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Modern Applied Science

Vol. 5, No. 1; February 2011

The Role of Manganese on Microstructure of High Chromium White

E-mail: [email protected]

Adnan Naama Abood

E-mail: [email protected]

Rabiha Saleh Yaseen

E-mail: [email protected]

Abstract

To determine the effect of austenite stabilizer element on the microstructure and behaviour of ascast high Cr
white cast iron Fe-21Cr-3Ni-1.7Mo-2.4C, different percentages of Mn (0.4, 0.9, 1.3, 1.7, 2.2 and 2.6 wt%) were
added. Detailed investigations were carried out using scanning electron microscopy, energy dispersive
spectroscopy analysis (EDS), X-ray diffraction and hardness test. It showed that with increasing Mn addition, the
austenite phase () of the as-cast alloys refine clearly. The morphology of the austenite phase for all alloys is a
mixture of dendrite and plate like. The austenite phase refines clearly with increasing manganese addition. The
major carbide phase formed in the as- cast alloys is M7C3 with minor carbides of (Fe,Cr)23C6 and Mo2C.
Microstructure analysis showed the presence of small amounts of martensite and delta ferrite in all as-cast alloys.
The hardness was decreased continuously with increasing Mn content. This is mainly attributed to the
morphology of carbides rather than to small variation in carbides content. It was observed that considerable
amounts of Mn were found in the carbides lower than that in the austenite matrix.
Keywords: As-cast white cast iron, Manganese, Austenite phase, EDS, Carbides, Austenite
1. Introduction

High alloyed chromium cast irons were used in applications with extreme demanding requirements such as
abrasive, erosion, heat and corrosion resistance (Carpenter, Carpenter and Pearce, 2004; Komarov, Sadovski,
Urbanovich and Lifshits, 2002). Also these cast irons were employed with unusual physical properties, such as low
thermal expansion or non magnetic properties are desired (Ogi, Yamomoto and MiyaKawat, 2003; Chenje, Simbi
and Navara, 2006; Tabrett and Sare, 2000). In the empirical development of alloyed cast irons the first prominent
advance was the introduction of the Ni-hard cast iron in which the Ni and Cr are converted the pearlitic matrix to
martensitic in the as cast state (Komarov and Sadovski, 2002; Asensio, Pero-Sanz and Verdiga, 2003; Zhou,
Nilsson, Anderson and Stahi, 2004). In further modifications, the eutectic carbide was refined somewhat to give
improved toughness (Baotong, Jingli and Stefano 2006). The M7C3 carbide is the predominant phase which is
harder than M3C present in unalloyed white cast irons and some Ni-hard cast irons, which cause a high abrasion
resistance (Bedolla Jacuinde, 2001; Petrovic, Markovic and Pavlovic, 2003; Jun, Cong, Haohuai, Hongshan,
Baoluo, Shenji and Sijiu, 2006).
Completely austenitic or completely martensitic matrix structure is desirable for wear resistance. High chromium
white cast irons have usually complex mixed iron chromium carbides which are significantly harder than the
cementite phase present in unalloyed and even low alloyed cast irons (Kuyucar and Liewiiyn, 2006; Alp, Wazzan
and Imaz, 2005). The increase in the carbon content of high-chromium cast irons causes a decrease in the heat
resistance and an increase in the rate of cracks propagation (Zhiping, Rulen and Baduo, 2002). On the other hand,

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Vol. 5, No. 1; February 2011

chromium has a negative effect on the resistance of the hypoeutectic alloys to thermo-cycling loads (Bedolla,
Correa, Quezada and Maldonado, 2005). Increasing manganese content will cause an increasing in retained
austenite at room temperature and a decreasing in hardness. Manganese is soluble in M7C3 and M3C carbides. It
provides hardenabiliy increases and prevents pearlite formation.
2. Experimental Procedures

The alloys used were made in a silica lined coreless high frequency induction melting furnace with 45 kg capacity,
1.2 KHz frequency, 150 kW power. The charge materials consisted of pig iron, ferrochromium (Fe-72%Cr),
ferromanganese (Fe-75%Mn), ferromolybdenum (Fe-65%Mo) and electrolytic nickel. The molten metal
temperature was measured with type-S calibrated thermocouple (Pt-Pt/Re). The pouring temperature was 1450C.
The manganese element added to the molten as ferromanganese, in six series depending on the Mn percentage
required. These alloys were poured into sand moulds to obtain square 12 mm12 mm cross section area and 60 mm
length bars. Table 1 lists the chemical composition for the six white cast irons produced. The only varied element
is manganese from 0.4 to 2.6 wt%.
Samples for metallographic were prepared using abrasive paper grades 220, 320, 400, 500, 800 and 1000
respectively and then polished with 1 m diamond paste. The specimens were etched using nital. Quantitative and
qualitative determinations of chemical composition of the phases in as cast and heat treated samples were made by
using the energy dispersive microanalyses. To aid in the identification of the phases present in the castings, X-ray
diffraction was performed. Carbide fraction computing was made to study the effect of manganese content on the
carbide fraction for the as cast. Average hardness of the as cast and heat treated specimens measured was using
HRC. -ferrite content determination for the as cast specimens was also carried out by ferrite Content Meter
(FCM).
3. Results and Discussion

High chromium white cast irons are usually produced as hypoeutectic composition, with austenite dendrites, either
partially or substantially transformed to martensite and eutectic containing carbides and austenite. Figure 1
illustrates the microstructure of the as cast high chromium alloyed cast irons with different amounts of manganese
addition. They compose of primarily proeutectic austenite dendrites and eutectic which consists of eutectic
austenite and eutectic carbides (mainly M7C3 type). It appears that the solidification of these kinds of alloys starts
by austenite dendrites formation, and as the temperature decreases these dendrites grow, till the remaining liquid
reaches the eutectic composition. At this stage the eutectic austenite/(Fe, Cr)7C3 carbide are formed. The austenite
phase and K2(M7C3) carbides developed from liquid phase around the primary austenite dendrite which grows
and formed as eutectic cells. The dendrites and the dendrites arm spacing differ with increasing manganese
content and the regularity of the grains increases positively with manganese content. These structures which
improved by the nucleation and growth of the austenite grain size are affected by the manganese content.
XRD analysis showed that there is small amount of martensite appeared as a thin dark-etching layer in the interface
between the eutectic phase and primary phase. This is because, during eutectic solidification the M7C3 carbide
which grows along the austenite absorbs carbon from its surrounding and narrow areas at the austenite/carbide
interphase become impoverished in carbon. The lack of carbon in these zones of austenite increases the Ms
temperature which allows these areas of austenite to transform to martensite during subsequent cooling down.
Therefore, it is common to find eutectic M7C3 carbides are surrounded by martensite.
Due to the nucleation and growth kinetics of phase and M7C3 carbides in the eutectic, "rosette" morphology
forms as a result of the early formation of a carbide crystal followed by rapid formation of around the former (Fig.
1). It appears that the eutectic solidified with a colony structure is consisting of a matrix of fine globular carbides in
the central region, string-like or granular. They developed towards the boundary and large massed in the boundary
area. At a higher percentage of manganese, the shape of the colony will differ and take another shape as indicated
in (Fig. 1) which represents 2.6% Mn-alloy.
The nucleation and growth of the eutectic chromium carbides lead to the depletion of its content in the remaining
liquid. This depletion is account for the chromium content of the subsequent and smaller carbide. In addition to
eutectic carbides, secondary carbides where precipitated from the austenite matrix during slow cooling. These
carbides precipitate due to decrease in C and Cr from the matrix and the destabilized the austenite as confirmed
from the energy dispersive spectroscopy (EDS). It transformed to martensite which causes an increase in the bulk
hardness. Besides martensite, the secondary carbides play important role in increasing the bulk hardness by their
dispersion hardening effect on the matrix.

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Presence of molybdenum in the alloys of high chromium white cast irons leads to the formation of Mo2C carbides.
Molybdenum is soluble in M7C3 carbide, so most of it partitions to the eutectic M7C3 carbide and some dissolve in
austenite. It is also possible that small part of Mo also forms M2C carbide (Mo2C) due to the presence of carbon in
the alloys. This type of carbide is found joined together with M7C3 as a lamellar shape (Fig. 2). It demonstrates that
Mo2C recrystalizes in a finely dispersed form as a eutectic in the final stage of solidification.
The shape and the size of eutectic M7C3 differ with manganese content. Hexagonal M7C3 eutectic carbides type
beginning to appear as the manganese content increases especially at 1.3 and 1.7% Mn (Figs. 1 and 2). Also the
average size of the carbide phase was increased with increasing manganese content in the alloys. The energy
dispersive spectroscopy analysis showed that the manganese percentage in the austenite and carbide increases as
its addition increases in the alloys. This leads to increase the retained austenite in the prepared white cast irons.
Also, it indicates that the manganese percentage in the austenite is more than its percentage in the carbides. This
means that the partition of manganese to the austenite is more than its partition to carbide (Table 2). Manganese
affects the austenite dendrites and the austenite dendrite arm spacing. Also the Cr percentage in the carbide phase
is more than 50% and its percentage in the phase is around 15% except specimen of 2.6%Mn. This is because
the analysis is made near the carbide phase. X-Ray diffraction analysis illustrates that the austenite () is the
predominant phase in all the prepared high chromium white cast alloys with different manganese additions.
Besides phase, (Fe, Cr)7C3 eutectic carbides also exist. Also there is a small amount of martensite and
molybdenum rich carbide (Mo2C) present.
Figure 3 shows that the hardness decreases with increasing manganese content. The hardness does not depend on
the carbide fraction only but also on the austenite shape and the percent of manganese content in this grain. The
shape of carbides was changed from rosette shape to large plate kind. The -ferrite content decreases as the
manganese content increases (Fig. 4). This indicates that increasing manganese content reduces the effect of
chromium in the content of - ferrite; with consideration that -ferrite is also affected by casting variables.
4. Conclusion

1) With increasing manganese content, the austenite matrix of the alloys refine considerably.
2) Presence of manganese in high Cr-white cast irons does not affect the tendency of chromium to stabilize the
carbides, but increasing in the amount of austenite.
3) There was also found that manganese has a high tendency to change the morphology of carbides formed and
decreasing the carbide fraction.
4) All cast alloys contain a small amount of martensite distributes on the interphase between austenite and M7C3
carbide.
5) The hardness of alloys decreased continuously with increasing manganese content which attributes mainly to
the morphologies of carbides rather than their content.
References

Alp, T., Wazzan, A.A. and Imaz, Y. (2005). Microstructure-properties relationship in cast irons, The abrasion
Journal for Science and Engineering, 30, 163.
Asensio, A., Pero-Sanz, J.A. and Verdiga, J.I. (2003). Microstructure selection criteria for cast irons with more
than 10 wt. % chromium for wear applications, Materials Characterization, 49, 83.
Baotong, L., Jingli, L. and Stefano, C. (2006). Corrosion and wear resistance of chrome white ironsA correlation
to their composition and microstructure, Metallurgical and Materials Transaction A, 37, 3029.
Bedolla, A., Correa, R., Quezada, J.G. and Maldonado, C. (2005). Effect of titanium on the as-Cast microstructure
of a 16 % chromium white iron, Materials Science and Engineering A, 398, 297.
Bedolla Jacuinde, A. (2001). Microstructure of vanadium, niobium and titanium-alloyed High-chromium white
cast irons, International Journal of Cast Metals Research (UK), 13, 343.
Carpenter, S.D., Carpenter, D. and Pearce, J.T.H. (2004). XRD and electron microscope study of an as-Cast 26.6 %
chromium white iron microstructure, Materials Chemistry and Physics, 85, 32.
Chenje, T.W., Simbi, D.J. and Navara, E. (2006). Relationship between microstructure, hardness, impact
toughness and wear performance of selected grinding media for mineral ore milling operations, Materials and
Design, 25, 11.
Jun, W., Cong, L., Haohuai, L., Hongshan, Y., Baoluo, S., Shenji, G. and Sijiu, H. (2006). The precipitation and
transformation of secondary carbides in a high chromium cast iron, Materials Characterization, 56, 73.
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Vol. 5, No. 1; February 2011

Komarov, K. and Sadovski, V.M. (2002). Thermal stability of highchromium cast iron, Metal Science and Heat
Treatment, 44, 32.
Komarov, O.S., Sadovski, V.M., Urbanovich, N.T. and Lifshits, G.F. (2002). Thermal stability of high-chromium
cast iron, Metal Science and Heat Treatment, 44, 32.
Kuyucar, S. and Liewiiyn, R. (2006). High-chrome white irons incorporating ultra-hard carbide-forming elements
for improved wear-resistance, Transactions-American Foundrymens Society, 114, 551.
Ogi, K., Yamomoto, K. and MiyaKawat, N. (2003). Alloy design for heat and abrasion resistant high alloy cast
iron, International Journal of Cast Metals Research, 16, 269.
Petrovic, S.T., Markovic, S. and Pavlovic, Z.A. (2003). The effect of boron on the stereological characteristic of
the structural phases present in the structure of the 13 % Cr white iron, Journal of Materials Science, 38, 3263.
Tabrett, C.P. and Sare, I.R. (2000). Fracture toughness of high chromium white irons: influence of cast structure,
Journal of Materials science, 35, 2069.
Zhiping, S., Rulen, Z. and Baduo, S. (2002). TEM study on precipitation and transformation of secondary carbides
in 16 Cr-1Mo-1Cu white iron subjected to subcritical treatment, Materials Characterization, 55, 403.
Zhou, J.M., Nilsson, A., Anderson, M. and Stahi, J.E. (2004). Machining characteristic of Novel- Abrasion
resistance iron, J. of Materials Processing Technology, 153-154, 751.

Table 1. Chemical composition of alloyed cast iron studied (wt%)

%C

% Cr

% Mo

% Ni

% Mn

% Si

%S

%P

2.48

21.76

1.79

3.17

0.4

1.88

0.0026

0.045

rem.

2.60

21.52

1.75

3.14

0.9

2.03

0.033

0.049

rem.

2.38

21.41

1.80

3.12

1.3

1.91

0.028

0.048

rem.

2.37

21.22

1.76

3.13

1.70

1.93

0.023

0.047

rem.

2.39

20.63

1.72

2.91

2.20

1.81

0.014

0.015

rem.

2.39

20.66

1.73

2.97

2.6

1.79

0.017

0.019

rem.

No.

% Fe

Table 2. EDS analysis of Mn and Cr in austenite ( ) and carbide phase (wt%)

182

% Mn
in alloy

% Mn
in

% Mn
in
carbide

% Cr
in

% Cr
in
carbide

0.4

0.76

0.23

14.89

56.81

0.9

1.01

0.52

14.7

57.67

1.3

1.4

1.17

15.45

56.16

1.7

1.81

1.4

15.18

57.78

2.2

2.6

2.14

14.17

51.95

2.6

3.0

2.2

29.17

57.83

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Vol. 5, No. 1; February 2011

Figure 1. SEM micrographs showing the colony shapes with rosette morphologies of high chromium white cast
irons with different percentages of manganese (a) 0.4 wt%, (b) 0.9 wt%, (c) 1.3 wt%, (d) 1.7 wt% and (e) 2.6 wt%.

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Figure 2. SEM micrographs showing the presence of molybdenum carbide in the high chromium white cast irons
at different percentages of manganese (a) 0.4 wt%, (b) 1.3 wt%, (c) 1.7 wt%, (d) 2.2 wt% and (e) 2.6 wt%.

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Vol. 5, No. 1; February 2011

as cast
50

HRC, Hardness

45

40

35
0

0.5

1.5

2.5

Wt.%Mn
wt%
Mn

Figure 3. Effect of percentage of manganese on hardness in the as-cast high chromium white cast iron

4.5

-Ferrite
%
o Ferrite

4
3.5
3
2.5
2
0

0.5

1.5

2.5

Mn
Wt. %
wt% Mn

Figure 4. Effect of % Mn on Ferrite in the as-cast high chromium white cast iron

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