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Figure 1: Schematic representation of the diffusion
processes and phase boundary reactions during the
oxidation of iron in oxygen, according to Hauffe [11]
Rajesh Ranjan Sinha, Assistant Professor, Department of Chemistry, NETGi, Ranchi, India
Dr. Brahm Deo Tripathi, Principal, GGSITM, Kamre, Ranchi, India
Dr. Mahendra Yadav, Associate Professor, Department of Applied Chemistry, Indian School of
Mines, Dhanbad, India
Corresponding author: Rajesh Ranjan Sinha, e-mail: rrsinha79@gmail.com:
Effect of rare earth additions on high-temperature oxidation
resistance of V and Mo alloyed steels
Rare earths (RE) have been used to improve the high temperature oxidation resistance of low alloy steel containing
elements like Cr, Al, V and Mo. Further, the RE can be added either to the alloy or by applying as an oxide coating
to the alloy surface. In this study the high temperature oxidation resistance of rare earth (RE) oxide coated 1Cr-
0.3Mo-0.25V alloy was determined. This paper presents the influence of surface additions of nano-crystalline oxides
CeO2 on the isothermal oxidation behavior of 1Cr-0.3Mo-0.25V alloys at temperatures ranging from 600 C to 900
C. The oxidation rate of RE oxide coated1Cr-0.3Mo-0.25V was significantly lower than that of the uncoated alloy.
The improvements in oxidation resistance are the reduced oxidation rates and the increased oxide scale adhesion.
Scanning electron microscopy (SEM), X-ray diffractometry (XRD), and electron probe micro analyzer (EPMA)
were employed for these analyses. The scale formed in the presence of RE oxides was very thin, fine grained and
adherent.
_____________________________________________________________________________
Introduction
Chromia scales that form on low-chromium content Fe-
Cr alloys at elevated temperatures grow relatively
slowly and usually provide good oxidation resistance.
Addition of small amounts of elements or their chemical
compounds, such as, cerium or their oxide dispersions
to these alloys greatly increases their oxidation
resistance under isothermal conditions. These so-called
reactive element effects have been extensively reviewed
by Whittle and Stringer [1] and more recently by Moon
and Bennet [2]. Oxidation resistance is also improved if
reactive element oxides are applied to the surfaces of
the alloys [3...7] or introduced by ion implantation [8;
9]. Rahmel et al. [10] showed that additions of 0.5 - 5.5
%Mo decrease the oxidation rate of iron by almost the
power of ten in the temperature range 500 - 1000 C;
Fig. 1 schematically shows that the oxidation of iron
proceeds with increasing temperature, different layers of
oxide scales, i.e., FeO, Fe3O4 and Fe2O3 are formed. In
case of iron, wustite is formed above 600C which is a
most ionic defective oxide. [11]
Very few definite conclusions can be drawn as to the
usefulness of the oxides of the rare-earth lanthanide
series. The thermodynamic properties of many of these
compounds have never been ascertained. Others have
been only estimated or assigned tentative values based
on qualitative or incomplete investigations. The
lanthanide series oxides, in general, appear to have
quite high melting points. Those known with some
degree of certainty are La2O3 (2305 C), CeO2 (2600
C), Nd2O3 (2270 C), Sm2O3 (2300 C), Eu2O3
(2050 C), Gd2O3 (2300 C), and Dy2O3 (2340 C)
[12] Very favorable free energies of formation at high
temperatures (about 418.4 KJ at 2000 K) [13] indicate
that these lanthanide oxides range among the most
stable oxides. Carbides of this series are also known to
exist, but data on the stability of these compounds have
not been reported. It is known that they have dicarbide
stoichiometry and that they are decomposed by water
vapor [14]. The use of reactive elements is well known,
especially rare earths (RE) to improve high temperature
oxidation resistance of chromium dioxide and alumina
forming alloys. The improvements are in the form of
reduced oxidation rates and increased scale adhesion
[15; 16].

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Figure 2: Weight gain per unit area vs. time plot of 1Cr-0.3-Mo-0.25V
steel at 600 C, 700 C , 800 C, 900 C
Figure 3: Weight gain per unit area vs. time plot of
CeO2 coated 1Cr-0.3-Mo-0.25V steel at 600 C, 700
C , 800 C, 900 C
In aqueous solution both vanadium and cerium oxides
can form ionic species:
Ce+4 + H2O (CeOH)+3 + H+ [17] (1)
2 (CeOH)+3 (Ce-O-Ce)+6 +H2O [17] (2)
V2O5 V+4 V4 +-OH[18] (3)
Starting from CeO2 and V2O5, a new phase CeVO4 is
formed via an intermediate state V2O5-X/CeO2-y in
which an unpaired electron is trapped at high
temperatures being responsible for the reducibility of
Ce4+ to Ce3+ and for the active sites on a ceria
supported vanadia catalyst [19...21].
Material and Methods
Boiler quality low alloy steel i.e. 1Cr-0.3Mo-0.25V
were hot rolled to 2.5 mm thickness. The plates were
obtained from RDCIS,
SAIL plant for oxidation
tests. These plates were de-
scaled and cut to the size of
2.5 15 25 mm3, approx.
The percentage of
chemical composition of
steel is Fe-97.63, C-0.12,
Mn-0.5, Si-0.20, S-0.015,
P-0.018, Cr-0.99, Mo-0.28,
V-0.24. Both the surfaces
of the specimens were
mechanically polished
using SiC papers of up to
600 grit. The prepared
samples were thoroughly
washed in distilled water
and rinsed with acetone,
then dried and stored in
desiccators. 2.5 g of cerium oxide
powder (ASTM mesh size -230 +325)
were mixed with 50 ml ethyl alcohol
to prepare the slurry. The samples
were dipped into the slurry to be
coated and the slurry was constantly
stirred to prevent the reactive oxide
particles from sedimentation. The
samples were dried in air at a
temperature of 100 C. The dipping
and drying process was repeated for
10 to 15 times until a uniform
thickness of the coating layer was
achieved on both the surfaces. The
difference between the initial and final
mass of the samples was measured and
the coating thickness was calculated to
range between 5 10-3 and 7 10-3
cm. Isothermal oxidation tests were
carried out in dry air under
atmospheric pressure by hanging all
the specimen with and without coat in
a vertical quartz tube reactor. The
reactor tube was closed with glass wool. The
temperature accuracy in the reactor tube was 5C. The
atmosphere in the reaction zone was natural air. A Pt-
Pt13%Rh thermocouple was inserted from the top of the
furnace to measure the temperature of the reaction zone.
This thermocouple connected to a PID controller was
placed inside the annular space between the furnace and
reactor wall. Electronic digital balance having an
accuracy of 0.1 mg was used for measuring the mass
changes of the sample during oxidation. A timer was
used for a fixed time interval to continuously record the
weight gain of the sample during oxidation.
Evaluation of the results
Kinetic studies. The oxidation kinetics data for 1Cr-
0.3Mo-0.25V low alloy steels with and without cerium
oxide coatings were conducted in the temperature range
of between 600 C and 900 C for 24 h. The weight
gains as a function of time for the above mentioned
three steels were plotted for different temperatures.
Figs. 2, 3 show the curves
for 1Cr-0.3Mo-0.25V
steel without coating and
CeO2 coated in the
temperature range from
600 C to 900 C,
respectively. Further, the
data were plotted as log
(weight gain per unit area)
vs. log t at temperatures
600 C to 900 C,
respectively, which is
shown in fig. 4. Further,
the slope vs. 1/T plot of
steel at 700C, 750 C and
800 C is shown in fig.5.
The kinetics data and rate
constants for the above
mentioned steels are also

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Figure 4: Log-log plot of 1Cr-0.3-Mo-0.25V steel at 600 C, 700
C, 800 C, 900 C

Figure 5: Slope vs. 1/T plot of 1Cr-0.3-Mo-0.25V
steel at 700 C, 750C, 800 C
available in the book [22]. Gibbs free energy of
uncoated and CeO2 coated oxidized steels were 86.31
KJ/mol and 136.86 KJ/mol respectively.
SEM, EPMA & XRD analyses. All the specimens
subjected to the different tests were weighed after each
cycle and their surfaces were examined in a scanning
electron microscope (SEM) and electron probe micro
analyzer (EPMA). The oxide scales were also analyzed
by X-ray diffraction (XRD). These analytical techniques
were used to understand the oxidation process in terms
of scale morphology and chemistry in the presence or
absence of ceria coatings. These techniques were also
used for analyzing the scale composition, the nature of
scale adhesion and for identifying the various phases
occurring in the oxide scale. SEM was used to study the
alloy/scale cross-sections of the uncoated and coated
oxidized steels which were oxidized in the temperature
range from 600 C to 900 C. SEM micrographs of the
above-mentioned steels at 800 C are represented in fig.
6. This clearly shows the occurrence of internal
oxidation. Similarly, EPMA and XRD micrographs of
the alloy/scale cross-sections formed on the coated
steels are shown in figs. 7 and 8, respectively.
Discussion of the results
Kinetic consideration. For the 1Cr-0.3Mo-0.25V type
steels data exists [23] suggesting that V-additions may
have distinct benefits as far as hydrogen embrittlement
in service is concerned, and this seems to be linked to
greater trapping and lower diffusivities in the V-
modified steels. Other work [24], indeed, indicated that
the problem of disbonding at cladded interfaces can be
reduced in V-modified steels. The possible consequence
of reduced hydrogen diffusivity on welding procedures
is observed in the fabrication of V-modified Cr-Mo
steels.
When an oxidant comes into contact with a metal, the
reactions proceed by forming a stable scale at the metal-
gas interface due to combination of metal
ions with oxidant ions. The growth of
scale at the interface was found to be rate
controlled process. The mechanically
polished samples were improved
oxidation resistance in the presence of
CeO2 coatings. In all cases, the rate of
weight gain was initially fast but after a
certain time, it was observed to increase
at a steady rate. This can be seen in the
plots of weight gain vs. time as shown in
fig. 2 - 3. The weight gain vs. Time plot
for 1Cr-0.3Mo-0.25V steel at 800 C
temperature shows the kinetics of
oxidation and slope were changed.
However, the curve was observed to be of
parabolic nature. In the presence of RE it
grows at the metal/oxide interface. The
result of Gibbs free analysis shows that
the stability of different oxides depends
on their standard Gibbs free energies of
formation ( GoMO), oxygen partial
pressure pO2 and temperature. It is possible to evaluate
the stabilities of different oxides in different
atmospheres by calculating the oxygen partial pressure
where the oxide dissociates. Dissociation oxygen partial
pressure (pO2)dissoc for the metal oxide (MO) is
calculated by the equation:
log (pO2) dissoc = 2G0MO /(2.303RT)
The oxygen partial pressure under atmospheric pressure
is greater than the dissociation oxygen partial pressure;
therefore, the oxide is thermodynamically stable. Gibbs
free energy analyses clearly show the marked increase
in the oxidation resistance of the molybdenum and
vanadium alloyed steels compared to those coated with
RE oxides. For each oxide, care has been taken to
optimize the RE oxide grain size and shape, to
consequently increase coverage and also to optimize the
chemical potentials of those two RE oxides having ionic
radii very close to each other.
SEM, EPMA and XRD investigation. Figs. 6 8
schematically show the oxide growth in the presence of

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Figure 6: SEM micrograph of 1Cr-0.3-Mo-0.25V Figure 7: EPMA micrograph of 1Cr-0.3-Mo-0.25V
steel at 800 C steel at 800 C
RE. SEM and EPMA clearly suggest that the scales
formed on the bare steel were of coarse-grained, non-
uniform character and depleted the substrate, whereas
fine-grained, compact, well adherent and uniform scales
were found to be formed on the CeO2 coated steel.
XRD analysis of the scales showed the presence of
simple, complex and mixed oxides (spinals), including
CeO2, Fe2O3, FeCe2O4, (FeOCe2O3), CeFeO3,
Fe21.34O32, CrO2 and FeOCr2O3 for ceria coated
oxidized 1Cr-0.3Mo-0.25V steel samples. The formed
FeOCe2O3 is thermodynamically more stable than
CeO2 under the present testing conditions. A
comparison of XRD analysis of steel showed that the
steel coated with cerium oxide shows superior oxidation
resistance compared to the others investigated here.
Conclusions
[1] In the above-mentioned steel, the kinetics of
oxidation were faster for an initial period of 100 min
after which it was decreased. This showed that the
diffusion of anions and cations were also decreased due
to the formation of a certain scale thickness;
[2] SEM studies showed that the outer layer of the oxide
scale was compact and the micrograph of fractured
interface showed the crystalline structure;
[3] the Mo and V alloyed steels coated with CeO2
exhibited higher oxidation resistance compared to the
uncoated alloys;
[4] the effect of CeO2 coating on the oxidation behavior
of 1Cr-0.3Mo-0.25V showed that the CeO2 coating
prevents scale formation in the temperature range from
600 C to 900 C;
[5] X-ray diffraction patterns for the CeO2 coated steel
showed the presence of CeO2 in the scale.
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Figure 8: XRD micrograph of 1Cr-0.3-Mo-0.25V steel at 800 C
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