in all cases. This can be and after iron oxide formation.
due to the large interaction volume of electron beam with Figure 6 shows the variation of oxide weight against
the substrate, which leads to the emission of x-ray from oxide thickness. As can be seen, in the austenitic stainless
material from both substrate and oxide layer. steels, there is not a linear relation between oxidation
Further investigation of Fe, Cr, Ni, Si, and O elemental thickness and oxidation weight, but it is linear in ferritic
distributions from the matrix to oxide layers after 342 h stainless steel. This nonlinear relationship in austenitic
of being under oxidation condition was performed by stainless steels can be related to the crack formation
SEM and corresponding and line scan analysis as during the cooling process. However, there is no signif-
presented in Fig. 5. It is seen in the SEM micrographs, icant crack in ferritic stainless, as shown in Fig. 1, which
unlike the previous conditions, the oxide layers are causes a linear relationship between oxidation thickness
composed of two internal and external oxide layers in and oxidation weight.
three alloys. However, both oxide layers in AISI 409 are
much thicker than two oxide layers in austenitic stainless C. Oxidation mechanism
steels. The result of the line scan shows uneven distribu-
tion of atoms in the oxide layers. In all cases, by Concerning the oxidation of stainless steels, several
proceeding from the metallic substrate toward the internal mechanisms have been suggested.14 It has been generally
oxide layer, at first, the concentration of Fe element accepted that the initial step in the oxidation is metal-
decreases and the concentration of Cr element increases. oxygen reaction in which some gases are adsorbed on the
By conditioning and approaching to the external oxide metal surface. Then, individually separated oxide nuclei
layer, the concentration of Fe element increases, and the are formed and laterally grown to form a continuous
concentration of Cr and Ni elements reaches zero. oxide film on the metal surface. At this stage, the metal
Furthermore, in austenitic stainless steels, a slightly and gas have been separated by oxide layer and reaction
higher concentration of Ni is observed near the oxide/ mechanism totally changes and proceeds by solid-state
metal interface in non-oxide area. The detailed chemical diffusion.14 Based on the EDS results, after 72 h of being
composition of internal oxide layers for three stainless exposed at 923 K, iron oxide is formed in the three
steels is summarized in Table III. Based on the EDS stainless steels. Due to the presence of diverse alloying
results of the three alloys, (Fe,Cr) spinal composition elements in alloys, the oxidation of alloys generally
with a chemical composition of (Fe,Cr)2O3 is suggested produces more than one oxide. In this case, first, the
for the internal oxide layer in three alloys. Cr2O3 is the least noble alloying element is oxidized as a result of
most stable oxide for enhancing oxidation resistance, selective oxidation. The formation of iron oxide can be
however, to have a continuous oxide film of Cr2O3, explained by Ellingham diagram as a very helpful display
a minimum Cr concentration is required, which will be for comparing the preferentiality of one oxide over
discussed in Sec. III. C. In addition, a small amount of Ni others. With increasing oxidation time, internal Cr-rich
oxide layers are observed in all alloys as shown in Fig. 5.
However, the thickness of internal oxide layer in ferritic
TABLE II. Chemical composition of oxide layers after 72 h holding AISI 409 stainless steel is much thicker in comparison to
under oxidation condition. other austenitic stainless steels. The formation of internal
oxide layer can be related to occurrence of selective
AISI 321 AISI 316 AISI 409
oxidation, which leads to IOZ formation. Selective
Elements wt% at.% wt% at.% wt% at.% oxidation is a process in which oxygen diffuses into an
O 22.43 51.03 22.96 50.71 5.43 15.92
alloy and causes subsurface precipitation.15
Si 0.61 0.78 0.87 1.09 0.00 0.00 To certify the formation of IOZ, some necessary
Cr 1.58 1.08 1.07 0.72 1.89 1.80 conditions should be fulfilled. First, from the thermody-
Mn 0.77 0.5 0.77 0.5 0.00 0.00 namical perspective, the value of standard Gibbs free
Fe 73.29 46.81 73.29 46.36 92.68 82.28 energy (DG0) of formation (per mole O2) for the solute
Ni 1.32 0.80 1.04 0.62 0.00 0.00
Total: 100 100 100 100 100 100
metal oxide must be more negative than DG0 of forma-
tion (per mole O2) for the base metal.15 The oxide

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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies

FIG. 5. SEM micrographs and corresponding line scan analysis results of (a and b) AISI 321, (c and d) AISI 316, and (e and f) AISI 409 stainless
steels, after 342 h holding under oxidation condition.

formation reactions and corresponding DG0 values are of (Fe,Cr)2O3 oxide formation (DGðFe;CrÞ2 O3 ) must be
given in Eqs. (2)–(4). negative. The value of DG is calculated for
2CrðsÞ þ 2FeðsÞ þ 3O2ðgÞ ¼ ðFe; CrÞ2 O3ðsÞ reaction as
4 2 shown in Eq. (5) for three stainless steels.
FeðsÞ þ O2ðgÞ ¼ Fe2 O3ðsÞ ; DG0 ¼ 385:55 kJ=mol ;
3 3
ð2Þ

aðFe;CrÞ2 O3
DG ¼ DG0  RT ln ; ð5Þ
aCr 2 aFe 2 pO3 3
4 2
CrðsÞ þ O2ðgÞ ¼ Cr2 O3ðsÞ ; DG0 ¼ 593:78 kJ=mol ;
3 3 where R is gas universal constant, T is temperature, PO2
ð3Þ is the oxygen pressure, and a is the activation for
indexed materials. The calculated values are
2 2 1
CrðsÞ þ FeðsÞ þ O2ðgÞ ¼ ðFe; CrÞ2 O3ðsÞ ; DG0 ¼ 489:66 kJ=mol ; 67399.91, 64972.80, and 63964.10 (kJ/mol) for
3 3 3
ð4Þ AISI 409, AISI 316, and AISI 321, respectively. It
should be stated that the mentioned thermodynamical
As can be seen, the Cr-containing oxides are more calculations refer to the equilibrium not for our experi-
negative than Fe2O3. Secondly, the formation free energy ments. However, due to the very long oxidation time, it

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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies

TABLE III. Chemical composition of internal oxide layers after 324 h


holding under oxidation condition. 1 Kc ðCr2 O3 Þ 1=2
min
NCr ¼F ; ð6Þ
AISI 321 AISI 316 AISI 409 2 ~
D
Elements wt% at.% wt% at.% wt% at.%
in which F is:
O 26.03 54.45 26.84 54.28 33.62 63.25 Z x
Si 0.54 0.64 2.92 3.36 0.54 0.58 2
ex dx
2
FðxÞ ¼ p1=2 xð1  erf ðxÞÞexpðx2 Þ; and erf ðxÞ ¼ pffiffiffi ;
Cr 23.15 14.90 42.71 26.57 18.43 10.66 p 0
Fe 46.37 27.78 22.16 12.83 45.97 24.77
ð7Þ
Ni 3.91 2.23 5.37 2.96 1.44 0.74
Total: 100 100 100 100 100 100
and Kc(Cr2O3) is the oxidation constant and D ~ is the
interdiffusion coefficient in the FeCr based substrate. The
diffusion coefficients for ferritic and austenitic stainless
steels are calculated from the equation, which has been
suggested by William and Faulkner.18 They determined
the chemical diffusion coefficients for chromium in
austenitic and ferritic steels by using electron probe
microanalysis techniques as shown for ferritic stainless
steel [Eq. (8)] and austenitic stainless steel [Eq. (9)].


~ a ¼ 0:15 exp 210615 cm2 s1
D ; ð8Þ
RT


~ 246616
Dc ¼ 0:15 exp cm2 s1 : ð9Þ
RT

In which D ~ c are the diffusion coefficient Cr

~ a and D
element in ferritic and austenitic steels, respectively.
Another term in Eq. (6), Kc, is calculated according to
the Eq. (10) for chromium oxide (Cr2O3):

2
MCr2 O3
Kc ¼ Kp ; ð10Þ
bqCr2 O3 MO

where MCr2 O3 and MO are, respectively, the molar mass of

FIG. 6. The variations oxide weights against oxide thickness in
(a) AISI 316 and AISI 321 and (b) AISI 409 stainless steels.
can be assumed that oxidation has happened close to
equilibrium condition. Moreover, these calculations can
be considered as an explanation, which is in good
consistence with experiments. Another point is the
minimum chromium content in steels for having a pro-
tective continuous stable oxide film. Wagner16 derived
an equation to determine minimum chromium content in
steels for leading to the formation of a protective film as
an essential factor for improvement oxidation resistance.
In other words, the formation of a continuous film of
Cr2O3 is possible if the Cr content is higher than
min
a critical point (NCr ), which is described by the
17
following equation :
the chromium oxide and the oxygen atom; b is the
number of the oxygen atoms, and qCr2 O3 is the oxide
density (5.21 g/cm3). Our calculation shows that the ratio
of minimum chromium content in ferritic stainless steel
minðaÞ minðcÞ
over austenitic stainless steel (NCr /NCr ) is equaled
to 1.23. Therefore, it can be concluded that for having
a continuous film of chromium oxide in AISI 409 ferritic
stainless steel, higher amount of chromium is needed. In
other words, the reaction front should penetrate more for
providing enough amount of Cr content, which resulted
in thicker oxide layer. This is in consistent with the
thickness of oxide layers as shown in Fig. 1 in which the
penetration depth of IOZ in AISI 409 stainless steel is
much higher than two other austenitic stainless steels.
The main reasons for thicker oxide layer are attributed to
the lower Cr content and higher diffusion coefficient in
ferritic stainless steel. Therefore, it can be suggested that
min
in austenitic stainless steels due to the lower NCr value,
the continuous oxide Cr2O3, which is the main key for

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 A. Movahedi-Rad et al.: Oxidation behavior of AISI 321, AISI 316, AISI 409 stainless steels: Kinetic, thermodynamic, diffusion studies

enhancing the oxidation resistance, is formed faster than approximately 10 times greater than austenitic matrix.11
ferritic stainless steel. As a result, in these alloys, the Our calculations show that the proportion of penetration
external oxide layers do not considerably grow. Conse- depth of IOZ in AISI 409 over AISI 316, and AISI 409
quently, the superior oxidation resistance of austenitic over AISI 321 are 3.21 and 3.46, respectively, which are in
stainless steels in comparison to the ferritic stainless steel good agreement with our SEM observations (Fig. 1).
is related to the higher Cr content. However, the reasons for differences between calculations
The thicker oxide layer in ferritic stainless steel can be and observations might be the detachment of loose sheets
also explained by using quasi-steady-state approximation, of scales during preparation process of samples. In
in which the concentration of oxygen obeys a linear addition, this can be related to the ignorance of Ni effect
relation across the IOZ in the planar specimen geometry. and other elements on the diffusion process.
In this case, it is rational to take the flux across the given
plane to be proportional to the concentration gradient
IV. CONCLUSIONS
across the IOZ and this can be described by using
empirical equation of Fick’s first law.19 If the x axis is In this paper, the oxidation behaviors of AISI 321,
taken parallel to the concentration gradient of component AISI 316, and AISI 409 stainless steels were studied at
i, @C=@x, the flux of component, Ji, can be described by 873 K for 72, 342, 1022, and 1202 h. The mass and
the Eq. (11), thickness of formed oxides were compared. It was

 observed that their masses and thicknesses increased with
@Ci oxidation time. In addition, among them, it was observed
Ji ¼ Di ; ð11Þ
@xi that the oxidation rate and oxide thickness of the AISI
409 ferritic stainless steels were considerably higher in
where Di is the diffusion coefficient. For our case, the comparison with two other AISI 316. Moreover, AISI
oxygen flux through the IOZ can be obtained by re- 321 austenitic stainless steels and AISI 321 demonstrated
writing Fick’s first law equation, in following form.15 the lowest oxide mass and thickness, which showed the
higher oxidation resistance. These data were taken into
NOMatrix account for further kinetical and thermodynamical calcu-
JO ¼ DO ; ð12Þ lations. From the kinetical point of view, the ionic
xVm
diffusion-controlled oxidation due to the parabolic oxi-
where DO is the diffusivity of oxygen in the ferritic or dation relationship was suggested as an oxidation mech-
austenitic steel (cm2/s), NOMatrix is the oxygen solubility in anism for three stainless steels. In all cases, two oxide
ferritic or austenitic steel, Vm is the molar volume of the layers were identified, which showed the formation of the
solvent metal or alloy (cm3/mol), and x is the penetration IOZ. It was observed that the IOZ was Cr-rich and its
depth of the IOZ. By assuming that the counter diffusion formation was explained based on the Gibbs free energy
of the Cr atoms is negligible, the penetration depth of expressions. However, it was observed that in the ferritic
IOZ can be demonstrated as the following equation15: stainless steel, IOZ layer was thicker than austenitic
stainless steels. To justify this observation, the minimum

1=2
2 NOMatrix DO chromium content for having a continuous film of pro-
x¼ t ; ð13Þ tective oxide was calculated. It was shown that in ferritic
m NCrInitial
stainless steel, it was higher than that in austenitic
where t is time, the m is the coefficient of oxygen in stainless steels, which meant more penetration of the
oxidation reaction of B 1 mO 5 BOm, and NCr Initial
is the reaction front for providing enough amount of Cr content.
initial solute concentration. So, the proportion of pene- This finding was also supported by quasi-steady-state
tration depth of IOZ in ferritic and austenitic stainless approximation based on the Fick’s first law.
steels can be expressed by Eq. (14).
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