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Materials Today: Proceedings 13 (2019) 235–240 www.materialstoday.com/proceedings

ICAMST 2018

High-temperature Oxidation Resistance of Martensitic Stainless

Steel 13Cr3Mo3Ni-cast after Heat Treated
Mochammad Syaiful Anwara,*, Septian Adi Chandraa, Rahma Nisa Hakima,
Siska Prifiharnia, Miftahb, Efendi Mabruria
a
Research Center for Metallurgy and Materials Indonesian Institute of Sciences (LIPI), Kawasan PUSPIPTEK Gd. 470,
Tangerang Selatan, 15314, Indonesia
b
Mechanical Engineering, Pamulang University, Indonesia

Abstract

The development of high-temperature steels for power plants application, i.e., steam turbine blade is being carried out intensively.
In this paper, martensitic stainless steel 13Cr3Mo3Ni-castwere studied to observe the oxidegrowth rate on the steel surface. The
steels were prepared by a sequencial process of induction melting, casting, austenitized and tempered. High-temperature
oxidation test was conducted in a muffle furnace at 700 °C until 144 h. The results were compared with control, austenitized and
tempered steels. The tempered steels have the lowest oxide growth rate on 13Cr3Mo3Ni-cast steels surface after a high-
temperature exposure.

© 2019 Elsevier Ltd. All rights reserved.

Peer-review under responsibility of the scientific committee of The 6th International Conference on Advanced Materials Science
and Technology 2018, 6th ICAMST.

Keywords:13Cr3Mo3Ni; cast; martensitic stainless steel; oxide growth rate; high temperature; oxidation

1. Introduction

Martensitic stainless steels containing 13% by weight of chromium which is commonly used in steam turbine
blades, marine turbine blades or compressor blades. They have good mechanical properties, moderate corrosion,

*
Corresponding author. Tel.: +62-813-5730-8827; fax: +62-21-756-0553
E-mail address: moch026@lipi.go.id

2214-7853© 2019 Elsevier Ltd. All rights reserved.

Peer-review under responsibility of the scientific committee of The 6th International Conference on Advanced Materials Science and Technology
2018, 6th ICAMST.
236 Anwar et al./ Materials Today: Proceedings 13 (2019) 235–240

andoxidation resistance when they are exposed to high temperatures [1]. However, the oxide layer deposited on the
blade surface has become a major problem inhigh-temperature applications such as loss of turbine efficiency,
unbalanced turbine blade rotation, corrosion and fracture of turbine blades. The growth rate of the oxide layer can be
affected by poor water treatment, oxygen, carbon dioxide, pH and higher temperature deposition [2]. The mechanism
of the oxide layer formed in the blades begins with the precipitating of impurities in the feed and boiler waters into
the turbine through dry steam-soluble salts, entrainment of boiler water droplets, injection feed water into steam to
superheat/reheat the temperature control and leakage of water boiler into superheat steam in the tubular
desuperheater. Impurities from steam can move to the turbine blade by deposition (steam to solid) and condensation
(steam to liquid) [3]. Stainless steel can form a layer of chromia (Cr2O3) on its surface at low temperatures, which
serves as a protective layer against corrosive elements. At higher temperatures, the Cr2O3 layer changes to M3O4
oxide type spinel (M = [Cr, Fe]). Then, with increasing exposure time, spinel oxide will grow with an element that is
rich in iron to transformto a hematite (Fe2O3) [4]. The reaction of the kinetics of the oxide layer on the blade surface
at high-temperature exposure can be classified as one of three types: linear, parabolic, or logarithmic. The law of
linear reaction kinetics is used when steel does not form a protective oxide, high porous oxide, or poor adhesion. The
linear kinetic reaction rate (k1) is formulatedas Equation 1.

( )= (1)

where W(t) is the mass gain per unit area at the timet,andk1 is the linear rate constant with the unit ofg cm s .
The parabolic reaction kinetics law describes the weight increase as a function of time where protective oxide and
with internal penetration by such corrosive matters as oxygen, carbon, or sulfur formed on the steel surface by
diffusion. The rate of parabolic reaction kinetic (k2) describes in equation 2. The law of parabolic reaction kinetics
describes weight gain as a function of time which the protective oxide and with internal penetration by corrosive
substances such as oxygen, carbon, or sulfur that form on the steel surface by diffusion. The parabolic kinetic
reaction rate (k2) is formulated by Equation 2.

( ) = (2)

where k2 is the parabolic rate constant with the unit ofg cm s .

The law of logarithmic kinetics reaction is used when steel is exposed to a low-temperature service test (<300 °C).
The logarithmic kinetics reaction rate is formulated in equation 3.

x = klog (t+t0)+A (3)

where A, klog, t0 are isothermal constants [5-6].

A lot of steel has been developed which aims to improve the properties of high-temperature oxidation resistance
which is applied as a rotating blade, HP and IP rotors of an ultra-supercritical turbine. In particular, Fe based alloys
with 15-25% by weight of chromium with or without nickel can withstand temperatures of 700 °C (ultra-supercritical
steam temperature) [7-8]. Unfortunately, increasing the composition of chromium in stainless steel can increase
material production costs. Substitutes with other alloys that have oxidation resistance and are relatively cheaper are
the solutions to minimize production costs. In this study, 13Cr3Mo3Ni-cast martensitic stainless steel was carried out
casting and heat treated process to observe oxidation resistance at 700 °C and the kinetic reaction rate of the oxide
layer.

2. Experimental

Martensitic stainless steels 13Cr3Mo3Ni is made by induction melting furnace and continued with gravitation
casting in a sand mold. The steel was cut into 1x1x1 cm3 for a heat treatment process in the muffle furnace
consisting of the austenitized process at 1020 °C for 4 hours then quenched in water and tempering at 650 °C for 2
hours then quenchedin the air. Heat treated steel was then tested for cyclic oxidation in the muffle furnace at 700 °C
for 114 hours, and gravimetry method was used to determine oxidation resistance of the steels. Scanning electron
 Anwar et al./ Materials Today: Proceedings 13 (2019) 235–240 237

microscopy-(SEM) integrated with elements mapping observation by Energy dispersive spectroscopy (ES) from
JEOL JSM-5400 were carried out on the sample to observe the oxide layer that occurs on the sample surface by
cross-section area. X-ray Diffraction (XRD) analysis with a Cu radiation from Bruker was used to observe the
oxides compound that formed on the sample surface.

3. Results and Discussion

3.1. Cyclic oxidation

Fig. 1. shows the curve of cyclic oxidation of 13Cr3Mo3Ni-cast steel at 700 °C for 144 hours. In this figure,
cyclic oxidation of tempered steel is compared with cyclic oxidation of control steel and austenitized steel. All of
steels show that weight of steels increases as a function of time exposure. The increasingweight of steels occur due
to the interaction between steel surface and atmospheric muffle furnace that thermodynamic and kinetic reaction act
on its surface.The control steel has the lowest weightof 0.06 mg/cm2. In the first of 96 hours, oxides of steels grow as
a linearas a function of time exposure. After 96 hours, the oxide of control steel grows on steel surface drastically as
a parabolic.Thelowest value of 0.23 mg/cm2in weight has been found in the tempered steels after oxidation of 144
hours. Based on Fig. 1., tempered steels have goodhigh-temperature oxidation resistance properties than control and
austenitized steels. The same result of high-temperature oxidation resistance curve also found in other research [9].

Fig. 1. Cyclic oxidation of 13Cr3Mo3Ni-cast steel at 700 °C for 144 hours

3.2. Kinetic analysis

Table 1. shows the constantrate k1 and k2 according to Equation 1 and Equation 2. The logarithmic of Equation 3
is not suitable for high temperature (>800 °C) oxidation. The growth oxide rate on steel for high-temperature
oxidation is often calculated according to Equation 1 and Equation 2. Linear constant (k1) in Equation 1 is where
oxide layer grows in function of time on steels surface with a porous structure and nonprotective from corrosion
substance. Parabolic constant (k2) in Equation 2 is where oxide layer grows in function of time on steels surface as a
protective oxide. In Table 1, the value k1 and k2 decrease as a function of heat treatment, as expected. It means that
the oxide layer formed on tempered steel surface is slowest than control and austenitized steels. In another research,
martensitic stainless steel results martensitic temper and a decrease of grain size after the process of tempering in
microstructure observations so that transformation of the microstructure can impact on the kinetic reaction of oxide
growth rate in high-temperature exposure [10-11].

Table 1.The rate of Constant (k1 and k22) according to Equation 1 and Equation 2
Heat treatment
Control Austenitizased at 1020 °C Tempering at 650 °C
( ) 1.0 x 10 5.4 x 10 4.4 x 10
( 3.2 x 10 2.3 x 10 1.0 x 10
238 Anwar et al./ Materials Today: Proceedings 13 (2019) 235–240

3.3. Characteristic of the oxide layer

Characteristic of the oxide layer was examined by X-ray Diffraction (XRD), Scanning electron microscope
(SEM), Mapping element and Energy Dispersive Spectroscopy (EDS). Fig. 2. shows the XRD pattern of
13Cr3Mo3Ni-cast heat treated steel after cyclic oxidation test of 144 hours. The XRD observation was run at
longitudinal steelsan. It is found that control steel shows many of oxides which dominated by Fe2O3 (hematite) on
the surface so that weight gain of control steel is highest. While steels after heat treatment process (austenitized and
tempered steel) have little of oxide that formed on the steel surface. It indicates that if steelspossess more oxide of
Fe2O3 on the surface after a cyclic oxidation test, they performe less resistance athigh-temperature oxidation.
However, a protective oxide of Cr2O3does not detect in the XRD pattern. It is probably due to the chemical content
of 13 %wt of chromium, and 3%wt of nickel in the steels cannot establishprotective oxide on its surface at a long
period in high-temperature condition.

Fig. 2. XRD patterns of 13Cr3Mo3Ni-cast steel heat treated after cyclic oxidation for 144 hours

Fig. 3. presents SEM images and Mapping Elements of 13Cr3Mo3Ni-cast steel after cyclic oxidation for 144
hours in magnification of 200X by cross section. It is observed that oxide layer forms on all surface of steels with or
without heat treatment. Bright and darkin colors in Fig. 3. of element mapping indicate the number of elements in
the oxide layer. More bright in color is higher content elements in oxide and viceversa. In Fig. 3., a protective oxide
of Cr2O3 layer seen firstly formed on the 13Cr3Mo3Ni-cast steel's surface and oxide of Fe2O3 layer secondly formed
on the steels after oxidation for 144 hours. These observations is supported by XRD analysis which only
detectsoxide of Fe2O3 on the surface of the steel. According to Fig. 3., the layer of Fe2O3 oxide covered a layer of
Cr2O3 oxide so that only layer of Fe2O3 oxide on its surface can be detected by XRD. When Cr2O3 oxide and Fe2O3
layer (rust) formed during oxidation test, the weight of steels will increase as a function of time. In Fig. 3(a), control
steel without heat treatment process has a relatively high content of Fe2O3 layer than Cr2O3 layer. This condition
cause decreasing of resistance of high-temperature oxidation. While in Fig. 3(b) and (c) which relatively high Cr2O3
layer than Fe2O3 layer on its surface, but weight gain of these steel are lower than control steel. The Cr2O3 has a
lower molecular weight of 151.99 g/mol than Fe2O3 (159.69 g/mol) so that it probably explains that high content of
Cr2O3 layer on austenitized and tempered surface steel show lower wight of steels. And also high content of Cr2O3 on
its surface can increasethe resistance of high-temperature oxidation.
 Anwar et al./ Materials Today: Proceedings 13 (2019) 235–240 239

Fe2O3 layer Cr2O3 layer

(a)

Fe2O3 layer

(b)

Cr2O3 layer
Fe2O3 layer

(c)

Fig. 3. SEM images and mapping elements of 13Cr3Mo3Ni-cast steel of (a) control; (b) austenitizased at 1020 °C; (c) tempered at 650 °C after
cyclic oxidation for 144 hours in magnification of 200X.

The quantitative data of elemental composition for varios samples is listed in Table 2.

Table 2. EDS result of 13Cr3Mo3Ni-cast steel after cyclic oxidation for 144 hours
Heat treated steel weight %
O Fe Cr Ni Mo
Control 5.74 75.77 13.04 2.80 2.65
Austenitizasedat 1020 °C 2.47 79.16 13.51 2.49 2.37
Tempered at 650 °C 5.49 71.45 16.66 3.31 3.09
240 Anwar et al./ Materials Today: Proceedings 13 (2019) 235–240

Table 2 confirms the chemical composition of 13Cr3Mo3Ni-cast steel after cyclic oxidation for 144 hours. The
element of Nickel and Molybdenum are not changed significantly after cyclic oxidation for 144 hours. It means that
element of Nickel and Molybdenum are not formed oxide compound layer on steel surface during cyclic oxidation
test. The element of Chromium in the oxidelayer is one of the importantelement that to improve high-temperature
resistance. The tempered steel has higherelement of chromium composition of 16.66 mass% so that this steel has the
highestresistance of high-temperature oxidation than control and austenized steel.

4. Conclusion

High-temperature oxidation of martensitic stainless steels 13Cr3Mo3Ni-cast has been carried out at 700 °C for
144 h. High-temperature oxidation resistance of steels is affected by the heat treatment process. Martensitic stainless
steels 13Cr3Mo3Ni-cast that has been experienced austenitized at 1020 °C and temperedat 650 °C exhibit the lowest
oxide growth rate at 700 °C for 144 h exposure. The oxide layer on steel surface is dominated by Fe2O3 (rust) and
Cr2O3. The Cr2O3layer on its steels is one of oxide that can improve resistant tohigh-temperature exposure. The
stabilization of the Cr2O3 layer on its steels is also affected by the heat treatment process. After high-temperature
oxidation exposure, the steels that contain high Cr2O3 content on its surface is found in the tempered steels.

Acknowledgments

This work was part of the development of high-temperature material for power plant research. The authors would
like to be obliged to Research Center for Metallurgy and Material of Indonesian Institute of Sciences for providing
laboratory facility and funding this research.

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