Materials Transactions, Vol. 47, No. 1 (2006) pp.

72 to 81
#2006 The Japan Institute of Metals

Eect of Alloying Elements on Heat Treatment Behavior

of Hypoeutectic High Chromium Cast Iron
Sudsakorn Inthidech1; * , Prasonk Sricharoenchai1 and Yasuhiro Matsubara2
1
2

Department of Metallurgical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok10330, Thailand

Department of Metallurgical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok10330, Thailand

The relationship between hardness and volume fraction of retained austenite (V
) was investigated in heat-treated 16 mass% and
26 mass%Cr hypoeutectic cast irons with and without addition of a third alloying element of Ni, Cu, Mo and V. In as-hardened state, hardness
changed remarkably depending on the V
. Overall, Ni and Cu decreased hardness but Mo increased it. Hardness increased in 16 mass%Cr cast
iron but decreased in 26 mass%Cr cast iron by V addition. The V
increased with Ni, Cu and Mo addition but diminished with V addition in
16 mass%Cr cast iron. In 26 mass%Cr cast iron, Ni and Mo increased the V
but Cu and V reduced it. Higher austenitization caused more V
.
Curves of tempered hardness showed an evident secondary hardening due to precipitation of special carbides and transformation of destabilized
austenite into martensite. High tempered hardness was obtained in the specimens with high V
in as-hardened state. Maximum tempered
hardness (HTmax ) was obtained when V
was less than 20% and it increased with an increase in Mo content. The HTmax slightly increased with V
content in 16 mass%Cr cast iron and decreased in 26 mass%Cr cast iron. Ni and Cu did not show signicant eects on HTmax . The highest value
of HTmax was obtained in both series of cast irons containing Mo.
(Received September 5, 2005; Accepted November 9, 2005; Published January 15, 2006)
Keywords: high chromium cast iron, alloying element, heat treatment, hardness, volume fraction of retained austenite

1.

Introduction

High chromium cast irons, which contain 12 to

30 mass%Cr and 1.8 to 3.6 mass%C are well known as
abrasion wear resistant materials. It is said that their
microstructures consisting of hard eutectic carbides of
(Cr,Fe)7 C3 or M7 C3 and strong supportive matrix provide
excellent wear resistance. Consequently, high chromium cast
irons have been widely used for parts or components in the
various industries. Their main and typical applications are for
rolling mill rolls in the steel-making industry, and for rollers,
tables and liners of pulverizing mills in cement, mining and
thermal power plant industries.
The high wear performance of high chromium cast iron
depends on both the amount and the type of eutectic carbide
and on the matrix structure. Many papers report that the wear
resistance increases with an increase in volume fraction of
eutectic carbide under abrasive wear conditions.1,2) However,
high volume fraction of eutectic carbide deteriorates the
toughness which is a critical factor, particularly, when the
high chromium cast iron is used for construction parts. In
order to get higher toughness, the volume fraction of eutectic
carbides must be limited and also coarse primary carbides be
avoided. Hence, high chromium cast iron with hypoeutectic
composition is widely used.
Solidication of high chromium cast iron has been studied
by many researchers14) and it is found that austenite (
)
dendrites solidify rst in hypoeutectic cast iron, followed by
a eutectic reaction of L !
M7 C3 . The eutectic is found
to grow with a cellular interface and to solidify as a colony
structure.4) The carbide morphology in the eutectic structure
depends on the type and the amount of carbide forming
elements, namely Cr, Mo, V and carbon content. The eutectic
morphology, i.e., the sizes of eutectic colony and individual
carbide particle can be controlled by solidication rate or
*Graduate

Student, Chulalongkorn University

cooling rate.4)
Once the high chromium cast iron has solidied, the
carbide morphology can be little modied by any means
except by plastic deformation. However, the matrix structure
can be widely changed by heat treatment. In the practical use
of high chromium cast irons, heat treatment has been
conducted in order to achieve the optimal combination of
hardness and quantity of retained austenite for abrasion wear
resistance and other mechanical properties. In particular, the
secondary carbides precipitated during destabilization heat
treatment and the carbides formed during subsequent tempering plays an important role for the wear resistance and
mechanical properties. It is said that the maximum macrohardness obtained after tempering is at most 800 HV30 in
high chromium cast iron without any alloy addition5) and that
the hardness in eutectic high chromium cast iron can be
increased by addition of Mo.6) In the case of hypoeutectic
cast iron, some alloying elements which improve the hardenability and simultaneously promote the formation of
secondary carbides with higher hardness than chromium
carbides should be added. In spite of many researches on high
chromium cast irons containing alloying elements, systematic and detailed investigations of the eects of alloying
elements on the behavior of hardness and retained austenite
during heat treatment are very limited.7,8)
In this study, therefore, hypoeutectic high chromium cast
irons, to which Ni or Cu is separately added to improve
mainly hardenability as well as Mo or V to promote
precipitation hardening, were employed. The investigation
was focused on the variation of hardness and the volume
fraction of retained austenite including their correlation with
the heat treatment conditions.
2.

Experimental Procedure

2.1 Preparation of test specimens

16 mass%Cr and 26 mass%Cr hypoeutectic cast irons

Eect of Alloying Elements on Heat Treatment Behavior of Hypoeutectic High Chromium Cast Iron

73

Table 1 Chemical composition of test specimens.

Element (mass%)

Number
C

Cr

Si

Mn

Ni

Cu

Mo

No. 1

3.01

16.48

0.62

0.78

No. 2

2.90

16.23

0.51

0.53

1.21

No. 3

2.95

16.00

0.55

0.56

2.14

No. 4

2.94

15.84

0.54

0.56

1.00

No. 5

2.96

15.90

0.54

0.53

2.02

No. 6
No. 7

2.97
2.97

16.12
15.93

0.52
0.51

0.50
0.51

0.96
2.03

No. 8

3.05

15.82

0.55

0.51

3.05

No. 9

2.96

16.13

0.50

0.51

1.00

No. 10

3.13

16.08

0.53

0.53

2.10

No. 11

3.06

16.06

0.47

0.50

3.05

No. 12

2.65

25.56

0.37

0.51

No. 13

2.65

26.16

0.48

0.48

1.18

No. 14
No. 15

2.64
2.62

25.91
26.31

0.47
0.50

0.51
0.50

2.06

1.03

No. 16

2.68

26.04

0.51

0.51

2.10

No. 17

2.66

25.84

0.48

0.50

0.98

No. 18

2.61

25.90

0.50

0.50

1.95

No. 19

2.64

26.40

0.49

0.47

2.96

No. 20

2.61

25.97

0.51

0.50

1.05

No. 21

2.64

25.91

0.51

0.51

2.02

No. 22

2.71

26.46

0.52

0.51

3.02

without alloy addition and with a separate addition of Ni or

Cu up to 2 mass% and Mo or V up to 3 mass% were produced
using a 30 kg-capacity high frequency induction furnace with
alumina lining. Raw materials such as mild steel, pig iron,
ferro-alloys and pure metals were used as charge materials.
The charge materials were melted down and superheated up
to 1853 K. After holding at the temperature, each melt was
poured from 17731793 K into preheated CO2 mold with a
cavity size of 25 mm in diameter and 65 mm in length, and
the surface of the top riser was immediately covered with dry
exothermic powder to prevent the riser from cooling. The
chemical compositions of the test bars are shown in Table 1.
The bars were sectioned by a wire-cut machine to obtain
disk-shaped test pieces, 7 mm in thickness.
2.2 Heat treatment
First of all, the as-cast specimens were annealed for
homogenizing by holding at 1173 K for 10.8 ks and then
cooled in a furnace. The annealed specimens were then
austenitized at 1273 and 1323 K for 5.4 ks and hardened by
forced air cooling with approximate cooling rate of 12 K/s.
The hardened specimens were tempered at 50 K intervals
between 573 and 873 K for 7.2 ks.
2.3 Measurement of hardness and retained austenite
The measurement of macrohardness was carried out by a
Vickers hardness tester with a load of 300 N (30 kgf). More
than ve indentations were taken at random and the measured
values were averaged. The volume fraction of retained
austenite (V
) was obtained by an X-ray diraction method
using a special goniometer with automatic rotating and tilting
sample stage. The diraction peaks used for V
determina-

tion were (200) and (220) planes for ferrite () or martensite
and (220) and (311) planes for austenite (
).
3.

Experimental Results and Discussions

3.1 Microstructure of test specimen

Typical as-cast microstructures of 16 mass%Cr cast irons
with and without alloying elements are shown in Fig. 1. The
microstructures consist of primary austenite dendrites and
eutectics structures. The microstructure of the alloy-free cast
iron consists of pearlitic matrix with rod-like and massive
eutectic M7 C3 carbides. The (
M7 C3 ) eutectic shows a
colony morphology that contains ne carbides in the central
region and coarse carbides at the boundary region. In the cast
irons with alloying element, the carbide morphology changes
little whereas the matrix remarkably changes depending on
the kind and the amount of alloying element. The matrix in
the cast irons alloyed with Ni or Mo is austenitic and that in
the cast iron with V is pearlitic. A major part of matrix in
the cast iron with 1 mass%Cu is pearlitic and that with
2 mass%Cu is mostly austenitic.
As for the microstructures of 26 mass%Cr cast irons, all the
matrices, with and without alloying element, were austenitic,
and possibly containing some martensite. It was also found
that the eutectic colony size of 26 mass%Cr cast iron was
smaller and the size of eutectic carbide particles was much
smaller than those of 16 mass%Cr cast iron.
3.2

Eect of alloying elements on hardness and volume

fraction of retained austenite (V )
3.2.1 As-hardened state
Macrohardness and V
were measured in all the as-

74

S. Inthidech, P. Sricharoenchai and Y. Matsubara

150 m

Alloy-free
%
Alloy

1%

2%

Ni

Cu

Mo

Fig. 1 As-cast microstructures of 16 mass%Cr cast irons free of and with third alloying element.

hardened specimens. The hardness depends on the type and

the volume fraction of carbide and matrix structure, and the
matrix hardness is directly related to the V
in hypoeutectic
cast iron. Generally, greater amounts of carbide leads to an
increase in hardness but greater amount of retained austenite
which is dependent on the type and amount of added alloying
element produces a decrease in hardness. The relationship
between alloying elements and macrohardness is shown in
Fig. 2. In all specimens, the hardness is decreased with an

increase in Ni content regardless of the austenitizing temperatures. Cu shows the same eect except for the 16 mass%Cr
specimens austenitized at 1273 K. An addition of Mo leads to
an increase in the hardness in all specimens. As V content
increases, the hardness rises in 16 mass%Cr specimens but
unexpectedly reduces in 26 mass%Cr cast irons. The highest
hardness is obtained in the 16 mass%Cr cast iron containing
V and 26 mass%Cr cast iron with Mo.
The macrohardness measured is closely related to the

Eect of Alloying Elements on Heat Treatment Behavior of Hypoeutectic High Chromium Cast Iron

16 mass%Cr cast iron

75

26 mass%Cr cast iron

(a)Austenitized at 1273 K

Alloy (mass%)

Fig. 2

Eect of alloying elements on macrohardness in as-hardened specimens with 16 mass% and 26 mass%Cr.

16 mass% Cr cast iron

26 mass% Cr cast iron

(mass%)

Fig. 3 Eect of alloying elements on volume fraction of retained austenite (V
) in as-hardened specimens with 16 mass%Cr and
26 mass%Cr.

matrix structure, particularly, volume fraction of retained

austenite. When the concentrations of Cr and C in austenite
are compared between 16 mass%Cr and 26 mass%Cr cast
irons, it is generally said that Cr content is lower and C

content is higher in 16 mass%Cr cast iron than those in

26 mass%Cr cast iron. It is accepted that in any austenitizing
condition, Ni and Cu which dissolve entirely in the austenite
depressed Ms temperature and as a result more austenite was

76

S. Inthidech, P. Sricharoenchai and Y. Matsubara

Alloy-free
Ni

Cu

1 mass%

1 mass%

2 mass%

2 mass%

Fig. 4 Relationship between hardness, volume fraction of retained austenite (V
) and tempering temperature in 16 mass%Cr specimens
free of alloying element and with Ni or Cu.

retained. On the other hand, Mo and V are strong carbide

formers and are consumed in the formation of carbides.
However, even when V, a very strong carbide former, is
added to 16 mass%Cr cast iron, sucient carbon remains in
the matrix to form martensite. In the case of 26 mass%Cr cast
iron, C in austenite combines with V reducing the C content
in the matrix and allowing transformation to pearlite.
The V
is increased when austenitizing temperature is
high. The eect of alloy content on the V
is shown in Fig. 3.
In 16 mass%Cr cast irons, the V
increases roughly in
proportion to Ni, Cu and Mo contents but gradually decreases
with an increase in V content. In the case of 26 mass%Cr cast
irons, the behavior of the V
is shown similar to that of
16 mass%Cr cast irons. In 26% Cr cast iron, however, the V

seems to decrease very slightly or it can be regarded that it is
almost same. At the same alloy content, the V
values in
16 mass%Cr cast irons are higher than those in 26 mass%Cr
cast irons. The reason why Cu increases the V
in 16% Cr cast
iron but changes it little in 26% Cr cast iron can be explained

as follows:
When specimens were hardened, the cooling rate is faster
than the critical cooling rate of their pearlite transformation.
Therefore, the V
could depend on the bainite transformation
which occurs at lower temperature. When the bainite
transformations are compared in high chromium cast irons
with similar chemical composition, the nose time in 2.6% C
27% Cr cast iron is located at short time side than that in 2.9%
C17% Cr0.5% Mo cast iron.9) Since the cooling rate of this
experiment is near the bainite transformation of 16% Cr cast
iron, the eect of Cu content on the bainite transformation
must be more in this 16% Cr cast iron than in 26% Cr cast
iron and the amount of bainite transformation could be
reduced with an increase in Cu content. Resultantly, the V

increases. From the relationship between the positions of
bainite transformation, the specimens of 26% Cr cast iron are
participated more in the bainite transformation. Even if the
bainite transformation is shifted by increasing the Cu content
up to 2% in 26% Cr cast iron, the amount of bainite

Eect of Alloying Elements on Heat Treatment Behavior of Hypoeutectic High Chromium Cast Iron

Mo

1 mass%

1 mass%

2 mass%

2 mass%

3 mass%

3 mass%

77

Fig. 5 Relationship between hardness, volume fraction of retained austenite (V
) and tempering temperature in 16 mass%Cr specimens
with Mo or V.

transformation is not inuenced so much by Cu content. Due

to these reasons, the V
change little by increasing Cu content
in 26% Cr specimens.
Here, the eects of V and Mo on as-hardened hardness can
be explained by referring to the V
. In 16 mass%Cr cast iron,
V containing specimens show the highest hardness because
as-hardened matrix contained small amounts of V
and large
portions of martensite. In the 26 mass%Cr cast irons, on the
contrary, the hardness decreases with V. This reason is
explained by the fact that although the as-hardened matrix
contains very low quantity of V
less than 5%, the remainder
was pearlite nor martensite. Since the amount of pearlite in
specimen with Mo is less, on the other hand, the hardness
depends mainly on the V
. It is reported that when the
hardness is related to the V
, the V
which provides the
highest hardness in alloyed white cast irons is said to be 20 to
30%.10) The V
at the maximum hardness in this experiment
is 15 to 20% which is in very close agreement.

3.2.2 Tempered state

It is reported that eutectic high chromium cast iron with the
carbide forming elements exhibits precipitation hardening
during heat treatment and the highest hardness is 900 HV30
in 26 mass%Cr cast iron with Mo.6) The eect of precipitation hardening in hypoeutectic irons must be greater than
in irons with eutectic composition because of the greater
portion of matrix area to be precipitated. During tempering,
the retained austenite in as-hardened state is decomposed by
the precipitation of carbides and the rest of the austenite
transforms into martensite during cooling after holding at the
tempering temperature. Martensite existing in as-hardened
state is simultaneously tempered and secondary carbides are
also formed by so-called carbide reaction.
The relationships between hardness, V
and tempering
temperature of alloyed 16 mass%Cr and 26 mass%Cr cast
irons are shown together with alloy-free cast irons in Figs. 4
to 7, respectively. In every case, the tempered hardness

78

S. Inthidech, P. Sricharoenchai and Y. Matsubara

Alloy-free
Ni

Cu

1 mass%

1 mass%

2 mass%

2 mass%

Fig. 6 Relationship between hardness, volume fraction of retained austenite (V
) and tempering temperature in 26 mass%Cr cast irons
free of alloying element and with Ni or Cu.

curves show evidence of secondary hardening. The degree of

secondary hardening, which is dened as the dierence in
hardness between the maximum tempered hardness (HTmax )
and the hardness at which the secondary hardening begins, is
larger in alloyed cast iron than that in alloy-free cast iron. It is
seen that the degree increases as both the alloy content and
the austenitizing temperature rise, and that the increase seems
to be related to the V
value in as-hardened state, the higher
the V
, the greater the degree of secondary hardening. From
the tempering curves of the specimens with 2 mass% alloying
element in both 16 mass%Cr and 26 mass%Cr cast irons, the
degree of secondary hardening is calculated and the results
are shown in Table 2. The specimen with Ni shows the
highest degree of secondary hardening followed by Cu, Mo
and V, respectively. According to the tempering curves
shown in Figs. 4 to 7, the V
begins to decrease abruptly or
sometimes gradually from the tempering temperature of
673 K and to be zero at the tempering temperatures between

748 and 800 K, except for the case of Mo addition, regardless

of austenitizing temperature and alloy content. The tempering temperatures that the V
becomes 0% are about 773 to
873 K in Mo added specimens. In both series of the cast irons,
the HTmax is obtained when the specimens are tempered at
748 to 823 K where the V
is reduced to less than 20%. The
HTmax is high in the case of high austenitizing temperature
and the temperature to obtain the HTmax shifts to the high
temperature side. This reason could be that a large amount of
retained austenite in as-hardened state needs high tempering
temperature to be decomposed in an optimum condition for a
xed holding time.
As mentioned above, the V
in as-hardened state is
similarly related to the HTmax under the same tempering
condition. Here, the HTmax is related to the V
in as-hardened
state as shown in Fig. 8(a) for 16 mass%Cr and Fig. 8(b) for
26 mass%Cr cast irons. In the case of 16 mass%Cr cast iron,
even when the V
increases, the HTmax does not change by an

Eect of Alloying Elements on Heat Treatment Behavior of Hypoeutectic High Chromium Cast Iron

Mo

1 mass%

1 mass%

2 mass%

2 mass%

3 mass%

3 mass%

79

Fig. 7 Relationship between hardness, volume fraction of retained austenite (V
) and tempering temperature in 26 mass%Cr specimens
with Mo or V.

Table 2 Degree of precipitation hardening in specimens with 2 mass%

alloying element.
Alloying
element

Degree of precipitation hardening (HV30)

16 mass%Cr

26 mass%Cr

Ni

181

87

Cu

175

85

Mo

158

66

35

48

increase in Ni and Cu content but it is gradually increased by

increasing Mo and V contents. In the 26 mass%Cr cast iron,
the HTmax increases with an increase in the V
except for the
cast iron with Ni in which HTmax does not change. The HTmax
of the specimens containing V abruptly increases in the small
range of V
from 2 to 5%. So, V in retained austenite may
promote the formation of its secondary special carbide. The
HTmax of 26 mass%Cr specimens with Cu rises in the range

less than 10%. In this range, the hardness could be inuenced

not only by V
but also by precipitated carbides formed from
martensite during tempering. Over 10% V
, the eect of V

on the HTmax is signicant in the specimens with Mo and V.
The eects of alloying elements on HTmax are shown in
Fig. 9. At the same alloy content, the HTmax is high in the
specimens hardened from higher austenitizing temperature.
In 16 mass%Cr cast iron, the HTmax increases remarkably as
Mo content increases and slightly with V content but does not
change by Ni and Cu contents. In 26 mass%Cr cast irons, the
HTmax increases largely with an increase in Mo content but it
is decreased by Ni and V contents. Cu has little eect on
the HTmax . The highest values of HTmax , 875 HV30 in 16
mass%Cr and 885 HV30 in 26 mass%Cr cast irons, were
obtained in the irons with 3% Mo. In spite of greater
secondary hardening, highest HTmax in hypoeutectic cast iron
with 3% Mo is a little lower than that in eutectic cast iron
with 3% Mo. This is due to the dierence in the volume
fraction of eutectic carbide (Vc ) between them, Vc of the

80

S. Inthidech, P. Sricharoenchai and Y. Matsubara

Fig. 8 Relationship between maximum tempered hardness (HTmax ) and volume fraction of retained austenite (V
) in the as-hardened state.
(a): 16 mass%Cr, (b): 26 mass%Cr cast irons.

16 mass% Cr

26 mass% Cr

Fig. 9 Eect of alloying elements on maximum tempered hardness (HTmax ) in 16 mass% and 26 mass%Cr cast irons. (a) and (b) for
16 mass%Cr, (c) and (d) for 26 mass%Cr.

former is 31.5% and that of the latter is 36.4%. Ni and Cu do

not contribute the increase in the HTmax , and therefore, such
elements should be added for the improvement of hardenability. Mo contributes more to increase the hardness because
the large amount of retained austenite in as-hardened state
contributed greatly to the secondary precipitation of M6 C
carbides with much higher hardness than chromium carbides
of M23 C6 , and as a result, the matrix hardness is increased. In
spite of the fact that V is strong carbide former and vanadium
carbide has extremely high hardness, the high hardness could
not be obtained in the specimens with V by this heat
treatment, and V rather lowers the tempered hardness in 26%
Cr specimens. This is because the cast iron with V produces
less retained austenite in as-hardened state since V shifts the
pearlite transformation to short time side.11) Also V increases

both the temperature of eutectoid transformation and a

critical cooling rate of pearlite transformation.12) Consequently, V in austenite promotes pearlite formation and then
less austenite with low V content is retained in as-hardened
state. In order to make V provides its full eect on an increase
in hardness, extremely high austenitizing temperature may be
introduced for more and more dissolution of V in the
austenite.
4.

Conclusions

General heat treatments, annealing, hardening and tempering, were conducted on 16 mass%Cr and 26 mass%Cr
hypoeutectic cast irons with and without the third alloying
element of Ni, Cu, Mo and V, each, and the relationship

Eect of Alloying Elements on Heat Treatment Behavior of Hypoeutectic High Chromium Cast Iron

among alloying elements, hardness and volume fraction of

retained austenite was claried. The conclusions drawn from
the experimental results are as followed.
4.1 In as-hardened state
(1) Hardness changed remarkably depending on the volume fraction of retained austenite (V
) which was
closely related to the kind and the amount of alloying
element. The hardness decreased with an increase in Ni
and Cu contents in both series of cast irons. Mo
increased the hardness overall. V increased the hardness
in 16 mass%Cr cast irons but reduced hardness in 26
mass%Cr cast irons.
(2) The V
increased with an increase in Ni, Cu and Mo
contents and it was reduced by increasing V content in
16 mass%Cr irons. In 26 mass%Cr irons, V
was
increased by Ni and Mo but reduced by Cu and V
additions. An increase in austenitizing temperature
caused V
more in all the specimens.
4.2 In tempered state
(1) Curves of tempered hardness showed evidence of
secondary hardening due to both the precipitation of
special carbides formed by carbide reaction and the
transformation of destabilized austenite into martensite.
(2) High tempered hardness was obtained in the irons with
high V
in as-hardened state which was produced in the
case of high austenitizing temperature.
(3) The degree of the precipitation hardening was much
larger in alloyed cast irons than that in alloy-free cast
irons except for the cast iron containing V, and it was
greater in the order of irons with Ni, Cu, Mo and V.
(4) The maximum tempered hardness (HTmax ) was obtained
when the V
was less than 20% after tempering. The
tempering temperature to obtain the HTmax shifted to
high temperature side and it ranged from 748 to 823 K.
(5) Mo increased the HTmax in the both series of cast irons.

81

V increased it slightly in 16 mass%Cr cast iron but

decreased it in 26 mass%Cr cast iron. Ni and Cu did not
show a signicant eect on the HTmax .
(6) The highest values of HTmax , 875 HV30 in 16 mass%Cr
and 885 HV30 in 26 mass%Cr cast irons with Mo, were
obtained respectively.
Acknowledgements
The authors would like to note with appreciation that
nancial support from the Thailand Research Fund through
the Royal Golden Jubilee Ph. D. Program (Grant No. PHD/
0165/2547) to students initials and advisors initials is
acknowledged.
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